LUBRICATING OIL COMPOSITIONS FOR HYBRID ENGINES AND METHODS OF USE AND TESTING THEREOF

Abstract

This invention relates to a lubricating oil composition for hybrid engines including a) an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group I, II, III or IV base oil, or combinations thereof; b) one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more); c) optionally one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 to 12.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is from 1.0 to 9.0 wt. % of the composition; and d) an overbased calcium salicylate or sulfonate detergent, an overbased magnesium salicylate or sulfonate detergent, an overbased mixed calcium and magnesium salicylate or sulfonate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and delivers at least 5 mmol of total soap to the composition. Also provided is a method of evaluating a lubricating oil composition for ranking its performance in a hybrid engine by running a bench scale test protocol based upon 3 test results: the emulsion dispersion and stability performance at all 4 test conditions in the Emulsion Stability test (modified ASTM D7563), the emulsion corrosion test, and the journal bearing wear test.

Claims

1. A lubricating oil composition for hybrid engines comprising or resulting from the admixing of: a) an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof; b) one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more); c) optionally one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.5 to 12.0 wt. % of the lubricating oil composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is from 1.5 to 9.0 wt. % of the lubricating oil composition; and d) an overbased calcium salicylate detergent, an overbased magnesium salicylate detergent, an overbased mixed calcium and magnesium salicylate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and delivers at least 5 mmol of total soap to the lubricating oil composition; wherein the lubricating oil composition has a total sulfated ash of less than or equal to 1.2 wt. %, a kinematic viscosity at 100 C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.4 wt. %; and wherein the lubricating oil composition results in a passing emulsion dispersion and stability performance at the four test conditions in the Emulsion Stability test (modified ASTM D7563: a) 10%/10% E85/water-24 h; b) 10%/10% E85/water-72 h; c) 15%/15% E85/water-24 h; and d) 15%/15% E85/water-72 h.

2. The composition of claim 1, wherein the lubricating oil composition results in a rating of at least 2 for emulsion corrosion resistance in the emulsion corrosion test; and or the lubricating oil composition results in a rating of at least 2 for bearing wear in the journal bearing wear test.

3. The composition of claim 1, wherein the lubricating oil composition further comprises: a) one or more zinc dialkyl dithiophosphate (ZDDP) compounds where the treat level of the one or more ZDDP compounds is from 0.4 wt. % to 2.0 wt. % of the lubricating oil composition; and or b) one or more corrosion inhibitors, rust inhibitors or combinations thereof at a treat rate of greater than or equal to 0.02 wt. % of the lubricating oil composition where the one or more corrosion and/or rust inhibitors are optionally selected from the group consisting of a non-ionic fatty alcohol ethoxylate, a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, a primary amine, a substituted carboxylic acid functional group, a substituted ester functional group, a substituted anhydride functional group, or a combination thereof.

4. The composition of claim 1, wherein the composition provides for substantially no aqueous separation of lubricating oil emulsions including the lubricating oil composition and up to 15 wt. % water at 0 C. and 25 C. in the Emulsion stability test (modified ASTM D7563).

5. The composition of claim 1, wherein the higher molecular weight PIBSA-PAM is borated, the optional lower molecular weight PIBSA-PAM is borated or a combination thereof, and is/are included at a treat level to deliver from 20 ppm to 1000 ppm by weight of boron to the composition; and/or wherein the one or more, optionally borated, higher molecular weight PIBSA-PAM dispersant is from 2.0 to 6.0 wt. % of the composition.

6. The composition of claim 1, wherein the oil of lubricating viscosity is at from 60 wt. % to 95 wt. % of the composition, comprises a Group II base oil, a Group III base oil, a Group IV base oil or combinations thereof, and is substantially free of Group I base oil.

7. The composition of claim 1, wherein the soap level is greater than or equal to 0.5 wt. % of the overall composition.

8. The composition of claim 1, further including one or more of the following components: one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more anti-foaming agents; one or more viscosity modifiers; one or more dispersants other than the higher molecular weight PIBSA-PAM and the lower molecular weight PIBSA-PAM; one or more inhibitors, one or more antirust agents; one or more seal swell agents; and/or one or more other anti-wear agents.

9. The composition of claim 8, wherein: 1) the one or more antioxidants includes one or more phenolic antioxidants, one or more sulfur based antioxidants, one or more aminic antioxidants or a combination thereof, and wherein the one or more antioxidants comprise from 1.0 to 6.0 wt. % of the composition; and or 2) the one or more friction modifier includes a dimeric molybdenum dialkyldithiocarbamate (moly dimer), a trimeric molybdenum dialkyldithiocarbamate (moly trimer), or a combination thereof at a treat level to deliver from 12 ppm to 1000 ppm by weight of molybdenum to the composition; and or 3) the one or more friction modifier includes an organic friction modifier selected from the group consisting of alkylated succinic anhydrides, alkylated succinic acids, alkylated carboxylic acids, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, and combinations thereof, wherein the organic friction modifier comprises from 0.01 to 5.0 wt. % of the composition; and or 4) the one or more pour point depressants include polymethacrylate, polyacrylate or a combination thereof, and wherein the one or more pour point depressants comprise from 0.01 to 5.0 wt. % of the composition.

10. The composition of claim 1, wherein the lubricating oil composition is used as a passenger vehicle lubricant (PVL) or a commercial vehicle lubricant (CVL).

11. A method of lubricating a hybrid engine comprising supplying to the engine a lubricating oil composition of claim 1.

12. A lubricating oil composition for hybrid engines comprising or resulting from the admixing of: a) an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof; b) one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more); c) optionally one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 to 12.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is from 1.0 (preferably 1.5) to 9.0 wt. % of the composition; d) an overbased calcium sulfonate detergent, an overbased magnesium sulfonate detergent, an overbased mixed calcium and magnesium sulfonate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and delivers less than or equal to 5 mmol of total soap to the composition; and e) one or more organic friction modifier at from 0.01 to 2.0 wt. % of the composition; wherein the lubricating oil composition has a total sulfated ash of less than or equal to 1.2 wt. %, a kinematic viscosity at 100 C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.4 wt. %; and wherein the lubricating oil composition results in a rating of at least 2 for emulsion corrosion resistance in the emulsion corrosion test.

13. The composition of claim 12, wherein the lubricating oil composition results in a rating of at least 2 for bearing wear in the journal bearing wear test.

14. The composition of claim 12, wherein the lubricating oil composition further comprises one or more zinc dialkyl dithiophosphate (ZDDP) compounds; and wherein the treat level of the one or more ZDDP compounds is from 0.4 wt. % to 2.0 wt. % of the lubricating oil composition; and or b) one or more corrosion inhibitors, rust inhibitors or combinations thereof at a treat rate of greater than or equal to 0.02 wt. % of the lubricating oil composition where the one or more corrosion and/or rust inhibitors are optionally selected from the group consisting of a non-ionic fatty alcohol ethoxylate, a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, a primary amine, a substituted carboxylic acid functional group, a substituted ester functional group, a substituted anhydride functional group, or a combination thereof.

15. The composition of claim 12, wherein the lubricating oil composition further comprises a functionalized polymer at from 0.01 to 20 wt. %, optionally 0.3 to 5 wt. %, based upon the total weight of the lubricating oil composition, wherein the functionalized polymer comprises a partially or fully saturated olefin homopolymer or copolymer backbone and at least one functional group: i) having an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization, ii) where the functional group is derived from an acylating agent and a compound containing amino and/or hydroxyl groups (including but not limited to where the polymer is functionalized with an acylating agent and subsequently reacted with a compound containing amino and/or hydroxyl groups), and iii) wherein the homopolymer or copolymer backbone is derived from monomers selected from the group consisting of C.sub.2 to C.sub.30 linear alpha olefins, and C.sub.4 to C.sub.20 conjugated dienes; wherein the functionalized polymer comprises an amide, imide, and/or ester functionalized partially or fully saturated polymer comprising C.sub.4-5 olefins having: i) an Mw/Mn of less than 2, ii) a Functionality Distribution (Fd) value of 3.5 or less, and iii) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization, provided that, if the polymer prior to functionalization is a copolymer of isoprene and butadiene, then the Mn of the copolymer is greater than 25,000 g/mol (GPC-PS).

16. The composition of claim 12, wherein the composition provides for substantially no aqueous separation of lubricating oil emulsions including the lubricating oil composition and up to 15 wt. % water at 0 C. and 25 C. in the Emulsion Stability test (modified ASTM D7563).

17. The composition of claim 12, wherein the higher molecular weight PIBSA-PAM is borated, the optional lower molecular weight PIBSA-PAM is borated or a combination thereof, and is/are included at a treat level to deliver from 20 ppm to 600 ppm by weight of boron to the composition, and or wherein the one or more, optionally borated, higher molecular weight PIBSA-PAM dispersant is from 2.0 to 4.5 wt. % of the composition.

18. The composition of claim 12, wherein the oil of lubricating viscosity is at from 60 wt. % to 95 wt. % of the composition, comprises a Group II base oil, a Group III base oil, a Group IV base oil or combinations thereof, and is substantially free of Group I base oil.

19. The composition of claim 12, wherein the detergent includes a combination of an overbased calcium salicylate detergent and an overbased magnesium salicylate detergent.

20. The composition of claim 12, further including one or more of the following components: one or more other friction modifiers; one or more antioxidants; one or more pour point depressants; one or more anti-foaming agents; one or more viscosity modifiers; one or more dispersants other than the higher molecular weight PIBSA-PAM and the lower molecular weight PIBSA-PAM; one or more inhibitors, one or more antirust agents; one or more seal swell agents; and/or one or more other anti-wear agents.

21. The composition of claim 20, wherein the one or more antioxidants includes one or more phenolic antioxidants, one or more sulfur based antioxidants, one or more aminic antioxidants or a combination thereof, and wherein the one or more antioxidants comprise from 1.0 to 6.0 wt. % of the composition; and or wherein the one or more other friction modifier includes a dimeric molybdenum dialkyldithiocarbamate (moly dimer), a trimeric molybdenum dialkyldithiocarbamate (moly trimer), or a combination thereof at a treat level to deliver from 12 ppm to 1000 ppm by weight of molybdenum to the composition; and or wherein the one or more organic friction modifier is selected from the group consisting of alkylated succinic anhydrides, alkylated succinic acids, alkylated carboxylic acids, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, and combinations thereof; and or wherein the one or more pour point depressants include polymethacrylate, polyacrylate or a combination thereof, and wherein the one or more pour point depressants comprise from 0.01 to 5.0 wt. % of the composition.

22. The composition of claim 12, wherein the lubricating oil composition is used as a passenger vehicle lubricant (PVL) or a commercial vehicle lubricant (CVL).

23. A method of lubricating a hybrid engine comprising supplying to the engine a lubricating oil composition of claim 12.

24. A concentrate comprising or resulting from the admixing of: from 1 to less than or equal to 50 wt. % of one or more base oils; from 2 to 40 wt. % of an overbased calcium salicylate detergent, an overbased magnesium salicylate detergent, an overbased mixed calcium and magnesium salicylate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500; and from 2 to 40 wt. % of one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more), and one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol).

25. The concentrate of claim 24, further including: 1) from 2 to 20 wt. % of one or more zinc hydrocarbyl diphosphate compounds, wherein the one or more zinc hydrocarbyl diphosphate compounds include hydrocarbyl groups derived from one or more primary alcohols, one or more secondary alcohols or a combination of primary and secondary alcohols; and or 2) from 0.10 to 10 wt. % of one or more corrosion inhibitors, rust inhibitors or combinations thereof selected from the group consisting of a non-ionic fatty alcohol ethoxylate, a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, a primary amine, a substituted carboxylic acid functional group, a substituted ester functional group, a substituted anhydride functional group or a combination thereof; and or 3) from 1 to 30 wt. %, such as 2 to 20 wt. %, based upon the weight of the concentrate, of one or more functionalized polymers, wherein the one or more functionalized polymers comprise a partially or fully saturated olefin homopolymer or copolymer backbone and at least one functional group, having: i) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization, ii) where the functional group is derived from an acylating agent and a compound containing amino and/or hydroxyl groups (including but not limited to where the polymer is functionalized with an acylating agent and subsequently reacted with a compound containing amino and/or hydroxyl groups), and, iii) wherein the homopolymer or copolymer backbone is derived from monomers selected from the group consisting of C.sub.2 to C.sub.30 linear alpha olefins, and C.sub.4 to C.sub.20 conjugated dienes;

26. The concentrate of claim 24, further comprising combining the concentrate with a base oil to form a lubricating oil composition comprising: a) an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof; b) one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more); c) optionally one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 to 12.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is from 1.0 to 9.0 wt. % of the composition; and d) an overbased calcium salicylate detergent, an overbased magnesium salicylate detergent, an overbased mixed calcium and magnesium salicylate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and delivers at least 5 mmol of total soap to the composition; wherein the lubricating oil composition has a total sulfated ash of less than or equal to 1.2 wt. %, a kinematic viscosity at 100 C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.4 wt. %; and wherein the lubricating oil composition results in a passing emulsion stability performance at all 4 test conditions in the Emulsion Stability test (modified ASTM D7563).

27. A concentrate comprising or resulting from the admixing of: from 1 to less than or equal to 50 wt. % of one or more base oils; from 2 to 40 wt. % of an overbased calcium sulfonate detergent, an overbased magnesium sulfonate detergent, an overbased mixed calcium and magnesium sulfonate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500; from 2 to 40 wt. % of one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more), and one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol); and from 0.5 to 10 wt. % of one or more organic friction modifier.

28. The concentrate of claim 27, further including: from 2 to 20 wt. % of one or more zinc hydrocarbyl diphosphate compounds, wherein the one or more zinc hydrocarbyl diphosphate compounds include hydrocarbyl groups derived from one or more primary alcohols, one or more secondary alcohols or a combination of primary and secondary alcohols; and or from 0.10 to 10 wt. % of one or more corrosion inhibitors, rust inhibitors or combinations thereof selected from the group consisting of a non-ionic fatty alcohol ethoxylate, a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, a primary amine, a substituted carboxylic acid functional group, a substituted ester functional group, a substituted anhydride functional group or a combination thereof; and or more functionalized polymers, wherein the one or more functionalized polymers comprise a partially or fully saturated olefin homopolymer or copolymer backbone and at least one functional group, having: i) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization, ii) where the functional group is derived from an acylating agent and a compound containing amino and/or hydroxyl groups (including but not limited to where the polymer is functionalized with an acylating agent and subsequently reacted with a compound containing amino and/or hydroxyl groups), and, iii) wherein the homopolymer or copolymer backbone is derived from monomers selected from the group consisting of C2 to C30 linear alpha olefins, and C4 to C20 conjugated dienes;

29. The concentrate of claim 27, further comprising combining the concentrate with a base oil to form a lubricating oil composition comprising: a) an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof; b) one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more), c) optionally one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 (preferably 1.5) to 12.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is from 1.0 to 9.0 wt. % of the composition; d) an overbased calcium sulfonate detergent, an overbased magnesium sulfonate detergent, an overbased mixed calcium and magnesium sulfonate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and delivers less than or equal to 5 mmol of total soap to the composition; and e) one or more organic friction modifier at from 0.01 to 2.0 wt. % of the composition; wherein the lubricating oil composition has a total sulfated ash of less than or equal to 1.2 wt. %, a kinematic viscosity at 100 C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.4 wt. %; and wherein the lubricating oil composition results in a rating of at least 2 for emulsion corrosion resistance in the emulsion corrosion test.

30. A method of evaluating a lubricating oil composition for ranking performance of the lubricating oil composition in a hybrid engine comprising the steps of: i) selecting a lubricating oil composition for bench scale testing; ii) testing the composition for emulsion dispersion and stability performance in the Emulsion Stability test (modified ASTM D7563) to determine its score from 0 to 3; iii) testing the composition for emulsion corrosion resistance in the emulsion corrosion test to determine its score from 0 to 3; iv) testing the composition for journal bearing wear in the journal bearing wear test to determine the change in the depth of the bearing pre-test and post-test in average maximum wear and assigning a wear result from 1 to 3; and v) combining test results from steps ii), iii) and iv) above to provide an overall performance rating for ranking the performance of the lubricating oil composition in a hybrid engine.

Description

DETAILED DESCRIPTION

[0080] The features of the disclosure relating, where appropriate, to each and all aspects of the disclosure, will now be described in more detail as follows.

Overview

[0081] It has now surprisingly been found by the present inventors that a lubricating oil composition including an oil of lubricating viscosity and a combination of one or more, optionally borated, higher molecular weight PIBSA-PAM dispersants or alternatively a mixture of one or more, optionally borated, lower molecular weight PIBSA-PAM dispersants and one or more, optionally borated, higher molecular weight PIBSA-PAM dispersants, and an overbased calcium salicylate detergent, an overbased magnesium salicylate detergent, an overbased mixed calcium and magnesium salicylate detergent or a combination thereof, when used in a hybrid engine results in improved emulsion dispersion and stability performance relative to lubrication oil compositions not including the combination of such components. More specifically, the inventors have unexpectedly and surprisingly discovered that a lubricating oil composition including an oil of lubricating viscosity and a combination of one or more, optionally borated, higher molecular weight PIBSA-PAM dispersants or alternatively a mixture of one or more, optionally borated, lower molecular weight PIBSA-PAM dispersants and one or more, optionally borated, higher molecular weight PIBSA-PAM dispersants, and an overbased calcium salicylate detergent, an overbased magnesium salicylate detergent, an overbased mixed calcium and magnesium salicylate detergent or a combination thereof, when used in a hybrid engine results in a passing emulsion dispersion and stability performance at all 4 test conditions in the Emulsion Stability test (modified ASTM D7563).

[0082] It has also been surprisingly found by the present inventors that a lubricating oil composition including an oil of lubricating viscosity and a combination of one or more, optionally borated, higher molecular weight PIBSA-PAM dispersants or alternatively a mixture of one or more, optionally borated, lower molecular weight PIBSA-PAM dispersants and one or more, optionally borated, higher molecular weight PIBSA-PAM dispersants, an overbased calcium sulfonate detergent, an overbased magnesium sulfonate detergent, an overbased mixed calcium and magnesium sulfonate detergent or a combination thereof, and one or more organic friction modifiers results when used in a hybrid engine results in improved emulsion corrosion resistance. More specifically, the inventors have unexpectedly and surprisingly discovered that a lubricating oil composition including an oil of lubricating viscosity and a combination of one or more, optionally borated, higher molecular weight PIBSA-PAM dispersants or alternatively a mixture of one or more, optionally borated, lower molecular weight PIBSA-PAM dispersants and one or more, optionally borated, higher molecular weight PIBSA-PAM dispersants, an overbased calcium sulfonate detergent, an overbased magnesium sulfonate detergent, an overbased mixed calcium and magnesium sulfonate detergent or a combination thereof, and one or more organic friction modifiers results when used in a hybrid engine results in a rating of at least 2 for emulsion corrosion resistance in the emulsion corrosion test.

[0083] The lubricating oil compositions of the present disclosure comprise components that may or may not remain the same chemically before and after mixing with an oleaginous carrier (such as a base oil) and/or other additives. This disclosure encompasses compositions which comprise the components before mixing, or after mixing, or both before and after mixing.

[0084] The inventors have also discovered a method of evaluating a lubricating oil composition for ranking performance of the lubricating oil composition in a hybrid engine that includes the steps of: i) selecting a lubricating oil composition for bench scale testing; ii) testing the composition for emulsion dispersion and stability performance in the Emulsion Stability test (modified ASTM D7563) to determine its score from 0 to 3; iii) testing the composition for emulsion corrosion resistance in the emulsion corrosion test to determine its score from 0 to 3; iv) testing the composition for journal bearing wear in the journal bearing wear test to determine the change in the depth of the bearing pre-test and post-test in average maximum wear and assigning a wear result from 1 to 3; and v) combining test results from steps ii), iii) and iv) above to provide an overall performance rating for ranking the performance of the lubricating oil composition in a hybrid engine.

Lubricating Oil Compositions For Hybrid Engines and Methods of Use of Such Compositions

[0085] This invention relates to a lubricating oil composition for hybrid engines comprising or resulting from the admixing of: a) an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof; b) one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more); c) optionally one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 (such as 1.5) to 12.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is from 1.0 (such as 1.5) to 9.0 wt. % of the composition; and d) an overbased calcium salicylate detergent, an overbased magnesium salicylate detergent, an overbased mixed calcium and magnesium salicylate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and delivers at least 5 mmol of total soap to the composition; wherein the lubricating oil composition has a total sulfated ash of less than or equal to 1.2 wt. %, a kinematic viscosity at 100 C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.4 wt. %; and wherein the lubricating oil composition results in a passing emulsion dispersion and stability performance at all 4 test conditions in the Emulsion Stability test (modified ASTM D7563).

[0086] This invention also relates to a method of lubricating a hybrid engine comprising: i) supplying to the engine a lubricating oil composition comprising or resulting from the admixing of: a) an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof; b) one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more); c) optionally one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 (such as 1.5) to 12.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is from 1.0 (such as 1.5) to 9.0 wt. % of the composition; and d) an overbased calcium salicylate detergent, an overbased magnesium salicylate detergent, an overbased mixed calcium and magnesium salicylate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and delivers at least 5 mmol of total soap to the composition; wherein the lubricating oil composition has a total sulfated ash of less than or equal to 1.2 wt. %, a kinematic viscosity at 100 C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.4 wt. %; and wherein the lubricating oil composition results in a passing emulsion dispersion and stability performance at all 4 test conditions in the Emulsion Stability test (modified ASTM D7563).

[0087] In another form, this invention relates to a lubricating oil composition for hybrid engines comprising or resulting from the admixing of: a) an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof; b) one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more); c) optionally one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 to 12.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is from 1.0 to 9.0 wt. % of the composition; d) an overbased calcium sulfonate detergent, an overbased magnesium sulfonate detergent, an overbased mixed calcium and magnesium sulfonate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and delivers less than or equal to 5 mmol of total soap to the composition; and e) one or more organic friction modifier at from 0.01 to 2.0 wt. % of the composition; wherein the lubricating oil composition has a total sulfated ash of less than or equal to 1.2 wt. %, a kinematic viscosity at 100 C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.4 wt. %; and wherein the lubricating oil composition results in a rating of at least 2 for emulsion corrosion resistance in the emulsion corrosion test.

[0088] In yet another form, this invention relates to a method of lubricating a hybrid engine comprising: i) supplying to the engine a lubricating oil composition comprising or resulting from the admixing of: a) an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof; b) one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more); c) optionally one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 to 12.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is from 1.0 to 9.0 wt. % of the composition; d) an overbased calcium sulfonate detergent, an overbased magnesium sulfonate detergent, an overbased mixed calcium and magnesium sulfonate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and delivers less than or equal to 5 mmol of total soap to the composition; and e) one or more organic friction modifier at from 0.01 to 2.0 wt. % of the composition; wherein the lubricating oil composition has a total sulfated ash of less than or equal to 1.2 wt. %, a kinematic viscosity at 100 C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.4 wt. %; and wherein the lubricating oil composition results in a rating of at least 2 for emulsion corrosion resistance in the emulsion corrosion test.

[0089] The lubricating oil composition for hybrid engines provided above may have a total sulfated ash of less than or equal 1.2 wt. %, or less than or equal to 1.0 wt. %, or less than or equal to 0.8 wt. %, or less than or equal to 0.6 wt. %, or less than or equal to 0.4 wt. %, as measured by ASTM D874-13a (2018). The lubricating oil composition for hybrid engines provided above may have a total phosphorous level of less than or equal to 0.12 wt. %, or less than or equal to 0.10 wt. %, or less than or equal to 0.09 wt. %, or less than or equal to 0.08 wt. %, or less than or equal to 0.07 wt. %, or less than or equal to 0.06 wt. %, or less than or equal to 0.05 wt. %, or less than or equal to 0.04 wt. %, or less than or equal to 0.03 wt. %. The lubricating oil composition for hybrid engines provided above may have a total sulfur level of less than or equal to 0.4 wt. %, or less than or equal to 0.35 wt. %, or less than or equal to 0.30 wt. %, or less than or equal to 0.25 wt. %, or less than or equal to 0.20 wt. %, or less than or equal to 0.15 wt. %, or less than or equal to 0.10 wt. %, or less than or equal to 0.05 wt. %, or less than or equal to 0.01 wt. %.

[0090] Generally, the kinematic viscosity at 100 C. (KV100) of the inventive lubricating compositions for use in hybrid engines may range from 5 to 25 cSt, or 6 to 18 cSt, or 8 to 16 cSt, such as 7 to 18 cSt, such as 10 to 15 cSt, or 13 to 16 cSt, or 8 to 17 cSt, as determined according to ASTM D 445-19a. The lubricating composition of the present disclosure may be a monograde oil identified by the viscometric descriptor SAE X, where X represents any one of 20, 30, 40, and 50; the characteristics of the different viscometric grades can be found in the SAE J300 classification. Alternately, the lubricating composition may be a multigrade oil identified by the viscometric descriptor of SAE 15W-X, SAE 1OW-X, SAE 5W-X or SAE OW-X, where X represents any one of 8, 12, 16, 20, 30, 40, and 50; the characteristics of the different viscometric grades can be found in the SAE J300 classification. In embodiments, the lubricating compositions described herein may have a viscometric descriptor of SAE 1OW-X, SAE 5W-X or SAE OW-X, where X represents any one of 8, 12, 16, 20, 30, 40. In preferred embodiments, the lubricating compositions described herein may have a viscometric descriptor of SAE OW-X, where X represents any one of 8, 12, 16, 20, 30, 40. In embodiments, the lubricating compositions described herein may have a viscometric descriptor of SAE 5W-40, OW-20 or OW-16.

[0091] The inventive lubricating oil compositions for hybrid engines and the method of lubricating a hybrid engine result in a passing emulsion dispersion and stability performance at all 4 test conditions, or at least 3 test conditions, or at least 2 test conditions, or at least 1 test condition in the Emulsion Stability test (modified ASTM D7563). The inventive lubricating oil compositions for hybrid engines and the method of lubricating a hybrid engine result in a rating of at least 1, or at least 2, or 3 for emulsion corrosion resistance in the emulsion corrosion test. The inventive lubricating oil compositions for hybrid engines and the method of lubricating a hybrid engine result in a rating of at least 2, or 3 for bearing wear in the journal bearing wear test.

[0092] The inventive lubricating oil compositions for hybrid engines and the method of lubricating a hybrid engine also provide for substantially no aqueous separation of lubricating oil emulsions including the lubricating oil composition and up to 15 wt. % water at 0 C. and 25 C. in the Emulsion Stability test (modified ASTM D7563). Substantially no aqueous separation means that less than 1 vol. %, or less than 0.5 vol. % of lubricating oil emulsion separates (as a clear colorless liquid at the bottom of the measurement cylinder) from the lubricating oil at 0 C. and 25 C. in the Emulsion Stability test (modified ASTM D7563).

[0093] The inventive lubricating oil compositions for hybrid engines and the method of lubricating a hybrid engine also provide for low oil separation of lubricating oil emulsions including the lubricating oil composition and up to 15 wt. % water at 0 C. and 25 C. in the Emulsion Stability test (modified ASTM D7563). Low oil separation means that 20 vol. % or less (such as 15 vol. % or less, such as 10 vol. % or less, such as 5 vol. % or less, such than 1 vol % or less) of lubricating oil emulsion separates (as oil at the top of the measurement cylinder) from the lubricating oil at 0 C. and 25 C. in the Emulsion Stability test (modified ASTM D7563). In preferred embodiments, the inventive lubricating oil compositions for hybrid engines have 0% oil separation and 0% aqueous separation at 25 C. for 24 hours (preferably 0% oil separation and 0% aqueous separation at 25 C. for at least 72 hours, preferably 0% oil separation and 0% aqueous separation at 25 C. for at least 168 hours, preferably 0% oil separation and 0% aqueous separation at 25 C. for at least 30 days, preferably 0% oil separation and 0% aqueous separation at 25 C. for at least 60 days, preferably 0% oil separation and 0% aqueous separation at 25 C. for at least 120 days.) In preferred embodiments, the inventive lubricating oil compositions for hybrid engines have Low oil separation and substantially no aqueous separation at 25 C. for 24 hours (preferably for at least 72 hours, preferably for at least 168 hours, preferably for at least 30 days, preferably for at least 60 days, preferably for at least 120 days.)

Base Oil(s)

[0094] The base oil or oil of lubricating viscosity used in the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided may have a KV100 viscosity of less than or equal to 20 cSt, or less than or equal to 15 cSt, or less than or equal to 12 cSt, or less than 10 cSt, or less than 9 cSt, or less than 8 cSt, or less than 7 cSt, or less than 6 cSt, or less than 5 cSt, or less than 4 cSt; and may be included at greater than 50 wt. %, or greater than 60 wt. %, or greater than 70 wt. %, or greater than 80 wt. %, or greater than 90 wt. %, or greater than 95 wt. % of the composition. In another form of the instant disclosure, the oil of lubricating viscosity constitutes from 60 wt. % to 95 wt. %, or 70 to 90 wt. %, or 75 to 85 wt. % of the composition, and comprises a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof, and is substantially free of the Group I base oil.

[0095] The lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine of the instant disclosure may have a total sulfated ash of less than or equal to 1.2 wt. % (such as 1.0 wt % or less, such as 0.9 wt % or less, such as 0.8 wt % or less), a kinematic viscosity at 100 C. of 3 to 20 cSt (such as 5 to 20 cSt, such as 3.8 to less than 16.3 cSt, such as 3.8 to less than 9.3 cSt,), a total phosphorous level of less than or equal to 0.12 wt. % (such as 0.11 wt % or less, such as 0.10 wt % or less, such as 0.5 wt % or less, such as 0.1 wt % or less, such as 0.09 wt % or less, such as 0.08 wt % or less), and a total sulfur level of less than or equal to 0.4 wt. %, or less than or equal to 0.35 wt %, or less than or equal to 0.30 wt %, or less than or equal to 0.25 wt %, or less than or equal to 0.20 wt %. Optionally, the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine of the instant disclosure may have a total sulfated ash of less than or equal to 0.8 wt %, a kinematic viscosity at 100 C. of 3.8 to less than 16.3 cSt (such as 3.8 to less than 9.3 cSt), a total phosphorous level of less than or equal to 0.1 wt %, and a total sulfur level of less than or equal to 0.30 wt %, or less than or equal to 0.25 wt % (or less than or equal to 0.20 wt %).

[0096] The lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include a Group V base oil as part of the oil of lubricating viscosity, wherein the Group V based oil is included in the lubricating oil composition at from 0.1 to 50 wt. %, or 0.5 to 40 wt. %, or 1.0 to 20 wt. % or 2.0 to 10 wt. %, or 3.0 to 5 wt. % of the overall composition.

[0097] In another embodiment, the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include a base oil comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, a Group V base oil or combinations thereof, wherein the base oil is included at greater than 60 wt. %, or greater than 70 wt. %, or greater than 80 wt. %, or greater than 90 wt. %, or greater than 95 wt. % of the composition.

[0098] In another embodiment, the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include a base oil comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof, wherein the base oil is included at greater than 60 wt. %, or greater than 70 wt. %, or greater than 80 wt. %, or greater than 90 wt. %, or greater than 95 wt. % of the composition. That is the base oil is substantially free of Group V base oil.

[0099] In yet another embodiment, the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include a base oil comprising a Group I base oil, a Group II base oil, a Group III base oil, or combinations thereof, wherein the base oil is included at greater than 60 wt. %, or greater than 70 wt. %, or greater than 80 wt. %, or greater than 90 wt. %, or greater than 95 wt. % of the composition. That is the base oil is substantially free of both Group IV base oil and Group V base oil.

[0100] In still yet another embodiment, the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include a base oil comprising a Group II base oil, a Group III base oil, or combinations thereof, wherein the base oil is included at greater than 60 wt. %, or greater than 70 wt. %, or greater than 80 wt. %, or greater than 90 wt. %, or greater than 95 wt. % of the composition. That is the base oil is substantially free of both Group I base oil, Group IV base oil, as well as Group V base oil.

Dispersants

[0101] The lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine includes one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more), and also optionally includes one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol, such as less that 1500 g/mol, such as less that 1400 g/mol, such as less that 1300 g/mol, such as less that 1200 g/mol, such as less than 1100 g/mol, such as less than 1000.0 g/mol, such as about 950 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 to 12.0 wt. %, based upon the lubricating oil composition (such as 1.10 to 10.0 wt. %, 1.20 to 9.0 wt. %, such as to 1.5 to 8.0 wt. %), preferably wherein: 1) the treat level of the higher molecular weight PIBSA-PAM is from 1.0 to 12.0 wt. % of the composition (such as 1.0 to 9.9 wt. %, such as 3 to 9.9 wt. %, such as 5 to 9.75), based upon the lubricating oil composition, and 2) the treat level of the lower molecular weight PIBSA-PAM is 0 wt. %,or 0.1 to 3.0 wt. %, such as 0.25 to 2.5 wt. %, such as 0.50 to 2.0 wt. %, based upon the lubricating oil composition. In embodiments, the treat level of the lower molecular weight PIBSA-PAM less than or equal to 3.0 wt. %. Hence, the inventive lubricating oil compositions including the higher molecular weight PIBSA-PAM in a borated form, the optional lower molecular weight PIBSA-PAM in a borated or a combination thereof, are included at a treat level to deliver from 20 to 1000 ppm, or 50 to 800 ppm, or 100 to 600 ppm, or 200 to 400 ppm, or 50 to 300 ppm by weight of boron to the composition. With regard to the treat level of the combination of the one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more), and one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), it may range from 1.0 to 12.0 wt %, or 2.0 to 10.0 wt. %, or 2.8 to 9.0 wt. %, or 3.0 to 8.0 wt. %, or 4.0 to 7.0 wt. %, or 5.0 to 6.0 wt. % of the composition. The treat level of the higher molecular weight PIBSA-PAM in the composition may range from 1.0 to 9.0 wt. %, or 1.5 to 8.0 wt. %, or 1.5 to 7.0 wt. %, or 1.8 to 6.0 wt. %, or 2.0 to 6.0 wt. %, or 2.0 to 5.0 wt. %, or 3.0 to 4.0 wt. %, or 1.0 to 4.0 wt. % of the composition. The treat level of the lower molecular weight PIBSA-PAM in the composition is less than or equal to 3.0 wt. %, or less than or equal to 2.8 wt. %, or less than or equal to 2.6 wt. %, or less than or equal to 2.4 wt. %, or less than or equal to 2.2 wt. %, or less than or equal to 2.0 wt. %, or less than or equal to 1.8 wt. %, or less than or equal to 1.6 wt. %, or less than or equal to 1.4 wt. %, or less than or equal to 1.2 wt. %, or less than or equal to 1.0 wt. %, or less than or equal to 0.8 wt. %, or less than or equal to 0.6 wt. %, or less than or equal to 0.4 wt. %, or 0 wt. %.

Zinc Dialkyl Dithiophosphate (ZDDP)

[0102] The lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided herein may include one or more zinc dialkyl dithiophosphate (ZDDP) compounds. The one or more zinc hydrocarbyl diphosphate compounds may provide more than 0.01 wt. % zinc, and less than or equal to 0.12 wt. % of phosphorus, based upon the weight of the lubricating oil composition. The ZDDP compounds may include a hydrocarbyl group of the zinc hydrocarbyl dithiophosphate which is derived from one or more primary alcohols, one or more secondary alcohols or a combination of primary and secondary alcohols. The one or more ZDDP compounds may be included in the lubricating oil at a treat level of from 0.08 wt. % to 2.0 wt, or 0.4 to 2.0 wt. %, or 0.1 to 1.7 wt. %, or 0.4 to 1.6 wt. %, or 0.6 to 1.5 wt. %, or 0.7 to 1.2 wt. %, or 0.8 to 1.0 wt % of the lubricating oil composition. In one advantageous form, the one or more zinc dialkyldithiophosphates (ZDDP) include greater than or equal to 85 wt. % secondary alcohols and less than or equal to 15 wt. % primary alcohols.

Detergents

[0103] With regard to the one or more overbased detergents of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine, in one form, they may be selected from an overbased calcium salicylate detergent, an overbased magnesium salicylate detergent, an overbased mixed calcium and magnesium salicylate detergent or a combination thereof. In this form, the one or more overbased detergents may have a Total Base Number (mgKOH/g) greater than or equal to 9 and less than or equal to 500, or alternatively 50 to 450, or alternatively 100 to 400, or 150 to 400, or 200 to 350, or 250 to 300 (mgKOH/g). In another form, the one or more overbased detergents may have a TBN of 100 mgKOH/g or more (such as 200 mgKOH/g or more), and typically will have a TBN of 250 mgKOH/g or more, such as 300 mgKOH/g or more, such as from 200 to 500 mgKOH/g, 225 to 450 mgKOH/g, 250 to 400 mgKOH/g, or 300 to 350 mgKOH/g. In this form, the one or more overbased detergents may be included in the lubricating oil composition at a treat level to deliver at least 5 mmol of total soap, or at least 10 mmol of total soap, or at least 15 mmol of total soap, or at least 20 mmol of total soap, or at least 30 mmol of total soap, or at least 50 mmol of total soap, or at least 70 mmol of total soap, or at least 90 mmol of total soap, or 100 mmol to total soap to the lubricating oil composition.

[0104] With regard to the one or more overbased detergents of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine, in another form, they may be selected from an overbased calcium sulfonate detergent, an overbased magnesium sulfonate detergent, an overbased mixed calcium and magnesium sulfonate detergent or a combination thereof. In this form, the one or more overbased detergents may have a Total Base Number (mgKOH/g) greater than or equal to 9 and less than or equal to 500, or alternatively 50 to 450, or alternatively 100 to 400, or 150 to 400, or 200 to 350, or 250 to 300 (mgKOH/g). In another form, the one or more overbased detergents may have a TBN of 100 mgKOH/g or more (such as 200 mgKOH/g or more), and typically will have a TBN of 250 mgKOH/g or more, such as 300 mgKOH/g or more, such as from 200 to 500 mgKOH/g, 225 to 450 mgKOH/g, 250 to 400 mgKOH/g, or 300 to 350 mgKOH/g. In this form, the one or more overbased detergents may be included in the lubricating oil composition at a treat level to deliver at least 5 mmol of total soap, or at least 10 mmol of total soap, or at least 15 mmol of total soap, or at least 20 mmol of total soap, or at least 30 mmol of total soap, or at least 50 mmol of total soap, or at least 70 mmol of total soap, or at least 90 mmol of total soap, or 100 mmol to total soap to the lubricating oil composition.

[0105] With regard to the one or more overbased detergents of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine, the metal of the one or more overbased metal detergents may be sodium, potassium, lithium, calcium, magnesium or combinations thereof. One particularly advantageous metal is calcium. In one advantageous form, the one or more overbased detergents of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine, may include a combination of a calcium salicylate detergent and magnesium salicylate detergent that delivers to the composition a total soap of greater than or equal to 0.5 wt. %, or greater than or equal to 0.6 wt. %, or greater than or equal to 0.7 wt. %, or greater than or equal to 0.8 wt. %, or greater than or equal to 0.9 wt. %, or greater than or equal to 1.0 wt. %.

Optional Functionalized Polymer Component

[0106] The inventive lubricating oil compositions for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include as part of the lubricating oil one or more functionalized polymers, wherein the functionalized polymer may be a functionalized-hydrogenated PolylsoPrene (F-H-PI) polymer, a functionalized-Olefin polymer or copolymer (f-OCP) or a combination of a functionalized-hydrogenated PolylsoPrene (F-H-PI) polymer and a functionalized-Olefin polymer or copolymer (f-OCP).

[0107] As described above, the lubricating oil compositions for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include a functionalized polymer at from 0.01 to 20 wt. %, or 0.2 to 20 wt. %, or 0.2 to 6 wt. %, or 0.2 to 2.0 wt. %, or 0.4 to 1.8 wt. %, or 0.6 to 1.6 wt. %, or 0.8 to 1.4 wt. %, or 1.0 to 1.2 wt. % or 0.3 to 5 wt. %, or 0.4 to 3 wt. %, or 0.5 to 2.0 wt. %, or 0.5 to 1.0 wt. %, or 0.7 to 0.9 wt. % of the composition, wherein the functionalized polymer comprises a partially or fully saturated olefin homopolymer or copolymer backbone and at least one functional group, having: [0108] i) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization, [0109] ii) where the functional group is derived from an acylating agent and a compound containing amino and/or hydroxyl groups (including but not limited to where the polymer is functionalized with an acylating agent and subsequently reacted with a compound containing amino and/or hydroxyl groups), and, [0110] iii) wherein the homopolymer or copolymer backbone is derived from monomers selected from the group consisting of C.sub.2 to C.sub.30 linear alpha olefins, and C.sub.4 to C.sub.20 conjugated dienes.

[0111] In another embodiment, the functionalized polymer described above of the lubricating oil compositions for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the functionalized polymer is at from 0.3 to 5 wt. % based upon the total weight of the lubricating oil composition, and the functionalized polymer comprises an amide, imide, and/or ester functionalized partially or fully saturated polymer comprising C.sub.4-5 olefins having: [0112] i) an Mw/Mn of less than 2, [0113] ii) a Functionality Distribution (Fd) value of 3.5 or less, and [0114] iii) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization, provided that, if the polymer prior to functionalization is a copolymer of isoprene and butadiene, then the Mn of the copolymer is greater than 25,000 g/mol (GPC-PS).

[0115] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include a polymer backbone derived from one or more of ethylene, propylene, butene, butadiene, isoprene, styrene, decene, and or dodecene.

[0116] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the homopolymer or copolymer backbone is derived from monomers selected from the group consisting of C.sub.2 to C.sub.12 linear alpha olefins and C.sub.4 to C.sub.12 conjugated dienes.

[0117] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the polymer backbone is a copolymer of isoprene and butadiene.

[0118] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the polymer backbone prior to functionalization comprises at least 90% isoprene repeat units, or at least 93% isoprene repeat units, or at least 96% isoprene repeat units, or at least 99% isoprene repeat units.

[0119] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the polymer backbone is homo-polyisoprene, or an ethylene-propylene copolymer.

[0120] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the polymer backbone comprises repeat units of one or more polar monomers.

[0121] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the one or more polar monomers are selected from the group consisting of fumarates, acrylates, maleates, methacrylates, acrylamides, acrylonitriles and combinations thereof.

[0122] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the polymer prior to functionalization has an Mn of 10,000 g/mol up to 100,000 g/mol (GPC-PS), or an Mn of 20,000 g/mol up to 80,000 g/mol (GPC-PS), or an Mn of 40,000 g/mol up to 80,000 g/mol (GPC-PS).

[0123] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the polymer prior to functionalization has an Mn of at least 25,000 g/mol (GPC-PS), or Mn of at least 45,000 g/mol (GPC-PS), or Mn of at least 65,000 g/mol (GPC-PS), or Mn of at least 85,000 g/mol (GPC-PS).

[0124] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein if the polymer prior to functionalization is a copolymer of isoprene and butadiene, the Mn of the copolymer is greater than 25,000 g/mol (GPC-PS), or greater than 45,000 g/mol (GPC-PS), or greater than 65,000 g/mol (GPC-PS), or greater than 85,000 g/mol (GPC-PS).

[0125] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the polymer backbone comprises at least about 50% %, or at least 60%, or at least 70% of 1,4 insertions of monomer.

[0126] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the acylating agent is maleic anhydride, itaconic anhydride, or an unsaturated carboxylic acid such as maleic acid, fumaric acid, cinnamic acid, or a corresponding ester.

[0127] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the functional group is selected from an amide, imide, or ester.

[0128] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the compound with which the acylated polymer backbone is reacted is a monoamine or a polyamine.

[0129] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the acylated polymer backbone is reacted with one or more amines selected from the group consisting of: polyhydrocarbyl polyamines, polyalkylene polyamines, hydroxy-substituted polyamines, polyoxyalkylene polyamines, and combinations thereof.

[0130] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the acylated polymer backbone is reacted with N-phenyl-p-phenylenediamine.

[0131] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the acylated polymer backbone is reacted with one or more hydroxy-substituted polyamine selected from the group consisting of: N-hydroxyalkyl-alkylene polyamines such as N-(2-hydroxyethyl)ethylene diamine, N-(2-hydroxyethyl)piperazine, and/or N-hydroxyalkylated alkylene diamines; or with one or more polyoxyalkylene polyamines of the group consisting of: polyoxyethylene and/or polyoxypropylene diamines.

[0132] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the compound with which the acylated polymer backbone is reacted is a hydroxyl-group containing compound.

[0133] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the functionalized polymer has a Functionality Distribution (Fd) value of 3.5 or less, or 3.0 or less, or 2.5 or less, or 2.0 or less.

[0134] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the functionalized polymer has an average functionality (Fv) of 1.4 to 20, or 2.0 to 18, or 4.0 to 16, or 6.0 to 14, or 8.0 to 12 functional group grafts/polymer chain.

[0135] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the functionalized polymer has a molecular weight distribution (Mw/Mn) of less than 2, or less than 1.8, or less than 1.6, or less than 1.4, or less than 1.2.

[0136] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the functionalized polymer is an amide or imide functionalized partially or fully saturated homo-polyisoprene having: [0137] (i) an Mw/Mn of less than 2, [0138] (ii) a Functionality Distribution (Fd) value of 3.5 or less, and [0139] (iii) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization.

[0140] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the functionalized polymer is an amide or imide functionalized partially or fully saturated homo-polyisoprene having: [0141] (i) an Mw/Mn of less than 1.8, [0142] (ii) a Functionality Distribution (Fd) value of 2.5 or less, [0143] (iii) an average functionality (Fv) of 4 to 10 functional group grafts/polymer chain, and [0144] (iv) an Mn of from 20,000 g/mol to 50,000 g/mol (GPC-PS) of the polymer prior to functionalization.

[0145] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the functionalized polymer is derived from a homo-polyisoprene that has been acylated with maleic anhydride or maleic acid and further reacted with an N-phenylphenylene diamine.

[0146] In another embodiment, the functionalized polymer described above of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include wherein the functionalized polymer is derived from an ethylene-propylene copolymer that has been acylated with maleic anhydride or maleic acid and further reacted with an N-phenylphenylene diamine.

[0147] In yet another embodiment, the functionalized polymer of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include at least 50%, or at least 60%, or at least 70% of 1,4-insertions of monomer. Furthermore, the functionalized polymer of the lubricating oil composition of the instant disclosure may include a partially or fully saturated homopolyisoprene containing one or more pendant amine groups and having an Mn of 25,000 to 100,000 g/mol, or 35,000 to 90,000 g/mol, or 45,000 to 80,000 g/mol, or 55,000 to 75,000 g/mol (GPC-PS) and at least 50%, or at least 60%, or at least 70% of 1,4-insertions prior to functionalization.

[0148] In yet another embodiment, the functionalized polymer of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively be absent of styrene repeat units, or absent of butadiene repeat units, or is not a homo-polyisobutylene, or is not a copolymer of isoprene and butadiene.

[0149] In yet another embodiment, the functionalized polymer of the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively also include a non-ionic fatty alcohol ethoxylate at from 1.0 to 20 wt. %, or 3.0 to 18.0 wt. %, or 5.0 to 15.0 wt %, or 7.0 to 13.0 wt. %, or 8.0 to 10.0 wt. % of the one or more functionalized polymers.

Other Additives

[0150] The lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may optionally include as part of the lubricating oil one or more of the following components: one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more anti-foaming agents; one or more viscosity modifiers; one or more dispersants other than the higher molecular weight PIBSA-PAM and the lower molecular weight PIBSA-PAM; one or more inhibitors; one or more antirust agents (rust inhibitors); one or more corrosion inhibitors; one or more seal swell agents; and/or one or more other anti-wear agents.

Corrosion Inhibitors/Rust Inhibitors

[0151] The lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may alternatively include as part of the lubricating oil one or more corrosion inhibitors, rust inhibitors or combinations thereof at a treat rate of greater than or equal to 0.02 wt. % of the lubricating oil composition. Water is a reaction product of the combustion of gasoline in a hybrid engine, and therefore corrosion of various internal components of the hybrid engine due to water exposure may be addressed with proper selection of corrosion inhibitor type and treat level in the lubricating oil composition. The corrosion inhibitor or rust inhibitor, may include, but is not limited to, a non-ionic fatty alcohol ethoxylate, a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, a primary amine, a substituted carboxylic acid functional group, a substituted ester functional group, a substituted anhydride functional group, or a combination thereof. The corrosion inhibitor and/or rust inhibitor may be included in the lubricating oil composition at a treat level of from of 0.01 wt. % to 6.0 wt. %, or 0.02 to 5.0 wt. %, or 0.05 to 4.5 wt. %, or 0.1 to 4.0 wt. %, or 0.5 to 3.5 wt. %, or 1.0 to 3.0 wt. %, or 2.0 to 2.5 wt. % of the lubricating oil composition.

[0152] The inventive lubricating oil compositions including one or more corrosion inhibitors, rust inhibitors or combinations at the treat levels indicated above provide for less than 5%, or less than 4%, or less than 3%, or less than 2%, or less than 10% corrosion or rust in the ASTM D1748 test for corrosion/rust protection. Additionally, the inventive lubricating oil compositions including one or more corrosion inhibitors, rust inhibitors or combinations at the treat levels indicated above provide for substantially no (as defined above) aqueous separation of lubricating oil emulsions including the lubricating oil composition and up to 10 wt. % water at 0 C. and 25 C. in the Emulsion Stability test (modified ASTM D7563).

Friction Modifiers

[0153] The lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided above may optionally include as part of the lubricating oil one or more friction modifiers including, but not limited to, dimeric molybdenum dialkyldithiocarbamate (moly dimer), a trimeric molybdenum dialkyldithiocarbamate (moly trimer), or a combination thereof at a treat level to deliver from 12 ppm to 1000 ppm, or 20 ppm to 800 ppm, or 30 ppm to 600 ppm, or 40 to 400 ppm, or 60 to 200 ppm, or 80 to 150 ppm, or 100 to 130 ppm by weight of molybdenum to the composition. In yet another advantageous form, the lubricating oil composition of the instant disclosure is substantially free of molybdenum, which means less than 10 ppm, or less than 5 ppm, or less than 3 ppm, or less than 2 ppm, or less than 1 ppm, based on the overall weight of the lubricating oil composition.

[0154] The lubricating oil compositions for hybrid engines and the method of lubricating a hybrid engine provided above may optionally include as part of the lubricating oil one or more organic friction modifiers including, but not limited to, alkylated succinic anhydrides, alkylated succinic acids, alkylated carboxylic acids, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, and combinations thereof. The one or more organic friction modifiers may be included in the overall lubricating oil composition at 0.01 to 5.0 wt. %, or 0.05 to 4.5 wt. %, or 0.1 to 4.0 wt. %, or 0.5 to 3.5 wt. %, or 1.0 to 3.0 wt. %, or 1.5 to 2.5 wt. % of the composition.

Antioxidants

[0155] The lubricating oil compositions for hybrid engines and the method of lubricating a hybrid engine provided above may also include as part of the lubricating oil one or more antioxidants selected from one or more phenolic antioxidants, one or more sulfur based antioxidants, one or more aminic antioxidants or a combination thereof, and wherein the one or more antioxidants comprise from 0.1 to 6.0 wt. %, or 1.0 to 5.0 wt. %, or 1.5 to 3.5 wt. %, or 2.0 to 3.0 wt. % of the overall lubricating oil composition.

Pour Point Depressants

[0156] The lubricating oil compositions for hybrid engines and the method of lubricating a hybrid engine provided above may also include as part of the lubricating oil one or more pour point depressants. Non-limiting exemplary pour point depressants include, polymethacrylate, polyacrylate or a combination thereof. The one or more pour point depressants may be included in the lubricating oil composition at from 0.01 to 5.0 wt. %, or 0.05 to 4.5 wt. %, or 0.1 to 4.0 wt. %, or 0.5 to 3.5 wt. %, or 1.0 to 3.0 wt. %, or 1.5 to 2.5 wt. % of the overall lubricating oil composition.

Methods of Using Such Compositions in Hybrid Engines

[0157] The lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided herein may be used to improve engine cleanliness as a passenger vehicle lubricant (PVL), or a commercial vehicle lubricant (CVL) by supplying to the engine as a lubricating oil such compositions.

[0158] As described above, the inventive lubricating oil compositions for hybrid engines and the method of lubricating a hybrid engine is typically used in a gasoline fueled hybrid engine, but may alternatively be used in a diesel fueled hybrid engine to improve fuel efficiency and reduce carbon emissions.

[0159] The lubricating oil composition for hybrid engines may be used in conjunction with various other fuel sources for combustion in the internal combustion engine. The fuel source may also include ethanol, natural gas, hydrogenated vegetable oil, fatty acid methyl esters (FAME), sustainable aviation fuel (SAF), ammonia, hydrogen, mogas, propane, diesel, or combinations thereof. Renewable fuel (such as hydrogenated vegetable oil, fatty acid methyl ester, sustainable aviation fuel (SAF), or combinations thereof) are particularly advantageous. In a preferred form, the fuel supplied to the hybrid engine comprises mogas and ethanol with the ethanol constituting from 5 to 20 vol. % of the fuel.

[0160] The lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided herein may be used such that the fuel and the lubricating oil composition are combined prior to injection into a combustion chamber of the hybrid ICE engine to form a fuel composition. Alternatively, the lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided herein may be used such that the fuel and the lubricating oil composition are combined in the combustion chamber ICE of the hybrid engine to form a fuel composition.

[0161] The lubricating oil composition for hybrid engines and the method of lubricating a hybrid engine provided herein may be used in conjunction with a hybrid engine that is spark ignited, compression ignited, or a combination thereof. The hybrid internal combustion engine may be a heavy duty or light duty internal combustion engine. The hybrid engine may optionally include a turbocharger or a supercharger prior to the gasoline fueled internal combustion engine of the hybrid engine.

[0162] In embodiments, the lubricating compositions disclosed herein may be used in heavy-duty hybrid engines (e.g., heavy-duty vehicles having a gross vehicle weight rating of 10,000 pounds or more).

[0163] In embodiments, the lubricating compositions disclosed herein may be used as passenger car motor oil.

[0164] In embodiments, the lubricating compositions disclosed herein may be used in a passenger car or heavy duty vehicle where the gasoline fueled internal combustion engine is a passenger car or heavy duty vehicle internal combustion engine (optionally also using natural gas, propane, renewable fuel, and/or diesel fuel).

[0165] In embodiments, the lubricating compositions disclosed herein may be for use in a heavy duty internal combustion engines or stationary internal combustion engines.

Methods of Evaluating Lubricants for Ranking Performance In a Hybrid ICE

[0166] Also disclosed herein is a method of evaluating a lubricating oil composition for ranking the performance of the lubricating oil composition in a hybrid engine. The method of evaluating a lubricating oil composition for ranking performance of the lubricating oil composition in a hybrid engine includes the following non-limiting steps of: i) selecting a lubricating oil composition for bench scale testing; ii) testing the composition for emulsion dispersion and stability performance in the Emulsion Stability test (modified ASTM D7563) to determine its score from 0 to 3; iii) testing the composition for emulsion corrosion resistance in the emulsion corrosion test to determine its score from 0 to 3; iv) testing the composition for journal bearing wear in the journal bearing wear test to determine the change in the depth of the bearing pre-test and post-test in average maximum wear and assigning a wear result from 1 to 3; and v) combining test results from steps ii), iii) and iv) above to provide an overall performance rating for ranking the performance of the lubricating oil composition in a hybrid engine.

Concentrates

[0167] A concentrate, also referred to as an additive package, adpak, or addpack, is a composition having less than 50 mass % (such as from 1 to 40 mass %, such as from 2 to 30 mass %, such as 3 to 25 mass %, such as 4 to 20 mass %, such as 5 to 15 mass %) base oil and lubricant composition additives (such as described herein) which is typically then further blended with additional Group I, II, III and/or Group IV base oil to form a lubricating oil product. The concentrate typically is absent Group IV base oil, such as polyalphaolefin, having a viscosity index of 100 or more, such as 120 or more, such as 140 or more as determined by ASTM D2270. Alternately the concentrate contains Group IV base oil, such as polyalphaolefin, having a viscosity index of 100 or more, such as 120 or more, such as 140 or more as determined by ASTM D2270 in amounts that the total concentration of the PAO in the final lubrication oil composition is less 70 mass % or less, such as 60 mass % or less, 50 mass % or less, such as 40 mass % or less, 30 mass % or less, such as 20 mass % or less, 10 mass % or less, such as 5 mass % or less, based upon the weight of the lubricating oil composition.

[0168] This disclosure also relates to concentrate compositions comprising or resulting from the admixing of: from 1 to less than or equal to 50 wt. % of one or more base oils; from 2 to 40 wt. % of an overbased calcium salicylate detergent, an overbased magnesium salicylate detergent, an overbased mixed calcium and magnesium salicylate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500; and from 2 to 40 wt. % of one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more).

[0169] This disclosure also relates to alternative concentrate compositions comprising or resulting from the admixing of: from 1 to less than or equal to 50 wt. % of one or more base oils; from 2 to 40 wt. % of an overbased calcium sulfonate detergent, an overbased magnesium sulfonate detergent, an overbased mixed calcium and magnesium sulfonate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500; from 2 to 40 wt. % of one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more), and one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), and from 0.5 to 10 wt. % of one or more organic friction modifier.

[0170] Alternatively, the concentrate compositions disclosed above may include from 2 to 20 wt. % of one or more zinc hydrocarbyl diphosphate compounds, wherein the one or more zinc hydrocarbyl diphosphate compounds include hydrocarbyl groups derived from one or more primary alcohols, one or more secondary alcohols or a combination of primary and secondary alcohols.

[0171] Alternatively, the concentrate compositions disclosed above include from 0.10 to 10 wt. % of one or more corrosion inhibitors, rust inhibitors or combinations thereof selected from the group consisting of a non-ionic fatty alcohol ethoxylate, a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, a primary amine, a substituted carboxylic acid functional group, a substituted ester functional group, a substituted anhydride functional group and combinations thereof.

[0172] Alternatively, the concentrate compositions disclosed above may include the one or more functionalized polymers and more particularly, comprising from 1 to 30 wt. %, such as 2 to 20 wt. %, based upon the weight of the concentrate, of one or more functionalized polymers, wherein the one or more functionalized polymers comprise a partially or fully saturated olefin homopolymer or copolymer backbone and at least one functional group, having: i) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization, ii) where the functional group is derived from an acylating agent and a compound containing amino and/or hydroxyl groups (including but not limited to where the polymer is functionalized with an acylating agent and subsequently reacted with a compound containing amino and/or hydroxyl groups), and, iii) wherein the homopolymer or copolymer backbone is derived from monomers selected from the group consisting of C.sub.2 to C.sub.30 linear alpha olefins, and C.sub.4 to C.sub.20 conjugated dienes.

[0173] The concentrate compositions disclosed herein may further comprise combining the concentrate with a base oil to form a lubricating oil composition comprising: a) an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof; b) one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more); c) optionally, one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 (such as 1.5) to 12.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is from 0.1 to 9.0 wt. % (such as 1.5 to 9.0 wt %) of the composition; and d) an overbased calcium salicylate detergent, an overbased magnesium salicylate detergent, an overbased mixed calcium and magnesium salicylate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and delivers at least 5 mmol of total soap to the composition; wherein the lubricating oil composition has a total sulfated ash of less than or equal to 1.2 wt. %, a kinematic viscosity at 100 C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.4 wt. %; and wherein the lubricating oil composition results in a passing emulsion stability performance at all 4 test conditions in the Emulsion Stability test (modified ASTM D7563).

[0174] The concentrate compositions disclosed herein may also further comprise combining the concentrate with a base oil to form a lubricating oil composition comprising: a) an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof; b) one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more); c) optionally, one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 to 12.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is from 0.1 to 9.0 wt. % (such as 1.0 to 9.0 wt. %) of the composition; and d) an overbased calcium sulfonate detergent, an overbased magnesium sulfonate detergent, an overbased mixed calcium and magnesium sulfonate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and delivers at least 5 mmol of total soap to the composition; and e) one or more organic friction modifier at from 0.01 to 2.0 wt. % of the composition; wherein the lubricating oil composition has a total sulfated ash of less than or equal to 1.2 wt. %, a kinematic viscosity at 100 C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.4 wt. %; and wherein the lubricating oil composition results in a rating of at least 2 for emulsion corrosion in the emulsion corrosion test.

[0175] Concentrates may be present in the lubricating oil compositions of the instant disclosure at from of 0.5 mass % to 35 mass %, such as 5 mass % to 30 mass %, such as 7.5 mass % to 25 mass %, such as 10 to 22.5 mass %, such as 15 to 20 mass %, such as 12 to 20 mass % based upon the mass of the lubricating oil composition.

[0176] Optionally, the concentrate may be absent functionalized oil.

[0177] In embodiments, the concentrate composition may optionally be absent solvent (such as aliphatic or aromatic solvent) and/or absent functionalized base oil.

[0178] Optionally, the concentrate may be absent phenolic antioxidant.

[0179] In embodiments, the concentrate may be substantially free of or absent aminic antioxidant, such as diphenylamine, such as di (nonylphenyl) amine.

[0180] In embodiments, the concentrate may comprise from 200 to 2000 ppm, or 500 to 1500 ppm, or 1000 to 1300 ppm boron. Alternately, the concentrate may be absent boron.

[0181] In embodiments, the concentrate may comprise less than or equal to 20 (such as 15, such as 10, such as 5, such as 3, such as 1) mass %, functionalized (such as aminated) polybutene (such as polyisobutylene), such as PIBSA-PAM.

[0182] In embodiments, the concentrate may comprise acylated polymers, such as polyisobutylene succinic acid, optionally, having an Mn of 500 to 50,000 g/mol, such as 600 to 5,000 g/mol, such as 700 to 3000 g/mol. In embodiments, the concentrate may comprise acylated polymers, such as polyisobutylene succinic acid, having an Mn of 500 1600 g/mol, such as 700 to 1200 g/mol.

[0183] In embodiments, the concentrate may comprise 20 (such as 15, such as 10, such as 5, such as 3, such as 1) mass % or less block copolymer, such as block, star, random, and/or tapered block copolymer.

[0184] In embodiments, the concentrate may be substantially free of or absent block copolymer, such as block, star, random, and/or tapered block copolymer.

[0185] In embodiments, the concentrate may comprise 20 mass % or less (such as 15 mass % or less, such as 10 mass % or less, such as 5 mass % or less, such as 3 mass % or less, such as 1) mass % or less styrenic copolymer, such as block, star, random, and/or tapered styrenic block copolymer).

[0186] In embodiments, the concentrate may be substantially free of or absent styrenic copolymer, such as block, star, random, and/or tapered sytrenic block copolymer).

[0187] In embodiments, the concentrate may comprise less than 20 (such as less than 15, such as 10, such as less than 5, such as less than 3, such as 1) mass % of functionalized diluent, such as functionalized oil.

[0188] In embodiments, the concentrate may substantially free of or absent functionalized diluent, such as functionalized oil.

[0189] In embodiments, the concentrate may comprise less than 0.5 (such as less than 0.4, such as less than 0.3, such as less than 0.2, such as 0.1, substantially absent) wt %, based upon the weight of the concentrate, of secondary hydrocarbyl amine compounds and tertiary hydrocarbyl amine compounds.

[0190] In embodiments, the concentrate may be substantially absent, or may comprise no secondary hydrocarbyl amine compounds and tertiary hydrocarbyl amine compounds.

[0191] In embodiments, the concentrate may have a kinematic viscosity at 100 C. of less than 1000 cSt, such as less than 500 cSt, such as less than 200 cSt.

[0192] In embodiments, the concentrate including the one or more of the functionalized polymers may further include a non-ionic fatty alcohol ethoxylate at from 1.0 to 20 wt. % of the one or more functionalized polymers.

[0193] This disclosure relates to methods of making concentrate compositions comprising combining: from 1 to less than or equal to 50 wt. % of one or more base oils; from 2 to 40 wt. % of an overbased calcium salicylate detergent, an overbased magnesium salicylate detergent, an overbased mixed calcium and magnesium salicylate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500; and from 2 to 40 wt. % of one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more), and one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol).

[0194] In an alternative form, the method of making concentrate compositions comprises combining: from 1 to less than or equal to 50 wt. % of one or more base oils; from 2 to 40 wt. % of an overbased calcium sulfonate detergent, an overbased magnesium sulfonate detergent, an overbased mixed calcium and magnesium sulfonate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500; from 2 to 40 wt. % of one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more), and one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol); and from 0.5 to 10 wt. % of one or more organic friction modifier.

Lubricating Oil Composition Components and Concentrate Components

A. Base Oil Component

[0195] The base oil (also referred to as base stock, lubricating oil basestock, or oil of lubricating viscosity) used herein may be a single oil or a blend of oils, and is typically a large liquid constituent of a lubricating composition, also referred to as a lubricant, into which additives and optional additional oils are blended, for example, to produce a lubricating composition, such as a final lubricant composition, a concentrate, or other lubricating composition.

[0196] A base oil may be selected from vegetable, animal, mineral, and synthetic lubricating oils, and mixtures thereof. It may range in viscosity from light distillate mineral oils to heavy lubricating oils, such as those for gas engine oil, mineral lubricating oil, motor vehicle oil, and heavy-duty diesel oil. Generally, the kinematic viscosity at 100 C. (KV100) of the base oil ranges from 1 to 30, such as 2 to 25 cSt, such as 5 to 20 cSt, as determined according to ASTM D445-19a, in particular, from 1.0 cSt to 10 cSt, from 1.5 cSt to 3.3 cSt, from 2.7 cSt to 8.1 cSt, from 3.0 cSt to 7.2 cSt, or from 2.5 cSt to 6.5 cSt. Generally, the high temperature high shear (HTHS) viscosity at 1500 C of the base oil ranges from 0.5 to 20 cP such as 1 to 10 cP, such as 2 to 5 cP as determined according to ASTM D4683-20.

[0197] Typically, when lubricating oil basestock(s) is used to make a concentrate, it may advantageously be present in a concentrate-forming amount to give a concentrate containing, from 5 wt % to 80 wt %, from 10 wt % to 70 wt %, or from 5 wt % to 50 wt % of active ingredient, based upon the weight of the concentrate.

[0198] Common oils useful as base oils include animal and vegetable oils (e.g., castor and lard oil), liquid petroleum oils, and hydrorefined and/or solvent-treated mineral lubricating oils of the paraffinic, naphthenic, and mixed paraffinic-naphthenic types. Oils derived from coal or shale are also useful base oils. Base stocks may be manufactured using a variety of different processes including, but not limited to, distillation, solvent refining, hydrogen processing, oligomerization, esterification, and re-refining.

[0199] Synthetic lubricating oils useful herein as base oils include hydrocarbon oils such as homopolymerized and copolymerized olefins, referred to as polyalphaolefins or PAO's or group IV base oils [according to the API EOLCS 1509 definition (American Petroleum Institute Publication 1509, see section E.1.3, 19.sup.th edition, January 2021, www.API.org)]. Examples of PAO's useful as base oils include: poly(ethylenes), copolymers of ethylene and propylene, polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes), homo- or co-polymers of C.sub.8 to C.sub.20 alkenes, homo- or co-polymers of C.sub.8, and/or C.sub.10, and/or C.sub.12 alkenes, C.sub.8/C.sub.10 copolymers, C.sub.8/C.sub.10/C.sub.12 copolymers, and C.sub.10/C.sub.12 copolymers, and the derivatives, analogues and homologues thereof.

[0200] In another embodiment, the base oil may comprise polyalphaolefins comprising oligomers of linear olefins having 6 to 14 carbon atoms, more preferably 8 to 12 carbon atoms, more preferably 10 carbon atoms having a Kinematic viscosity at 100 C. of 10 or more (as measured by ASTM D445); and preferably having a viscosity index (VI), as determined by ASTM D2270, of 100 or more, preferably 110 or more, more preferably 120 or more, more preferably 130 or more, more preferably 140 or more; and/or having a pour point of 5 C. or less (as determined by ASTM D97), more preferably 10 C. or less, more preferably 20 C. or less.

[0201] In another embodiment polyalphaolefin oligomers useful in the present disclosure may comprise C.sub.20 to C.sub.1500 paraffins, preferably C.sub.40 to C.sub.1000 paraffins, preferably C.sub.50 to C.sub.750 paraffins, preferably C.sub.50 to C.sub.500 paraffins. The PAO oligomers are dimers, trimers, tetramers, pentamers, etc., of C.sub.5 to C.sub.14 alpha-olefins in one embodiment, and C.sub.6 to C.sub.12 alpha-olefins in another embodiment, and Cs to C.sub.12 alpha-olefins in another embodiment. Suitable olefins include 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. In one embodiment, the olefin is a combination of 1-octene, 1-decene, and 1-dodecene, or alternately may be substantially 1-decene, and the PAO is a mixture of dimers, trimers, tetramers, and pentamers (and higher) thereof. Useful PAO's are described more particularly in, for example, U.S. Pat. Nos. 5,171,908 and 5,783,531, and in Synthetic Lubricants and High-Performance Functional Fluids 1-52 (Leslie R. Rudnick & Ronald L. Shubkin, ed. Marcel Dekker, Inc. 1999).

[0202] PAO's useful in the present disclosure typically possess a number average molecular weight of from 100 to 21,000 g/mol in one embodiment, and from 200 to 10,000 g/mol in another embodiment, and from 200 to 7,000 g/mol in yet another embodiment, and from 200 to 2,000 g/mol in yet another embodiment, and from 200 to 500 g/mol in yet another embodiment. Desirable PAO's are commercially available as SpectraSyn Hi-Vis, SpectraSyn Low-Vis, SpectraSyn plus, SpectraSyn Elite PAO's (ExxonMobil Chemical Company, Houston Texas) and Durasyn PAO's from Ineos Oligomers USA LLC.

[0203] Synthetic lubricating oils useful as base oils also include hydrocarbon oils such as homopolymerized and copolymerized: alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenols (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers, and alkylated diphenyl sulfides; and the derivatives, analogues, and homologues thereof.

[0204] Another suitable class of synthetic lubricating oils useful as base oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) reacted with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.

[0205] Esters useful as synthetic oils herein also include those made from C.sub.5 to C.sub.12 monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol.

[0206] Desirable ester base oils are commercially available as Esterex Esters (ExxonMobil Chemical Company, Houston, Texas).

[0207] Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic lubricants useful herein; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes, and poly(methylphenyl)-siloxanes.

[0208] Other synthetic lubricating oils useful herein include liquid esters of phosphorous-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.

[0209] Unrefined, refined, and re-refined oils can be used in the lubricating compositions of the present disclosure. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process and used without further treatment is considered an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration, and percolation are used by those in the art. Re-refined oils are oils obtained by processes similar to those used to obtain refined oils where the refining processes are applied to previously refined oils which have been previously used in service. Such re-refined oils are also referred to as reclaimed or reprocessed oils and often are additionally processed for removal of spent additive and oil breakdown products. A re-refined base oil is preferably substantially free from materials introduced through manufacturing, contamination, or previous use.

[0210] Other examples of useful base oils are gas-to-liquid (GTL) base oils, i.e., the base oil is an oil derived from hydrocarbons made from synthesis gas (syn gas) containing H2 and CO using a Fischer-Tropsch catalyst. These hydrocarbons typically require further processing in order to be useful as a base oil. For example, they may, by methods known in the art, be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed. For further information on useful GTL base oils and blends thereof, please see U.S. Pat. No. 10,913,916 (col 4, ln 62 to col 5, ln 60) and U.S. Pat. No. 10,781,397 (col 14, ln 54 to col 15, ln 5, and col 16, ln 44 to col 17, ln 55).

[0211] In particular, oils from renewable sources, i.e., based in part on carbon and energy captured from the environment, such as biological sources, are useful herein.

[0212] The various base oils are often categorized as Group I, II, III, IV, or V according to the API EOLCS 1509 definition (American Petroleum Institute Publication 1509, see section E.1.3, 22 ns edition, October 2023, www.API.org). Generally speaking, Group I base stocks have a viscosity index of between about 80 to 120 and contain greater than about 0.03% sulfur and/or less than about 90% saturates. Group II base stocks have a viscosity index of between about 80 to 120 and contain less than or equal to about 0.03% sulfur and greater than or equal to about 90% saturates. Group III base stocks have a viscosity index greater than about 120 and contain less than or equal to about 0.03% sulfur and greater than about 90% saturates. Group IV base stocks include polyalphaolefins (PAO). Group V base stocks include base stocks not included in Groups I-IV. (Viscosity index measured by ASTM D 2270, saturates is measured by ASTM D2007, and sulfur is measured by ASTM D5185, ASTM D2622, ASTM D4294, ASTM D4927, and ASTM D3120).

[0213] Base oils for use in the formulated lubricating compositions useful in the present disclosure are any one, two, three, or more of the variety of oils described herein. In desirable embodiments, base oils for use in the formulated lubricating compositions useful in the present disclosure are those described as API Group I(including Group I+), Group II (including Group II+), Group III (including Group III+), Group IV, and Group V oils and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils and mixtures thereof. The base oil may be a Group III, Group III+, IV, and Group V base oils due to their exceptional volatility, stability, viscometric, and cleanliness features. Minor quantities of Group I basestock, such as the amount used to dilute additives for blending into formulated lube oil products, can be tolerated but are typically kept to a minimum, e.g., amounts only associated with their use as diluent/carrier oil for additives used on an as-received basis. In regard to the Group II stocks, it is often more useful that the Group II base stock be in the higher quality range associated with that stock, i.e., a Group II stock having a viscosity index in the range from 100 to 120.

[0214] The base oil useful herein may be selected from any of the synthetic, natural, or re-refined oils (such as those typically used as crankcase lubricating oils for spark-ignited and compression-ignited engines). Mixtures of synthetic and/or natural and/or re-refined base oils may be used if desired. Multi-modal mixtures (such as bi- or tri-modal mixtures) of Group I, II, III, IV, and/or V base stocks may be used if desired.

[0215] The base oil or base oil blend used herein conveniently has a kinematic viscosity at 1000 C (KV100, as measured according to ASTM D445-19a, and reported in units of centistoke (cSt) or it its equivalent, mm2/s), of about 2 to about 40 cSt, alternately of 3 to 30 cSt, alternately 4 to 20 cSt at 100 C., alternately 5 to 10 cSt, alternately the base oil or base oil blend may have a kinematic viscosity at 100 C. of 2 to 20 cSt, of 2.5 to 12 cSt, and preferably of about 2.5 cSt to about 9 cSt.

[0216] The base oil or base oil blend preferably has a saturate content of at least 65 mass %, more preferably at least 75 mass %, such as at least 85 mass %, such as at least than 90 mass % as determined by ASTM D2007.

[0217] Preferably, the base oil or base oil blend will have a sulfur content of less than 1 mass %, preferably less than 0.6 mass %, most preferably less than 0.4 mass %, such as less than 0.3 mass %, based on the total mass of the lubricating composition, as measured by ASTM D5185.

[0218] In embodiments, the volatility of the base oil or base oil blend, as measured by the Noack test (ASTM D5800, procedure B), is less than or equal to 30 mass %, such as less than or equal to 25 mass %, such as less than or equal to 20 mass %, such as less than or equal to 16 mass %, such as less than or equal to 12 mass %, such as less than or equal to 10 mass %, based on the total mass of the lubricating composition.

[0219] In embodiments, the viscosity index (VI) of the base oil is at least 95, preferably at least 110, more preferably at least 120, even more preferably at least 125, most preferably from about 95 to 145, in particular from about 100 to 135 (as determined by ASTM D2270).

[0220] The base oil may be provided in a major amount, in combination with a minor amount of one or more additive components as described hereinafter, constituting a lubricant. This preparation may be accomplished by adding the additives directly to the oil or by adding the one or more additives in the form of a concentrate thereof to disperse or dissolve the additive(s). Additives may be added to the oil by any method known to those skilled in the art, either before, at the same time as, or after addition of other additives.

[0221] The base oil may be provided in a minor amount, in combination with minor amounts of one or more additive components as described hereinafter, constituting an additive concentrate. This preparation may be accomplished by adding the additives directly to the oil or by adding the one or more additives in the form of a solution, slurry or suspension thereof to disperse or dissolve the additive(s) in the oil. Additives may be added to the oil by any method known to those skilled in the art, either before, at the same time as, or after addition of other additives.

[0222] The base oil typically constitutes the major component of an engine oil lubricant composition of the present disclosure and typically is present in an amount ranging from about 50 to about 99 wt %, preferably from about 60 to about 95 wt %, preferably from about 70 to about 95 wt %, and more preferably from about 80 to about 95 wt %, based on the total weight of the composition.

[0223] Typically, one or more base oils are present in the lubricating composition in an amount of 32 wt % or more, alternately 55 wt % or more, alternately 60 wt % or more, alternately 65 wt % or more, based on the total weight of the lubricating composition. Typically, one or more base oils are present in the lubricating composition at an amount of 98 wt % or less, more preferably 95 wt % or less, even more preferably 90 wt % or less. Alternately, one or more base oils are present in the lubricating composition at from 1 to 99 mass %, alternately 50 to 97 mass %, alternately to 60 to 95 mass alternately 70 to 95 mass %, based upon the weight of the lubricating composition.

[0224] The base oils and blends thereof described above are also useful for making concentrates as well as for making lubricants therefrom.

[0225] Concentrates constitute a convenient means of handling additives before their use, as well as facilitating solution or dispersion of additives in lubricants. When preparing a lubricant that contains more than one type of additive (sometime referred to as additive components), each additive may be incorporated separately, each in the form of a concentrate. In many instances, however, it is convenient to provide a so-called additive package (also referred to as an addpack) comprising one or more additives/co-additives, such as described hereinafter, in a single concentrate.

[0226] Typically, one or more base oils are present in the concentrate composition in an amount of 50 wt % or less, alternately 40 wt % or less, alternately 30 wt % or less, alternately 20 wt % or less, based on the total weight of the concentrate composition. Typically, one or more base oils are present in the concentrate composition at an amount of 0.1 to 49 mass %, alternately 1 to 40 mass %, alternately 5 to 40 mass %, alternately to 10 to 30 mass %, alternately 15 to 25 mass %, based upon the weight of the concentrate composition.

[0227] In one form of the lubricating oil compositions disclosed herein, the compositions may comprise a Group I, Group II base oil, a Group III base oil, a Group IV base oil (preferably a Group II base oil, a Group III base oil, a Group IV base oil), or combinations thereof. In another form of the lubricating oil compositions disclosed herein, the compositions may comprise a Group II base oil, and is substantially free of the Group III base oil and the Group IV base oil.

B. Functionalized Polymer Component

i. F-OCP Functionalized Polymers

[0228] This disclosure relates to a functionalized polymer comprising a polymer that prior to functionalization has an Mn of about 10,000 g/mol or more, such as 20,000 g/mol or more, such as 25,000 g/mol or more, such as 30,000 g/mol or more, such as 35,000 g/mol or more (GPC-PS). Alternately, functionalized polymer comprises a polymer that prior to functionalization has an Mn of 10,000 to 300,000 g/mol, such as 20,000 to about 150,000 g/mol, such as 30,000 to about 125,000 g/mol, such as 35,000 to about 100,000 g/mol, such as 40,000 to 80,000 g/mol (GPC-PS). The polymer prior to functionalization may have an Mw/Mn of less than 2 (such as less than 1.6, such as less than 1.5, such as 1.4 or less, such as from 1 to 1.3, such as from 1.0 to 1.25, such as from 1.0 to 1.2, such as 1.0 to 1.15, such as from 1.0 to 1.1 as determined by GPC-PS). The polymer prior to functionalization may comprise repeat units of one or more olefins having 4 to 5 carbon atoms (preferably conjugated dienes having 4 to 5 carbon atoms) or comprise one or more C.sub.2 to C.sub.20 (such as C.sub.2 to C.sub.12, cush as C.sub.2 to C.sub.6) linear alpha olefins (such as ethylene and or propylene). Prior to functionalization the polymer (such as a C.sub.4-5 polymer or a copolymer of ethylene and or propylene) is preferably fully or partially saturated (such as fully or partially hydrogenated). The functionalized polymer may be obtained by reacting the polymer with an acylating agent to form acylated polymer and then reacting acylated polymer with an amine or alcohol to form an amide, imide, ester, or combination thereof. The functionalized polymer may also be obtained by reacting an acylated polymer (such as a commercially available maleated fully or partially hydrogenated C.sub.4-5 polymer, or a maleated olefin copolymer of ethylene and propylene) with an amine to form an amide, imide or combination thereof.

[0229] This disclosure further relates to amide, imide, and/or ester functionalized saturated (such as hydrogenated) polymers of C.sub.4-5 conjugated dienes described herein obtained by reacting fully or partially saturated (such as fully or partially hydrogenated) polymers of C.sub.4-5 conjugated dienes having an Mw/Mn of less than 2, with an acylating agent, such as maleic acid or maleic anhydride and thereafter reacting the acylated polymer with an amine (such as a polyamine) to form an imide, amide or combination thereof.

[0230] This disclosure further relates to amide, imide, and/or ester functionalized saturated (such as hydrogenated) polymers of C.sub.2 to C.sub.20 alpha olefins (such as C.sub.2 to C.sub.12 linear alpha olefins, such as ethylene and propylene homopolymers and copolymers) described herein obtained by reacting fully or partially saturated (such as fully or partially hydrogenated) polymers of C.sub.2-20 alpha olefins having an Mw/Mn of less than 3 (preferably less than 2), with an acylating agent, such as maleic acid or maleic anhydride and thereafter reacting the acylated polymer with an amine (such as a polyamine) to form an imide, amide or combination thereof.

[0231] This disclosure relates to polymers containing one or more pendant amine groups and comprising or resulting from the admixing of: at least partially (preferably completely) hydrogenated C.sub.4-5 olefin polymers and or C.sub.2-20 polymers (such as copolymers of ethylene and propylene) with an acylating agent, such as maleic acid or maleic anhydride, and thereafter reacting the acylated polymer with a polyamine to form an imide, amide or combination thereof.

[0232] In embodiments, the functionalized polymer is not prepared in aromatic solvent (such as benzene or toluene), or aromatic solvent is present at 2 wt % or less (such as 1 wt % or less, such as 0.5 wt % or less), based upon the weight of solvent, diluent, and polymer.

[0233] In embodiments, the functionalized polymer is not prepared in an alkylated naphthylenic solvent, or alkylated naphthylenic solvent is present at 5 wt % or less (such as 3 wt % or less, such as 1 wt % or less), based upon the weight of solvent, diluent, and polymer.

[0234] In embodiments, the polymer useful herein to prepare the functionalized polymer may be a homopolymer of a C.sub.2 to C.sub.20 alpha olefin (such as a homopolymer or copolymer of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and the like, such as a copolymer of ethylene and propylene).

[0235] The polymer useful herein to prepare the functionalized polymer may be a homopolymer of butadiene, isoprene, or the like.

[0236] In embodiments, the polymer useful herein to prepare the functionalized polymer may be a homopolymer of isoprene, or a copolymer of isoprene and less than 5 mol % (such as less than 3 mol %, such as less than 1 mol %, such as less than 0.1 mol %) comonomer.

[0237] The polymer useful herein to prepare the functionalized polymer may be copolymer of isoprene and one or more of styrene, methyl-styrene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3 pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene, 2-p-tolyl-1,3-butadiene 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene, and 3,5-decadiene, [optionally the comonomer(s) are present at less than 20 mol %, less than 5 mol %, such as less than 3 mol %, such as less than 1 mol %, such as less than 0.1 mol %].

[0238] Generally, the polymerized conjugated diene polymer useful herein to prepare the functionalized polymer includes a mixture of 1,4- and 1,2-insertions (a.k.a. 2,1-insertions; forbutadiene, 1,2-insertions are the same as 3,4-insertions). As measured by 1H NMR, the polymerized conjugated diene polymer useful herein to prepare the functionalized polymer contains at least about 50% of 1,4-insertions, such as at least about 75% of 1,4 insertions, such as at least about 80% of 1,4 insertions, such as at least about 90% of 1,4 insertions, such as at least about 95% of 1,4 insertions, such as at least 98% of 1,4 insertions, based upon the total of the 2,1 insertions, 1,4 insertions, and 3,4 insertions of isoprene. For purposes of this disclosure: 1) the phrase 1,4 insertion includes 1,4 and 4,1 insertions, 2) the phrase 2,1 insertion includes 2,1 and 1,2 insertions, and 3) the phrase 3,4 insertion includes 3,4 and 4,3 insertions.

[0239] Optionally, styrene repeat units may be absent in the polymer useful herein to prepare the functionalized polymer. Optionally, styrene repeat units may be absent in the functionalized hydrogenated/saturated polymers.

[0240] Optionally, butadiene repeat units may be absent in the polymer useful herein to prepare the functionalized polymer. Optionally, butadiene repeat units may be absent in the functionalized hydrogenated/saturated polymers.

[0241] Optionally, the polymer useful herein to prepare the functionalized polymer may be not homopolybutylene. Optionally, the functionalized hydrogenated/saturated polymer may be not homopolybutylene.

[0242] Optionally, the polymer useful herein to prepare the functionalized polymer may be not homopolyisobutylene. Optionally, the functionalized hydrogenated/saturated polymer may be not homopolyisobutylene.

[0243] Optionally, the polymer useful herein to prepare the functionalized polymer may not be a copolymer of isoprene and butadiene. Optionally, the functionalized hydrogenated/saturated polymer may not be a copolymer of isoprene and butadiene.

[0244] The polymer useful herein to prepare the functionalized polymer may be copolymer of C.sub.2 to C.sub.20 alpha olefin, such as C.sub.2 to C.sub.12 alpha olefin (such as a homopolymer or copolymer of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and the like, such as a copolymer of ethylene and propylene).

[0245] The polymer useful herein to prepare the functionalized polymer and/or the functionalized polymer may be homopolymer or copolymer. The copolymer may be a random copolymer, a tapered block copolymer, a star copolymer, or a block copolymer. Block copolymers are formed from a monomer mixture comprising one or more first monomers (such as isobutylene), wherein, for example, a first monomer forms a discrete block of the polymer joined to a second discrete block of the polymer formed from a second monomer (such as butadiene). While block copolymers have substantially discrete blocks formed from the monomers, a tapered block copolymer may be composed of, at one end, a relatively pure first monomer and, at the other end, a relatively pure second monomer. The middle of the tapered block copolymer may be more of a gradient composition of the two monomers.

[0246] The polymer useful herein to prepare the functionalized polymer may typically have an Mn of 10,000 to 150,000 g/mol, alternately 20,000 to 150,000 g/mol, alternately 20,000 to about 150,000 g/mol, alternately 30,000 to about 125,000 g/mol, alternately 35,000 to about 100,000 g/mol, alternately 40,000 to 80,000 g/mol (GPC-PS).

[0247] Polymers useful herein to prepare the functionalized polymers may typically have an Mw/Mn (as determined by GPC-PS) of 1 to 2, alternately greater than 1 to less than 2, alternately 1.1 to 1.8, alternately 1.2 to 1.5. Alternately, the polymers useful herein to prepare the functionalized polymers may typically have an Mw/Mn of 1 or greater than 1 to less than 2 (such as less than 1.8, such as less than 1.7, such as less than 1.6, such as less than 1.5, such as less than 1.4, such as less than 1.3, such as less than 1.2, such as less than 1.15, such as less than 1.12, such as less than 1.10).

[0248] The polymers used to prepare the functionalized polymers may have an Mz (as determined by GPC-PS) of 20,000 to 150,000 g/mol, alternately 20,000 to about 150,000 g/mol, alternately 30,000 to about 125,000 g/mol, alternately 35,000 to about 100,000 g/mol, alternately 40,000 to 80,000 g/mol, alternately 40,000 to 60,000 g/mol (GPC-PS).

[0249] Polymers useful herein to prepare the functionalized polymers may have a glass transition temperature (Tg) of 25 C. or less, such as 40 C. or less, such as 50 C. or less, as determined by Differential Scanning calorimetry (DSC) using a Perkin Elmer or TA Instrument Thermal Analysis System (sample is heated from ambient to 2100 C at 100 C/minute and held at 210 C. for 5 minutes, then cooled down to 40 C. at 10 C./minute and held for 5 minutes.)

[0250] Polymers useful herein to prepare the functionalized polymers typically have a residual unsaturation of less than 3%, such less than 2%, such less than 1%, such as less than 0.5%, such as less than 0.25% based upon number of double bonds in the non-hydrogenated polymer.

[0251] Polymers useful herein to prepare the functionalized polymers typically have a residual metal (such as Li, Co, and Al) content of less than 100 ppm, such less than 50 ppm, such as less than 25 ppm, such as less than 10 ppm, such as less than 5 ppm.

Hydrogenation

[0252] The C.sub.4-5 polymers and or C.sub.2-20 linear alpha olefin polymers useful herein to prepare the functionalized polymer can be hydrogenated partially or completely by any hydrogenating agent known to one of ordinary skill in the art. For example, a saturated or partially saturated polymer can be prepared by (a) providing a C.sub.4-5 polymer and or a C.sub.2-20 linear alpha olefin polymer containing unsaturations (such as double or triple bonds); and (b) hydrogenating at least a portion or all of the unsaturations (such as double or triple bonds) in the polymer in the presence of a hydrogenation reagent. In some embodiments, the polymer is fully hydrogenated. In some embodiments, the polymer is partially hydrogenated. In some embodiments, the polymer is saturated (hydrogenated) at 50% or more, such as 60% or more, such as 70% or more, such as 80% or more, such as 90% or more, such as 95% or more, such as 98% or more, such as 99% or more, such as from 50 to 100% saturated (hydrogenated), as determined by ozone adsorption method described in Martino N. Smits and Dirkman Hoefman, Quantative Determination of Olefinic Unsaturation by Measurement of Ozone Absorption Analytical Chemistry Vol 44, No. 9, pg. 1688, 1972, Martino N. Smits.

[0253] In embodiments, the hydrogenation reagent can be hydrogen in the presence of a hydrogenation catalyst. In some embodiments, the hydrogenation catalyst is Pd, Pd/C, Pt, PtO.sub.2, Ru(PPh.sub.3).sub.2Cl.sub.2, Raney nickel, or a combination thereof. In embodiments, the catalyst is a Pd catalyst. In another embodiment, the catalyst is 5% Pd/C. In a further embodiment, the catalyst may comprise or be 10% Pd/C in a high-pressure reaction vessel and the hydrogenation reaction is allowed to proceed until completion. Generally, after completion, the reaction mixture can be washed, concentrated, and dried to yield the corresponding hydrogenated product. Alternatively, any reducing agent that can reduce a CC double bond to a CC single bond can also be used. For example, the olefin polymer can be hydrogenated by treatment with hydrazine in the presence of a catalyst, such as 5-ethyl-3-methyllumiflavinium perchlorate, under an oxygen atmosphere to give the corresponding hydrogenated products. The reduction reaction with hydrazine is disclosed in Imada et al., J Am. Chem. Soc., 127, pp. 14544-14545, (2005), which is incorporated herein by reference.

Acylation

[0254] The fully or partially saturated (hydrogenated) polymer may be chemically modified (functionalized) to provide a polymer having at least one polar functional group, such as, but not limited to, halogen, epoxy, hydroxy, amino, nitrilo, mercapto, imido, carboxy, and sulfonic acid groups of combinations thereof. The functionalized polymers can be further modified to give a more desired type of functionality. In a preferred case, the fully or partially hydrogenated polymer is functionalized by a method, which includes reacting the fully or partially hydrogenated polymer with an unsaturated carboxylic acid (or derivative thereof, such as maleic anhydride) to provide an acylated polymer (which may then be further functionalized as described below).

[0255] In some embodiments, a carboxylic acid functionality or a reactive equivalent thereof is grafted onto the polymer to form an acylated polymer. An ethylenically unsaturated carboxylic acid material is typically grafted onto the polymer backbone. These materials which are attached to the polymer typically contain at least one ethylenic bond (prior to reaction) and at least one, such as two, carboxylic acid (or its anhydride) groups or a polar group which is convertible into said carboxyl groups by oxidation or hydrolysis. Maleic anhydride or a derivative thereof is suitable. It grafts onto the polymer, to give two carboxylic acid functionalities. Examples of additional unsaturated carboxylic materials include itaconic anhydride, or the corresponding dicarboxylic acids, such as maleic acid, fumaric acid and their esters, as well as cinnamic acid and esters thereof.

[0256] The ethylenically unsaturated carboxylic acid material may be grafted onto the polymer in a number of ways. It may be grafted onto the polymer in solution or in essentially pure (molten) form with or without using a radical initiator. Free-radical induced grafting of ethylenically unsaturated carboxylic acid materials may also be conducted in solvents, such as hexane or mineral oil. It may be carried out at an elevated temperature in the range of 100 C. to 250 C., e.g., 120 C. to 190 C., or 150 C. to 180 C., e.g., above 160 C.

[0257] The free-radical initiators which may be used include peroxides, hydroperoxides, and azo compounds, typically those which have a boiling point greater than about 1000 C and which decompose thermally within the grafting temperature range to provide free radicals. Representative of these free-radical initiators include azobisisobutyronitrile and 2,5-dimethyl-hex-3-yne-2,5-bis-tertiary-butyl peroxide. The initiator may be used in an amount of 0.005% to 1% by weight based on the weight of the reaction mixture solution. The grafting may be carried out in an inert atmosphere, such as under nitrogen blanketing. The resulting acylated polymer intermediate is characterized by having carboxylic acid acylating functions as a part of its structure.

[0258] In embodiments, the acylated polymer may have 2 or more anhydride groups per polymer molecule and may exhibit less than 10% gel. Alternately, the acylated polymer may have less than 2 anhydride groups per polymer molecule and may exhibit less than 10% gel. (See also col 17, ln 14-col 18, ln 11 of U.S. Pat. No. 5,429,758).

[0259] Alternately, in some embodiments, the acylated polymer may have a gel content of less than about 5 wt %, less than 3 wt %, less than 2 wt %, less than 1 wt %, less than 0.5 wt %, less than 0.1 wt %, or 0 wt %, where the gel content is measured by determining the amount of material that is extractable from the polymer by using boiling xylene (or cyclohexane) as an extractant. The percent of soluble and insoluble (gel) material in a polymer composition is determined by soaking a nominally 0.5 mm thick thin film specimen of polymer for 48 hours in cyclohexane at 230 C or refluxing the thin film specimen in boiling xylene for one half hour, removing the solvent, weighing the dried residue and calculating the amount of soluble and insoluble (gel) material. This method is generally described in U.S. Pat. No. 4,311,628, which is incorporated herein by reference. For purposes of this disclosure, gel content is measured using boiling xylene, unless the sample is not soluble in xylene, then the cyclohexane method is used.

[0260] In embodiments, the acylated polymer may have a Saponification Number (SAP) of 5 g/KOH or more, such as 10 g/KOH or more, such as 20 g/KOH or more, such as 30 g/KOH or more, such as 50 g/KOH or more, such as 10 to 60 g/KOH, such as 20 to 40 g/KOH as determined by ASTM D94.

[0261] In embodiments, the acylated polymer composition may have less than 5 wt % unreacted acylating agent (such as maleic anhydride), such as less than 4 wt %, such as less than 3 wt %, such as less than 1 wt %, such as less than 0.5 wt %, such as less than 0.25 wt %, such as less than 0.1 wt %, based upon the weight of the acylated polymer composition (i.e., polymer, acylating agent, and diluent).

[0262] In embodiments, the acylation reactions described herein may take place in base oil diluent. As a side product, functionalized base oil can be produced. The oil may become acylated itself. For example, maleated base oil may be present after the acylation reactions described herein.

[0263] It is contemplated that the functionalized base oil may comprise the acylated oil and/or the reaction product of the acylated oil with an amine to form an amide, imide or combination thereof.

[0264] Preferably, the acylated oil and/or reaction product of the acylated oil with an amine or alcohol to form an amide, imide, ester, or combination thereof, may be present in a concentrate in an amount of 40 wt % or less, alternately 20 wt % or less, alternately 10 wt % or less, alternately 5 wt % or less, alternately 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably at 0.1 mass % or less, preferably at 0 mass % (such as 0 to 40 mass %, alternately 0.01 to 40 mass %, alternately 0.1 to 20 mass %, alternately to 1 to 10 mass %, alternately 1.5 to 5 mass %), based upon the weight of the concentrate composition.

[0265] Preferably one or more functionalized base oils, such as acylated oil and/or reaction product of the acylated oil with an amine or alcohol to form an amide, imide, ester, or combination thereof, may be present in the lubricating oil composition at an amount of 0.01 to 40 mass %, alternately 0.1 to 20 mass %, alternately to 1 to 10 mass %, alternately 1.5 to 5 mass %, (such as at 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably at 0.1 mass % or less, preferably at 0 mass %), based upon the weight of the lubricating oil composition.

[0266] In embodiments, the acylation reactions described herein take place in solvent containing media. As a side product, acylated/functionalized solvent can be produced. In embodiments, acylated and/or functionalized solvent may be present in a concentrate composition at 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably at 0.1 mass % or less, preferably at 0 mass %, based upon the weight of the concentrate composition. In embodiments, functionalized solvent may be present in a lubricating oil composition at 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably at 0.1 mass % or less, preferably at 0 mass %, based upon the weight of the lubricating oil composition.

[0267] In embodiments, the acylating agent maybe added in such away as to minimize side reactions (such as reaction with base oil or other diluent present in the reaction vessel).

[0268] In embodiments, the acylating reaction may occur where the acylating agent (such as maleic acid or maleic anhydride) is added in a continuous or semi-continuous (such as intermittent) stream (such as, for example, in controlled relatively equal portions over the reaction time, or larger and/or smaller portions at different points in the reaction) to minimize functionalized base oil and other side reactions. As an example, the acylating agent may be added in a continuous fashion where the amounts of polymer and acylating agents are added in controlled stoichiometric amounts. As another example, the polymer may be added to a reaction vessel in batch fashion and the acylating agent added slowly or in a semi-continuous fashion (such as adding the acylating agent in 2 or more, such as 5 or more, such as 10 or more, such as 20 or more, such as 30 or more, such as 40 or more, such as 50 or more, such as 60 or more discrete amounts or portions). Alternately, the polymer can be added to the reaction vessel in X number of portions and the acylating agent added in 1.5 or more (such as 2 or more, such as 5 or more, such as 10 or more, such as 20 or more, such as 30 or more, such as 40 or more, such as 50 or more, such as 60 or more) number of portions. This same effect may also be achieved by diluting or concentrating a polymer solution and/or the acylating agent solution to the same or different extents.

[0269] Preferably, the acylating agent may be added in such a way as to minimize side reactions, such as in a continuous or semi-continuous fashion.

[0270] The reaction may also be run so as to minimize side reactions by using high concentrations of the polymer in diluent, such as 45 wt % or more, or 50 wt % or more, or 55 wt % or more, or 60 wt % or more in batch, semi-continuous, or continuous reactor operations. For example, the polymer (such as a hydrogenated isoprene polymer, such as hydrogenated homo-polyisoprene) may be introduced into batch, semi-continuous, or continuous reactor operations as solution or suspension (such as a slurry) in diluent (such as oil (e.g., base oil, such as a Group I, II, III, IV, and/or V base oil, such as a Group II and/or Group III base oil) or alkane solvent or diluent or a combination thereof), where the polymer may be present in the solution or suspension at 45 wt % or more (or 50 wt % or more, or 55 wt % or more, or 60 wt % or more), based upon the weight of the polymer and diluent.

[0271] In embodiments, the side reactions may be minimized by: 1) adding the acylating agent in a continuous or semi-continuous fashion, and/or 2) the polymer is introduced into batch, semi-continuous or continuous reactor operations as solution or suspension in diluent where the polymer is present at 45 wt % or more, based upon the weight of the polymer and diluent.

[0272] In embodiments, side reactions are minimized, optionally by adding the acylating agent in a continuous or semi-continuous fashion, and/or by introducing the fully or partially hydrogenated polymer (such as isoprene polymer) into batch, semi-continuous, or continuous reactor operations as solution or suspension in diluent, said solution or suspension comprising 45 wt % or more (or 50 wt % or more, or 55 wt % or more, or 60 wt % or more), of the fully or partially hydrogenated polymer, based upon the weight of the fully or partially hydrogenated polymer and diluent.

[0273] In embodiments, side reactions are minimized, optionally by adding the acylating agent in a continuous or semi-continuous fashion, and by introducing the fully or partially hydrogenated polymer (such as isoprene polymer) into batch, semi-continuous, or continuous reactor operations as solution or suspension in diluent, said solution or suspension comprising 45 wt % or more (or 50 wt % or more, or 55 wt % or more, or 60 wt % or more), of the fully or partially hydrogenated polymer, based upon the weight of the fully or partially hydrogenated polymer and diluent.

Functionalization

[0274] In embodiments, the acylated polymer may be reacted with an alcohol or an amine to form an amide, imide, ester or combinations thereof. The reaction may consist of condensation to form an imide, an amide, a half-amide, amide-ester, diester, or an amine salt. A primary amino group will typically condense to form an amide or, in the case of maleic anhydride, an imide. It is noted the amine may have a single primary amino group or multiple primary amino groups.

[0275] Suitable amines may include one or more aromatic amines, such as amines wherein a carbon atom of the aromatic ring structure is attached directly to the amino nitrogen. The amine may also be aliphatic. In embodiments aliphatic amines can be used alone or in combination with each other or in combination with aromatic amines. The amount of aromatic amine may, in some embodiments, be a major or minor amount compared with the amount of the non-aromatic amines, or in some instances, the composition may be substantially free of aromatic amine. Alternately, the composition may be substantially free of aliphatic amine.

[0276] Examples of aromatic amines which may be used herein include one or more N-arylphenylenediamine(s) represented by the formula:

##STR00001##

wherein R.sub.7 is H, NHaryl, NHalkaryl, or a branched or straight chain hydrocarbyl radical having from about 4 to about 24 carbon atoms selected from alkyl, alkenyl, alkoxyl, aralkyl or alkaryl; R.sub.9 is NH.sub.2, (NH(CH.sub.2).sub.n).sub.mNH.sub.2, NHalkyl, NHaralkyl, CH.sub.2-aryl-NH.sub.2, in which n and m each have a value from about 1 to about 10; and R.sub.8 is hydrogen, or alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl, having from about 4 to about 24 carbon atoms.

[0277] Suitable N-arylphenylenediamines include N-phenylphenylenediamines (NPPDA), for example, N-phenyl-4,4-phenylenediamine, N-phenyl-1,3-phenylenediamine, and N-phenyl-1,2-phenylenediamine and N-naphthyl-1,4-phenylenediamine. Other derivatives of NPPDA may also be included, such as N-propyl-N-phenylphenylenediamine.

[0278] In embodiments, the amine reacted with the acylated polymer is an amine having at least 3 or 4 aromatic groups and may be represented by the following formula:

##STR00002##

wherein independently each variable, R.sup.1 may be hydrogen or a C.sub.1 to C.sub.5 alkyl group (typically hydrogen); R.sup.2 may be hydrogen or a C.sub.1 to C.sub.5 alkyl group (typically hydrogen); U may be an aliphatic, alicyclic or aromatic group, with the proviso that when U is aliphatic, the aliphatic group may be linear or branched alkylene group containing 1 to 5, or 1 to 2 carbon atoms; and w may be 1 to 10, or 1 to 4, or 1 to 2 (typically 1).

[0279] Other examples of aromatic amines include aniline, N-alkylanilines such as N-methyl aniline, and N-butylaniline, di-(para-methylphenyl)amine, naphthylamine, 4-aminodiphenylamine, N,N-dimethylphenylenediamine, 4-(4-nitro-phenylazo)aniline (disperse orange 3), sulfamethazine, 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetanilide, 4-amino-2-hydroxy-benzoic acid phenyl ester (phenyl amino salicylate), N-(4-amino-5-methoxy-2-methyl-phenyl)-benzamide (fast violet B), N-(4-amino-2,5-dimethoxy-phenyl)-benzamide (fast blue RR), N-(4-amino-2,5-diethoxy-phenyl)-benzamide (fast blue BB), N-(4-amino-phenyl)-benzamide and 4-phenylazoaniline. Suitable amines are referenced in U.S. Pat. No. 7,790,661 and are hereby incorporated by reference.

[0280] In embodiments, the compound condensing with the acylated polymer can be represented by the following formulas:

##STR00003##

wherein X is an alkylene group containing about 1 to about 4 carbon atoms; R.sup.2, R.sup.3 and R.sup.4 are hydrocarbyl groups.

##STR00004##

wherein X is an alkylene group containing about 1 to about 4 carbon atoms; R.sup.3 and R.sup.4 are hydrocarbyl groups.

[0281] Alternately, the amine may be an amine having at least 4 aromatic groups and an aldehyde (such as formaldehyde). The aromatic amine may be represented by formula:

##STR00005##

wherein, R.sup.1 is hydrogen or a C alkyl group (typically hydrogen); R.sup.2 is hydrogen or a C.sub.1-5 alkyl group (typically hydrogen); U is an aliphatic, alicyclic or aromatic group, optionally with the proviso that when U is aliphatic, the aliphatic group may be linear or branched alkylene group containing 1, 2, 3, 4, or 5, or 1 to 2 carbon atoms; and w is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, such as 0, 1, 2, or 3 or 0 or 1 (typically 0). For further information on such amines see, e.g., US 2017/0073606, page 5 paragraph [0064]-[0070] and European Patent No, 2 401 348.

[0282] Examples of compounds capable of condensing with the acylating agent and further having a tertiary amino group can include but are not limited to: dimethylaminopropylamine, N,N-dimethyl-aminopropy-lamine, N,N-diethyl-aminopropylamine, N,N-dimethyl-ami-noethylamine ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, the isomeric butylenediamines, pentanediamines, hexanediamines, heptanediamines, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetraamine, tetraethylene pentaamine, pentaethylenehexaamine, hexamethylenetetramine, and bis(hexamethylene) triamine, the diaminobenzenes, the diaminopyridines or mixtures thereof. The compounds capable of condensing with the acylating agent and further having a tertiary amino group can further include aminoalkyl substituted heterocyclic compounds such as 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-di-amino-N-methyldipropylamine, 3,3-aminobis(N,N-dimethylpropylamine). Another example of compounds capable of condensing with the acylating agent and having a tertiary amino group include alkanolamines including, but not limited to, triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-di-ethylaminopropanol, N,N-diethylaminobutanol, N,N,N-tris (hydroxyethyl)amine, N,N,N-tris(hydroxymethyl)amine.

[0283] In embodiments, the polymer may be reacted with a polyether aromatic compound. Typically, the polyether aromatic compound will have at least two functional groups, each capable of reacting with a monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester thereof, or mixtures thereof. In embodiments, the polyether aromatic compound is derived from an aromatic compound containing at least one amine group and wherein the poly ether is capable of reacting with a monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester thereof.

[0284] Examples of suitable polyether aromatic amines include compounds having the following structure:

##STR00006##

in which A represents an aromatic aminic moiety wherein the ether groups are linked through at least one amine group on the aromatic moiety; R.sub.1 and R.sub.6 are independently hydrogen, alkyl, alkaryl, aralkyl, or aryl or mixtures thereof; R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are independently hydrogen or alkyl containing from about 1 to about 6 carbon atoms of mixtures thereof; and a and x are independently integers from about 1 to about 50.

[0285] The acylated polymer may be reacted with a polyether amine or polyether polyamine. Typical polyether amine compounds contain at least one ether unit and are chain terminated with at least one amine moiety. The polyether polyamines can be based on polymers derived from C.sub.2-C.sub.6 epoxides such as ethylene oxide, propylene oxide, and butylene oxide. Examples of polyether polyamines are sold under the Jeffamine brand and are commercially available from Huntsman Corporation.

[0286] Amines useful herein for combination with the acylated polymer include one or more of: N-phenyldiamines (such as N-phenyl-1,4-phenylenediamine, N-phenyl-p-phenylenediamine (a.k.a. 4-amino-diphenylamine, ADPA), N-phenyl-1,3-phenylenediamine, N-phenyl-1,2-phenylenediamine), nitroaniline (such as 3-nitroaniline), N-phenylethane-diamine (such as N1-phenylethane-1,2-diamine), N-aminophenylacetamide (such as N-(4-aminophenyl)acetamide), morpholinopropanamine (such as 3-morpholinopropan-1-amine), and aminoethylpiperazine (such as 1-(2-aminoethyl)piperazine).

[0287] In embodiments, the functionalization (such as amination) reactions described herein may take place in diluent (such as base oil or alkane solvent). As a side product, functionalized diluent (such as functionalized base oil) can be produced. It is contemplated that the functionalized diluent (such as functionalized base oil) may comprise reaction product of the acylated diluent (such as acylated base oil) with an amine to form an amide, imide or combination thereof.

[0288] Preferably, the reaction product of the acylated diluent (such as acylated oil) with an amine or alcohol to form an amide, imide, ester, or combination thereof, may be present in a concentrate in an amount of 40 wt % or less, alternately 20 wt % or less, alternately 10 wt % or less, alternately 5 wt % or less, alternately 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably at 0.1 mass % or less, preferably at 0 mass % (such as 0 to 40 mass %, alternately 0.01 to 40 mass %, alternately 0.1 to 20 mass %, alternately to 1 to 10 mass %, alternately 1.5 to 5 mass %), based upon the weight of the concentrate composition.

[0289] Preferably one or more functionalized base oils, such as the reaction product of the acylated diluent (such as acylated base oil) with an amine or alcohol to form an amide, imide, ester, or combination thereof, may be present in the lubricating oil composition at an amount of 0.01 to 40 mass %, alternately 0.1 to 20 mass %, alternately to 1 to 10 mass %, alternately 1.5 to 5 mass %, (such as at 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably at 0.1 mass % or less, preferably at 0 mass %), based upon the weight of the lubricating oil composition.

[0290] In embodiments, the functionalization (such as amination) reactions described herein may take place in solvent-containing media. As a side product, functionalized solvent can be produced. In embodiments, the functionalized solvent may be present in a concentrate composition at 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably at 0.1 mass % or less, preferably at 0 mass %, based upon the weight of the concentrate composition. In embodiments, functionalized solvent may be present in a lubricating oil composition at 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably at 0.1 mass % or less, preferably at 0 mass %, based upon the weight of the lubricating oil composition.

[0291] In embodiments, the acylated base oil/solvent may be removed prior to functionalization.

ii. Conjugated Diene Functionalized Polymer

[0292] The functionalized polymer may be a homopolymer of C.sub.4 or C.sub.5 olefins, such as butadiene and isoprene.

[0293] In embodiments, the functionalized polymer may be a homopolymer of isoprene, or a copolymer of isoprene and less than 5 mol % (such as less than 3 mol %, such as less than 1 mol %, such as less than 0.1 mol %) comonomer.

[0294] The functionalized polymer may comprise or be a copolymer of isoprene and one or more of styrene, methyl-styrene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3 pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene, 2-p-tolyl-1,3-butadiene 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene, and 3,5-decadiene, (optionally the comonomer(s) are present at less than 20 mol %, less than 5 mol %, such as less than 3 mol %, such as less than 1 mol %, such as less than 0.1 mol %)

[0295] In embodiments, the functionalized polymer comprises 10 (such as 9, such as 8, such as 7, such as 6, such as 5, such as 4, such as 3, such as 2, such as 1) wt %, or less, based upon the weight of the functionalized polymer, of styrene monomer.

[0296] In embodiments, styrene repeat units may be absent in the functionalized polymer.

[0297] In embodiments, the functionalized polymer may be a block or tapered block copolymer that does not comprise a styrene block.

[0298] In embodiments, the functionalized polymer may be a block or tapered block copolymer comprising (or consisting of or consisting essentially of) isoprene.

[0299] In embodiments, the functionalized polymer may be a block or tapered block copolymer comprising 50 wt % or more isoprene, based upon the weight of the copolymer.

[0300] In embodiments, the functionalized polymer may be a block or tapered block copolymer comprising (or consisting of or consisting essentially of) C.sub.4-5 conjugated diene, preferably comprising 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) wt % or more C.sub.4-5 conjugated diene, based upon the weight of the copolymer.

[0301] In embodiments, the functionalized polymer may be a copolymer comprising 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) wt % or more isoprene, based upon the weight of the copolymer.

[0302] In embodiments, the functionalized polymer may be a copolymer comprising 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) wt % or more butadiene, based upon the weight of the copolymer.

[0303] In embodiments, the functionalized polymer may be a copolymer comprising 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) wt % or more butadiene and isoprene, based upon the weight of the copolymer.

[0304] In embodiments, the functionalized polymer may be a di-block copolymer comprising at least one block of isoprene homo- or co-polymer.

[0305] Optionally, butadiene repeat units may be absent in the functionalized polymer.

[0306] Optionally, the functionalized polymer may be not homopolyisobutylene.

[0307] Optionally, the functionalized polymer may be not a copolymer of isoprene and butadiene.

[0308] Generally, the polymerized conjugated diene in the functionalized polymer includes monomer units that have been inserted in the growing polymer chain by conjugated addition and non-conjugated addition In embodiments the functionalized polymer contains at least about 50% of by conjugated addition insertions, such as at least about 75% of by conjugated addition insertions, such as about 80% of by conjugated addition insertions, such as from about 85% to about 100% of by conjugated addition insertions, based upon the total number of by conjugated addition and non-conjugated insertions, as measured by .sup.13C NMR.

[0309] The insertion of isoprene most often occurs by 2,1 insertions, 1,4 insertions (trans and cis), and 3,4 insertions of isoprene. (Measurements of the insertion geometry are determined by .sup.1H NMR.) As measured by .sup.1H NMR, the functionalized isoprene polymer contains at least about 50% of 1,4-insertions, such as at least about 75% of 1,4 insertions, such as at least about 80% of 1,4 insertions, such as at least about 90% of 1,4 insertions, such as at least about 95% of 1,4 insertions, such as at least 98% of 1,4 insertions, based upon the total of the 2,1 insertions, 1,4 insertions, and 3,4 insertions of isoprene. For purposes of this disclosure: 1) the phrase 1,4 insertion includes 1,4 and 4,1 insertions, 2) the phrase 2,1 insertion includes 2,1 and 1,2 insertions, and 3) the phrase 3,4 insertion includes 3,4 and 4,3 insertions.

[0310] The functionalized polymer may be homopolymer or copolymer. Optionally, the functionalized polymer comprises a homopolymer or copolymer of isoprene. The copolymer may be a random copolymer, a tapered block copolymer, a star copolymer, or a block copolymer.

[0311] The functionalized polymer may typically have an Mn of 20,000 to 150,000 g/mol, alternately 20,000 to about 150,000 g/mol, alternately 30,000 to about 125,000 g/mol, alternately 35,000 to about 100,000 g/mol, alternately 40,000 to 80,000 g/mol (GPC-PS).

[0312] The polymer prior to functionalization may typically have an Mn/Mw (GPC-PS) of 1.0 to 2, such as 1.1 to 1.5, such as 1.1 to 1.3, such as 1.1 to 1.2. As functionalization occurs, Mw/Mn broadening may occur.

[0313] The functionalized polymer may typically have an Mw/Mn (GPC-PS) of 1 to 3, alternately 1 to 2, alternately greater than 1 to less than 2, alternately 1.05 to 1.9, alternately 1.10 to 1.8, alternately 1.10 to 1.7, alternately 1.12 to 1.6, alternately 1.13 to 1.5, alternately 1.15 to 1.4, alternately 1.15 to 1.3. Alternately, the functionalized polymer may typically have an Mw/Mn of 1 or greater than 1 to less than 2 (such as less than 1.8, such as less than 1.7, such as less than 1.6, such as less than 1.4, such as less than 1.2, such as less than 1.15, such as less than 1.12, such as less than 1.10).

[0314] In embodiments, the functionalized polymer may have a Saponification Number (SAP) of 25 (such as 28, such as 30, such as 32, such as 34) mgKOH/g or more, as determined by ASTM D94.

[0315] In embodiments, the functionalized polymer may contribute 17% or more (such as 20% or more, such as 17 to 40%, such as 20 to 30%) to the Saponification Number of the lubricating oil composition.

[0316] In embodiments, the functionalized polymer may have an average functionality of 1.4 to 20 FG grafts/polymer chain, such as 1.4 to 15 FG grafts/polymer chain, such as 3 to 12.5 FG grafts/polymer chain, such as 4 to 10 FG grafts/polymer chain, as determined by GPC-PS.

[0317] The functionalized polymer may have an average functionality of 15 (such as 14, 13, 12, 11, 10, 9, 8, 7, or 6) or less FG grafts/polymer chain, as determined by GPC-PS.

[0318] The functionalized polymer may have an average functionality of 1 (such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0) or more FG grafts/polymer chain, as determined by GPC-PS.

[0319] The functionalized polymer may have an average functionality from 1 (such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0) to 15 (such as 14, 13, 12, 11, 10, 9, 8, 7, or 6) FG grafts/polymer chain, as determined by GPC-PS.

[0320] In embodiments, the functionalized polymer may have an aromatic content of 5% or less, such as 3% ore less, such as 1% or less, such as 0%, based upon the weight of the polymer.

[0321] In embodiments, the functionalized polymer may comprise acylated polymers of branched C.sub.4 5 monomers having an Mn of 20,000 to 500,000 g/mol having an Mw/Mn of 2 or less, such as from 1 to 2.0, as determined by GPC-PS.

[0322] In embodiments, the functionalized polymer may have a number average molecular weight (Mn) of 20,000 (such as 25,000, such as 30,000, such as 35,000 such as 40,000) g/mol or more, as determined by GPC-PS.

[0323] In embodiments, the functionalized polymer may have a weight average molecular weight (Mw) of 50,000 (such as 40,000, such as 35,000) g/mol or less, as determined by GPC-PS. In embodiments, the functionalized polymer may have a weight average molecular weight (Mw) of 1000 to 50,000 g/mol, such as 5000 to 40,000 g/mol as determined by GPC-PS.

[0324] In embodiments, the functionalized polymer may have a z average molecular weight (Mz) of 5000 to 150,000 g/mol, such as 10,000 to 150,000 g/mol, such as 15,000 to 70,000 g/mol, such as 20,000 to 150,000 g/mol, alternately 20,000 to about 150,000 g/mol, alternately 30,000 to about 125,000 g/mol, alternately 35,000 to about 100,000 g/mol, alternately 40,000 to 80,000 g/mol, alternately 40,000 to 60,000 g/mol (GPC-PS).

[0325] In embodiments, the functionalized polymer may have a gel content of less than about 5 wt %, less than 3 wt %, less than 2 wt %, less than 1 wt %, less than 0.5 wt %, less than 0.1 wt %, or 0 wt %, where the gel content is measured by determining the amount of material that is extractable from the polymer by using boiling xylene (or cyclohexane) as an extractant. The percent of soluble and insoluble (gel) material in a polymer composition is determined as described herein.

[0326] In embodiments, the functionalized polymer may have a Functionality Distribution (Fd) value of 3.5 or less (such as 3.4 or less, such as from 1 to 3.3, such as from 1.1 to 3.2, such as from 1.2 to 3.0, such as 1.4 to 2.9, as determined by GPC-PS) (Functionality Distribution (Fd) value is determined as set out in the Example section below) and an average functionality of 1.4 to 20 FG grafts/polymer chain, such as 1.4 to 15 FG grafts/polymer chain, such as 3 to 12.5 FG grafts/polymer chain, such as 4 to 10 FG grafts/polymer chain, as determined by GPC-PS.

[0327] This disclosure relates to amide, imide, and/or ester functionalized hydrogenated/saturated polymers comprising (consisting essentially of or consisting of) C.sub.4-5 olefins having an Mw/Mn of less than 2, a Functionality Distribution (Fd) value of 3.5 or less (such as 3.4 or less, such as from 1 to 3.3, such as from 1.1 to 3.2, such as from 1.2 to 3.0, such as 1.4 to 2.9, as determined by GPC-PS, and wherein, if the polymer prior to functionalization is a C.sub.4 olefin polymer such as polyisobutylene, polybutadiene, or a copolymer thereof (preferably a polyisobutylene or a copolymer of isobutylene and butadiene), then the C.sub.4 olefin polymer has an Mn of 10,000 g/mol or more (GPC-PS), and if the polymer prior to functionalization is a C.sub.4/C.sub.5 copolymer of isoprene and butadiene, then the Mn of the copolymer is greater than 25,000 Mn (GPC-PS).

[0328] This disclosure also relates to amide, imide, and/or ester functionalized hydrogenated/saturated polymers comprising 90 mol % or more isoprene repeat units, having an Mw/Mn of less than 2, a Functionality Distribution (Fd) value of 3.5 or less (such as 3.4 or less, such as from 1 to 3.3, such as from 1.1 to 3.2, such as from 1.2 to 3.0, such as 1.4 to 2.9, as determined by GPC-PS), and wherein the polymer prior to functionalization has an Mn of 30,000 g/mol or more (GPC-PS).

[0329] This disclosure also relates to amide, imide, and/or ester functionalized hydrogenated/saturated homopolymers of isoprene having an Mw/Mn of less than 2, a Functionality Distribution (Fd) value of 3.5 or less (such as 3.4 or less, such as from 1 to 3.3, such as from 1.1 to 3.2, such as from 1.2 to 3.0, such as 1.4 to 2.9, as determined by GPC-PS), and wherein the polymer prior to functionalization has an Mn of 30,000 g/mol or more (as determined by GPC-PS).

[0330] The functionalized alpha olefin polymer may be a homopolymer or copolymer of C.sub.2 to C.sub.20 linear alpha olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, styrene, octene, nonene, decene, undecene, dodecene, and the like, such as a copolymer of ethylene and propylene).

[0331] In embodiments, the functionalized polymer maybe a homopolymer of ethylene or propylene, or a copolymer of ethylene and or propylene. In embodiments, in a copolymer comprising ethylene and propylene copolymer, the ethylene is present in a greater molar amount. In embodiments, in a copolymer comprising ethylene and propylene copolymer, the propylene is present in a greater molar amount.

[0332] In embodiments, styrene repeat units may be absent in the functionalized polymer.

[0333] In embodiments, the functionalized polymer may be a block or tapered block copolymer that does not comprise a styrene block.

[0334] In embodiments, the functionalized polymer may be a block or tapered block copolymer comprising (or consisting of or consisting essentially of) ethylene and or propylene.

[0335] In embodiments, the functionalized polymer may be a block or tapered block copolymer comprising 50 wt % or more ethylene, based upon the weight of the copolymer.

[0336] The functionalized polymer may be homopolymer or copolymer. Optionally, the functionalized polymer comprises a homopolymer or copolymer of isoprene. The copolymer may be a random copolymer, a tapered block copolymer, a star copolymer, or a block copolymer.

[0337] The functionalized polymer may typically have an Mn of 20,000 to 150,000 g/mol, alternately 20,000 to about 150,000 g/mol, alternately 30,000 to about 125,000 g/mol, alternately 35,000 to about 100,000 g/mol, alternately 40,000 to 80,000 g/mol (GPC-PS).

[0338] The polymer prior to functionalization may typically have an Mn/Mw (GPC-PS) of 1.0 to 3, such as 1.1 to 2, such as 1.1 to 1.9, such as 1.1 to 1.8. As functionalization occurs, Mw/Mn broadening may occur.

[0339] The functionalized polymer may typically have an Mw/Mn (GPC-PS) of 1 to 3, alternately 1 to 2, alternately greater than 1 to less than 2, alternately 1.05 to 1.9, alternately 1.10 to 1.8, alternately 1.10 to 1.7, alternately 1.12 to 1.6, alternately 1.13 to 1.5, alternately 1.15 to 1.4, alternately 1.15 to 1.3. Alternately, the functionalized polymer may typically have an Mw/Mn of 1 or greater than 1 to less than 2 (such as less than 1.8, such as less than 1.7, such as less than 1.6, such as less than 1.4, such as less than 1.2, such as less than 1.15, such as less than 1.12, such as less than 1.10).

[0340] In embodiments, the functionalized polymer may have a Saponification Number (SAP) of 25 (such as 28, such as 30, such as 32, such as 34) mgKOH/g or more, as determined by ASTM D94.

[0341] In embodiments, the functionalized polymer may contribute 17% or more (such as 20% or more, such as 17 to 40%, such as 20 to 30%) to the Saponification Number of the lubricating oil composition.

[0342] In embodiments, the functionalized polymer may have an average functionality of 1.4 to 20 FG grafts/polymer chain, such as 1.4 to 15 FG grafts/polymer chain, such as 3 to 12.5 FG grafts/polymer chain, such as 4 to 10 FG grafts/polymer chain, as determined by GPC-PS.

[0343] The functionalized polymer may have an average functionality of 15 (such as 14, 13, 12, 11, 10, 9, 8, 7, or 6) or less FG grafts/polymer chain, as determined by GPC-PS.

[0344] The functionalized polymer may have an average functionality of 1 (such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0) or more FG grafts/polymer chain, as determined by GPC-PS.

[0345] The functionalized polymer may have an average functionality from 1 (such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0) to 15 (such as 14, 13, 12,11, 10, 9, 8, 7, or 6) FG grafts/polymer chain, as determined by GPC-PS.

[0346] In embodiments, the functionalized polymer may have a weight average molecular weight (Mw) of 50,000 (such as 40,000, such as 35,000) g/mol or less, as determined by GPC-PS. In embodiments, the functionalized polymer may have a weight average molecular weight (Mw) of 1000 to 50,000 g/mol, such as 5000 to 40,000 g/mol as determined by GPC-PS.

[0347] In embodiments, the functionalized polymer may have a z average molecular weight (Mz) of 5000 to 150,000 g/mol, such as 10,000 to 150,000 g/mol, such as 15,000 to 70,000 g/mol, such as 20,000 to 150,000 g/mol, alternately 20,000 to about 150,000 g/mol, alternately 30,000 to about 125,000 g/mol, alternately 35,000 to about 100,000 g/mol, alternately 40,000 to 80,000 g/mol, alternately 40,000 to 60,000 g/mol (GPC-PS).

[0348] In embodiments, the functionalized polymer may have a gel content of less than about 5 wt %, less than 3 wt %, less than 2 wt %, less than 1 wt %, less than 0.5 wt %, less than 0.1 wt %, or 0 wt %, where the gel content is measured by determining the amount of material that is extractable from the polymer by using boiling xylene (or cyclohexane) as an extractant. The percent of soluble and insoluble (gel) material in a polymer composition is determined as described herein.

[0349] In embodiments, the functionalized polymer may have a Functionality Distribution (Fd) value of more than 3.5 (such as 3.5 to 10, such as from 3.8 to 8, such as from 4.7 to 7, as determined by GPC-PS) (Functionality Distribution (Fd) value is determined as set out in the Example section below) and an average functionality of 1.4 to 20 FG grafts/polymer chain, such as 1.4 to 15 FG grafts/polymer chain, such as 3 to 12.5 FG grafts/polymer chain, such as 4 to 10 FG grafts/polymer chain, as determined by GPC-PS.

[0350] This disclosure also relates to amide, imide, and/or ester functionalized hydrogenated/saturated homopolymers of isoprene having an Mw/Mn of less than 2, a Functionality Distribution (Fd) value of more than 3.5 (such as 4.0 or more, such as 4.5 or more, such as 5 or more, such as 6 or more, such as 7 or more, such as from more than 3.5 to 10, such as from 4.0 to 8.5, such as from 5 to 8.0, such as 3.8 to 7, as determined by GPC-PS).

[0351] In embodiments, the functionalized polymer may have a Functionality Distribution (Fd) value of more than 3.5 (such as 3.8 or more, such as from 3.8 to 8, such as from 4.7 to 7, as determined by GPC-PS) (Functionality Distribution (Fd) value is determined as set out in the Example section below) and an average functionality of 1.4 to 20 FG grafts/polymer chain, such as 1.4 to 15 FG grafts/polymer chain, such as 3 to 12.5 FG grafts/polymer chain, such as 4 to 10 FG grafts/polymer chain, as determined by GPC-PS.

iii. F-H-PI Functionalized Polymers

[0352] The functionalized polymer component of the lubricating oil compositions and concentrate compositions disclosed herein comprises a polymer that prior to functionalization has an Mn of about 10,000 g/mol or more, such as 20,000 g/mol or more, such as 25,000 g/mol or more, such as 30,000 g/mol or more, such as 35,000 g/mol or more (GPC-PS). Alternately, functionalized polymer comprises a polymer that prior to functionalization has an Mn of 10,000 to 300,000 g/mol, such as 20,000 to about 150,000 g/mol, such as 30,000 to about 125,000 g/mol, such as 35,000 to about 100,000 g/mol, such as 40,000 to 80,000 g/mol (GPC-PS). The polymer prior to functionalization may have an Mw/Mn of less than 2 (such as less than 1.6, such as less than 1.5, such as 1.4 or less, such as from 1 to 1.3, such as from 1.0 to 1.25, such as from 1.0 to 1.2, such as 1.0 to 1.15, such as from 1.0 to 1.1 as determined by GPC-PS). The polymer prior to functionalization may comprise repeat units of one or more olefins having 4 to 5 carbon atoms (preferably conjugated dienes having 4 to 5 carbon atoms). Prior to functionalization the C.sub.4-5 polymer is preferably fully or partially saturated (such as fully or partially hydrogenated). The functionalized polymer may be obtained by reacting the C.sub.4-5 polymer with an acylating agent to form acylated polymer and then reacting acylated polymer with an amine or alcohol to form an amide, imide, ester, or combination thereof. The functionalized polymer may also be obtained by reacting an acylated C.sub.4-5 polymer (such as a commercially available maleated fully or partially hydrogenated C.sub.4-5 polymer) with an amine to form an amide, imide or combination thereof.

[0353] This disclosure further relates to lubricating oil compositions including functionalized polymers including amide, imide, and/or ester functionalized saturated (such as hydrogenated) polymers of C.sub.4-5 conjugated dienes described herein obtained by reacting fully or partially saturated (such as fully or partially hydrogenated) polymers of C.sub.4-5 conjugated dienes having an Mw/Mn of less than 2, with an acylating agent, such as maleic acid or maleic anhydride and thereafter reacting the acylated polymer with an amine (such as a polyamine) to form an imide, amide or combination thereof.

[0354] This disclosure relates to lubricating oil compositions including functionalized polymers containing one or more pendant amine groups and comprising or resulting from the admixing of: at least partially (preferably completely) hydrogenated C.sub.4-5 olefin polymers with an acylating agent, such as maleic acid or maleic anhydride, and thereafter reacting the acylated polymer with a polyamine to form an imide, amide or combination thereof.

[0355] In embodiments, the functionalized polymer is not prepared in aromatic solvent (such as benzene or toluene), or aromatic solvent is present at 2 wt % or less (such as 1 wt % or less, such as 0.5 wt % or less), based upon the weight of solvent, diluent, and polymer.

[0356] In embodiments, the functionalized polymer is not prepared in an alkylated naphthylenic solvent, or alkylated naphthylenic solvent is present at 5 wt % or less (such as 3 wt % or less, such as 1 wt % or less), based upon the weight of solvent, diluent, and polymer.

[0357] The polymer useful herein to prepare the functionalized polymer may be a homopolymer of butadiene, isoprene, or the like.

[0358] In embodiments, the polymer useful herein to prepare the functionalized polymer may be a homopolymer of isoprene, or a copolymer of isoprene and less than 5 mol % (such as less than 3 mol %, such as less than 1 mol %, such as less than 0.1 mol %) comonomer.

[0359] The polymer useful herein to prepare the functionalized polymer may be copolymer of isoprene and one or more of styrene, methyl-styrene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3 pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene, 2-p-tolyl-1,3-butadiene 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene, and 3,5-decadiene, [optionally the comonomer(s) are present at less than 20 mol %, less than 5 mol %, such as less than 3 mol %, such as less than 1 mol %, such as less than 0.1 mol %].

[0360] Generally, the polymerized conjugated diene polymer useful herein to prepare the functionalized polymer includes a mixture of 1,4- and 1,2-insertions (a.k.a. 2,1-insertions; forbutadiene, 1,2-insertions are the same as 3,4-insertions). As measured by 1H NMR, the polymerized conjugated diene polymer useful herein to prepare the functionalized polymer contains at least about 50% of 1,4-insertions, such as at least about 75% of 1,4 insertions, such as at least about 80% of 1,4 insertions, such as at least about 90% of 1,4 insertions, such as at least about 95% of 1,4 insertions, such as at least 98% of 1,4 insertions, based upon the total of the 2,1 insertions, 1,4 insertions, and 3,4 insertions of isoprene. For purposes of this disclosure: 1) the phrase 1,4 insertion includes 1,4 and 4,1 insertions, 2) the phrase 2,1 insertion includes 2,1 and 1,2 insertions, and 3) the phrase 3,4 insertion includes 3,4 and 4,3 insertions.

[0361] Optionally, styrene repeat units may be absent in the polymer useful herein to prepare the functionalized polymer. Optionally, styrene repeat units may be absent in the functionalized hydrogenated/saturated polymers.

[0362] Optionally, butadiene repeat units may be absent in the polymer useful herein to prepare the functionalized polymer. Optionally, butadiene repeat units may be absent in the functionalized hydrogenated/saturated polymers.

[0363] Optionally, the polymer useful herein to prepare the functionalized polymer may be not homopolybutylene. Optionally, the functionalized hydrogenated/saturated polymer may be not homopolybutylene.

[0364] Optionally, the polymer useful herein to prepare the functionalized polymer may be not homopolyisobutylene. Optionally, the functionalized hydrogenated/saturated polymer may be not homopolyisobutylene.

[0365] Optionally, the polymer useful herein to prepare the functionalized polymer may not be a copolymer of isoprene and butadiene. Optionally, the functionalized hydrogenated/saturated polymer may not be a copolymer of isoprene and butadiene.

[0366] The polymer useful herein to prepare the functionalized polymer and/or the functionalized polymer may be homopolymer or copolymer. The copolymer may be a random copolymer, a tapered block copolymer, a star copolymer, or a block copolymer. Block copolymers are formed from a monomer mixture comprising one or more first monomers (such as isobutylene), wherein, for example, a first monomer forms a discrete block of the polymer joined to a second discrete block of the polymer formed from a second monomer (such as butadiene). While block copolymers have substantially discrete blocks formed from the monomers, a tapered block copolymer may be composed of, at one end, a relatively pure first monomer and, at the other end, a relatively pure second monomer. The middle of the tapered block copolymer may be more of a gradient composition of the two monomers.

[0367] The polymer useful herein to prepare the functionalized polymer may typically have an Mn of 20,000 to 150,000 g/mol, alternately 20,000 to about 150,000 g/mol, alternately 30,000 to about 125,000 g/mol, alternately 35,000 to about 100,000 g/mol, alternately 40,000 to 80,000 g/mol (GPC-PS).

[0368] Polymers useful herein to prepare the functionalized polymers may typically have an Mw/Mn (as determined by GPC-PS) of 1 to 2, alternately greater than 1 to less than 2, alternately 1.1 to 1.8, alternately 1.2 to 1.5. Alternately, the polymers useful herein to prepare the functionalized polymers may typically have an Mw/Mn of 1 or greater than 1 to less than 2 (such as less than 1.8, such as less than 1.7, such as less than 1.6, such as less than 1.5, such as less than 1.4, such as less than 1.3, such as less than 1.2, such as less than 1.15, such as less than 1.12, such as less than 1.10).

[0369] The polymers used to prepare the functionalized polymers may have an Mz (as determined by GPC-PS) of 20,000 to 150,000 g/mol, alternately 20,000 to about 150,000 g/mol, alternately 30,000 to about 125,000 g/mol, alternately 35,000 to about 100,000 g/mol, alternately 40,000 to 80,000 g/mol, alternately 40,000 to 60,000 g/mol (GPC-PS).

[0370] Polymers useful herein to prepare the functionalized polymers may have a glass transition temperature (Tg) of 25 C. or less, such as 40 C. or less, such as 50 C. or less, as determined by Differential Scanning calorimetry (DSC) using a Perkin Elmer or TA Instrument Thermal Analysis System (sample is heated from ambient to 2100 C at 100 C/minute and held at 2100 C for 5 minutes, then cooled down to 40 C. at 10 C./minute and held for 5 minutes.)

[0371] Polymers useful herein to prepare the functionalized polymers typically have a residual unsaturation of less than 3%, such less than 2%, such less than 1%, such as less than 0.5%, such as less than 0.25% based upon number of double bonds in the non-hydrogenated polymer.

[0372] Polymers useful herein to prepare the functionalized polymers typically have a residual metal (such as Li, Co, and Al) content of less than 100 ppm, such less than 50 ppm, such as less than 25 ppm, such as less than 10 ppm, such as less than 5 ppm.

Hydrogenation

[0373] The C.sub.4-5 polymer useful herein to prepare the functionalized polymer can be hydrogenated partially or completely by any hydrogenating agent known to one of ordinary skill in the art. For example, a saturated or partially saturated polymer can be prepared by (a) providing a C.sub.4-5 polymer containing unsaturations (such as double or triple bonds); and (b) hydrogenating at least a portion or all of the unsaturations (such as double or triple bonds) in the polymer in the presence of a hydrogenation reagent. In some embodiments, the polymer is fully hydrogenated. In some embodiments, the polymer is partially hydrogenated. In some embodiments, the polymer is saturated (hydrogenated) at 50% or more, such as 60% or more, such as 70% or more, such as 80% or more, such as 90% or more, such as 95% or more, such as 98% or more, such as 99% or more, such as from 50 to 100% saturated (hydrogenated), as determined by ozone adsorption method described in Martino N. Smits and Dirkman Hoefman, Quantative Determination of Olefinic Unsaturation by Measurement of Ozone Absorption Analytical Chemistry Vol 44, No. 9, pg. 1688, 1972, Martino N. Smits.

[0374] In embodiments, the hydrogenation reagent can be hydrogen in the presence of a hydrogenation catalyst. In some embodiments, the hydrogenation catalyst is Pd, Pd/C, Pt, PtO2, Ru(PPh3)2Cl2, Raney nickel, or a combination thereof. In embodiments, the catalyst is a Pd catalyst. In another embodiment, the catalyst is 5% Pd/C. In a further embodiment, the catalyst may comprise or be 10% Pd/C in a high-pressure reaction vessel and the hydrogenation reaction is allowed to proceed until completion. Generally, after completion, the reaction mixture can be washed, concentrated, and dried to yield the corresponding hydrogenated product. Alternatively, any reducing agent that can reduce a CC bond to a CC bond can also be used. For example, the olefin polymer can be hydrogenated by treatment with hydrazine in the presence of a catalyst, such as 5-ethyl-3-methyllumiflavinium perchlorate, under an oxygen atmosphere to give the corresponding hydrogenated products. The reduction reaction with hydrazine is disclosed in Imada et al., J Am. Chem. Soc., 127, pp. 14544-14545, (2005), which is incorporated herein by reference.

Acylation

[0375] The fully or partially saturated (hydrogenated) polymer may be chemically modified (functionalized) to provide a polymer having at least one polar functional group, such as, but not limited to, halogen, epoxy, hydroxy, amino, nitrilo, mercapto, imido, carboxy, and sulfonic acid groups of combinations thereof. The functionalized polymers can be further modified to give a more desired type of functionality. In a preferred case, the fully or partially hydrogenated polymer is functionalized by a method, which includes reacting the fully or partially hydrogenated polymer with an unsaturated carboxylic acid (or derivative thereof, such as maleic anhydride) to provide an acylated polymer (which may then be further functionalized as described below).

[0376] In some embodiments, a carboxylic acid functionality or a reactive equivalent thereof is grafted onto the polymer to form an acylated polymer. An ethylenically unsaturated carboxylic acid material is typically grafted onto the polymer backbone. These materials which are attached to the polymer typically contain at least one ethylenic bond (prior to reaction) and at least one, such as two, carboxylic acid (or its anhydride) groups or a polar group which is convertible into said carboxyl groups by oxidation or hydrolysis. Maleic anhydride or a derivative thereof is suitable. It grafts onto the polymer, to give two carboxylic acid functionalities. Examples of additional unsaturated carboxylic materials include itaconic anhydride, or the corresponding dicarboxylic acids, such as maleic acid, fumaric acid and their esters, as well as cinnamic acid and esters thereof.

[0377] The ethylenically unsaturated carboxylic acid material may be grafted onto the polymer in a number of ways. It may be grafted onto the polymer in solution or in essentially pure (molten) form with or without using a radical initiator. Free-radical induced grafting of ethylenically unsaturated carboxylic acid materials may also be conducted in solvents, such as hexane or mineral oil. It may be carried out at an elevated temperature in the range of 100 C. to 250 C., e.g., 120 C. to 190 C., or 150 C. to 180 C., e.g., above 160 C.

[0378] The free-radical initiators which may be used include peroxides, hydroperoxides, and azo compounds, typically those which have a boiling point greater than about 100 C. and which decompose thermally within the grafting temperature range to provide free radicals. Representative of these free-radical initiators include azobisisobutyronitrile and 2,5-dimethyl-hex-3-yne-2,5-bis-tertiary-butyl peroxide. The initiator may be used in an amount of 0.005% to 1% by weight based on the weight of the reaction mixture solution. The grafting may be carried out in an inert atmosphere, such as under nitrogen blanketing. The resulting acylated polymer intermediate is characterized by having carboxylic acid acylating functions as a part of its structure.

[0379] In embodiments, the acylated polymer may have 2 or more anhydride groups per polymer molecule and may exhibit less than 10% gel. Alternately, the acylated polymer may have less than 2 anhydride groups per polymer molecule and may exhibit less than 10% gel. (See also col 17, ln 14-col 18, ln 11 of U.S. Pat. No. 5,429,758).

[0380] Alternately, in some embodiments, the acylated polymer may have a gel content of less than about 5 wt %, less than 3 wt %, less than 2 wt %, less than 1 wt %, less than 0.5 wt %, less than 0.1 wt %, or 0 wt %, where the gel content is measured by determining the amount of material that is extractable from the polymer by using boiling xylene (or cyclohexane) as an extractant. The percent of soluble and insoluble (gel) material in a polymer composition is determined by soaking a nominally 0.5 mm thick thin film specimen of polymer for 48 hours in cyclohexane at 230 C or refluxing the thin film specimen in boiling xylene for one half hour, removing the solvent, weighing the dried residue and calculating the amount of soluble and insoluble (gel) material. This method is generally described in U.S. Pat. No. 4,311,628, which is incorporated herein by reference. For purposes of this disclosure, gel content is measured using boiling xylene, unless the sample is not soluble in xylene, then the cyclohexane method is used.

[0381] In embodiments, the acylated polymer may have a Saponification Number (SAP) of 5 g/KOH or more, such as 10 g/KOH or more, such as 20 g/KOH or more, such as 30 g/KOH or more, such as 50 g/KOH or more, such as 10 to 60 g/KOH, such as 20 to 40 g/KOH as determined by ASTM D94.

[0382] In embodiments, the acylated polymer composition may have less than 5 wt % unreacted acylating agent (such as maleic anhydride), such as less than 4 wt %, such as less than 3 wt %, such as less than 1 wt %, such as less than 0.5 wt %, such as less than 0.25 wt %, such as less than 0.1 wt %, based upon the weight of the acylated polymer composition (i.e., polymer, acylating agent, and diluent).

[0383] In embodiments, the acylation reactions described herein may take place in base oil diluent. As a side product, functionalized base oil can be produced. The oil may become acylated itself. For example, maleated base oil may be present after the acylation reactions described herein.

[0384] It is contemplated that the functionalized base oil may comprise the acylated oil and/or the reaction product of the acylated oil with an amine to form an amide, imide or combination thereof.

[0385] Preferably, the acylated oil and/or reaction product of the acylated oil with an amine or alcohol to form an amide, imide, ester, or combination thereof, may be present in a concentrate in an amount of 40 wt % or less, alternately 20 wt % or less, alternately 10 wt % or less, alternately 5 wt % or less, alternately 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably at 0.1 mass % or less, preferably at 0 mass % (such as 0 to 40 mass %, alternately 0.01 to 40 mass %, alternately 0.1 to 20 mass %, alternately to 1 to 10 mass %, alternately 1.5 to 5 mass %), based upon the weight of the concentrate composition.

[0386] Preferably one or more functionalized base oils, such as acylated oil and/or reaction product of the acylated oil with an amine or alcohol to form an amide, imide, ester, or combination thereof, may be present in the lubricating oil composition at an amount of 0.01 to 40 mass %, alternately 0.1 to 20 mass %, alternately to 1 to 10 mass %, alternately 1.5 to 5 mass %, (such as at 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably at 0.1 mass % or less, preferably at 0 mass %), based upon the weight of the lubricating oil composition.

[0387] In embodiments, the acylation reactions described herein take place in solvent containing media. As a side product, acylated/functionalized solvent can be produced. In embodiments, acylated and/or functionalized solvent may be present in a concentrate composition at 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably at 0.1 mass % or less, preferably at 0 mass %, based upon the weight of the concentrate composition. In embodiments, functionalized solvent may be present in a lubricating oil composition at 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably at 0.1 mass % or less, preferably at 0 mass %, based upon the weight of the lubricating oil composition.

[0388] In embodiments, the acylating agent maybe added in such away as to minimize side reactions (such as reaction with base oil or other diluent present in the reaction vessel).

[0389] In embodiments, the acylating reaction may occur where the acylating agent (such as maleic acid or maleic anhydride) is added in a continuous or semi-continuous (such as intermittent) stream (such as, for example, in controlled relatively equal portions over the reaction time, or larger and/or smaller portions at different points in the reaction) to minimize functionalized base oil and other side reactions. As an example, the acylating agent may be added in a continuous fashion where the amounts of polymer and acylating agents are added in controlled stoichiometric amounts. As another example, the polymer may be added to a reaction vessel in batch fashion and the acylating agent added slowly or in a semi-continuous fashion (such as adding the acylating agent in 2 or more, such as 5 or more, such as 10 or more, such as 20 or more, such as 30 or more, such as 40 or more, such as 50 or more, such as 60 or more discrete amounts or portions). Alternately, the polymer can be added to the reaction vessel in X number of portions and the acylating agent added in 1.5 or more (such as 2 or more, such as 5 or more, such as 10 or more, such as 20 or more, such as 30 or more, such as 40 or more, such as 50 or more, such as 60 or more) number of portions. This same effect may also be achieved by diluting or concentrating a polymer solution and/or the acylating agent solution to the same or different extents.

[0390] Preferably, the acylating agent maybe added in such away as to minimize side reactions, such as in a continuous or semi-continuous fashion.

[0391] The reaction may also be run so as to minimize side reactions by using high concentrations of the polymer in diluent, such as 45 wt % or more, or 50 wt % or more, or 55 wt % or more, or 60 wt % or more in batch, semi-continuous, or continuous reactor operations. For example, the polymer (such as a hydrogenated isoprene polymer, such as hydrogenated homo-polyisoprene) may be introduced into batch, semi-continuous, or continuous reactor operations as solution or suspension (such as a slurry) in diluent (such as oil (e.g., base oil, such as a Group I, II, III, IV, and/or V base oil, such as a Group II and/or Group III base oil) or alkane solvent or diluent or a combination thereof), where the polymer may be present in the solution or suspension at 45 wt % or more (or 50 wt % or more, or 55 wt % or more, or 60 wt % or more), based upon the weight of the polymer and diluent.

[0392] In embodiments, the side reactions may be minimized by: 1) adding the acylating agent in a continuous or semi-continuous fashion, and/or 2) the polymer is introduced into batch, semi-continuous or continuous reactor operations as solution or suspension in diluent where the polymer is present at 45 wt % or more, based upon the weight of the polymer and diluent.

[0393] In embodiments, side reactions are minimized, optionally by adding the acylating agent in a continuous or semi-continuous fashion, and/or by introducing the fully or partially hydrogenated polymer (such as isoprene polymer) into batch, semi-continuous, or continuous reactor operations as solution or suspension in diluent, said solution or suspension comprising 45 wt % or more (or 50 wt % or more, or 55 wt % or more, or 60 wt % or more), of the fully or partially hydrogenated polymer, based upon the weight of the fully or partially hydrogenated polymer and diluent.

[0394] In embodiments, side reactions are minimized, optionally by adding the acylating agent in a continuous or semi-continuous fashion, and by introducing the fully or partially hydrogenated polymer (such as isoprene polymer) into batch, semi-continuous, or continuous reactor operations as solution or suspension in diluent, said solution or suspension comprising 45 wt % or more (or 50 wt % or more, or 55 wt % or more, or 60 wt % or more), of the fully or partially hydrogenated polymer, based upon the weight of the fully or partially hydrogenated polymer and diluent.

Functionalization

[0395] In embodiments, the acylated polymer may be reacted with an alcohol or an amine to form an amide, imide, ester or combinations thereof. The reaction may consist of condensation to form an imide, an amide, a half-amide, amide-ester, diester, or an amine salt. A primary amino group will typically condense to form an amide or, in the case of maleic anhydride, an imide. It is noted the amine may have a single primary amino group or multiple primary amino groups.

[0396] Suitable amines may include one or more aromatic amines, such as amines wherein a carbon atom of the aromatic ring structure is attached directly to the amino nitrogen. The amine may also be aliphatic. In embodiments aliphatic amines can be used alone or in combination with each other or in combination with aromatic amines. The amount of aromatic amine may, in some embodiments, be a major or minor amount compared with the amount of the non-aromatic amines, or in some instances, the composition may be substantially free of aromatic amine. Alternately, the composition may be substantially free of aliphatic amine.

[0397] Examples of aromatic amines which may be used herein include one or more N-arylphenylenediamine(s) represented by the formula:

##STR00007##

wherein R.sub.7 is H, NHaryl, NHalkaryl, or a branched or straight chain hydrocarbyl radical having from about 4 to about 24 carbon atoms selected from alkyl, alkenyl, alkoxyl, aralkyl or alkaryl; R.sub.9 is NH.sub.2, (NH(CH.sub.2).sub.n).sub.mNH.sub.2, NHalkyl, NHaralkyl, CH.sub.2-aryl-NH.sub.2, in which n and m each have a value from about 1 to about 10; and R.sub.8 is hydrogen, or alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl, having from about 4 to about 24 carbon atoms.

[0398] Suitable N-arylphenylenediamines include N-phenylphenylenediamines (NPPDA), for example, N-phenyl-4,4-phenylenediamine, N-phenyl-1,3-phenylenediamine, and N-phenyl-1,2-phenylenediamine and N-naphthyl-1,4-phenylenediamine. Other derivatives of NPPDA may also be included, such as N-propyl-N-phenylphenylenediamine.

[0399] In embodiments, the amine reacted with the acylated polymer is an amine having at least 3 or 4 aromatic groups and may be represented by the following formula:

##STR00008##

wherein independently each variable, R.sup.1 may be hydrogen or a C.sub.1 to C.sub.5 alkyl group (typically hydrogen); R.sup.2 may be hydrogen or a C.sub.1 to C.sub.5 alkyl group (typically hydrogen); U may be an aliphatic, alicyclic or aromatic group, with the proviso that when U is aliphatic, the aliphatic group may be linear or branched alkylene group containing 1 to 5, or 1 to 2 carbon atoms; and w may be 1 to 10, or 1 to 4, or 1 to 2 (typically 1).

[0400] Other examples of aromatic amines include aniline, N-alkylanilines such as N-methyl aniline, and N-butylaniline, di-(para-methylphenyl)amine, naphthylamine, 4-aminodiphenylamine, N,N-dimethylphenylenediamine, 4-(4-nitro-phenylazo)aniline (disperse orange 3), sulfamethazine, 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetanilide, 4-amino-2-hydroxy-benzoic acid phenyl ester (phenyl amino salicylate), N-(4-amino-5-methoxy-2-methyl-phenyl)-benzamide (fast violet B), N-(4-amino-2,5-dimethoxy-phenyl)-benzamide (fast blue RR), N-(4-amino-2,5-diethoxy-phenyl)-benzamide (fast blue BB), N-(4-amino-phenyl)-benzamide and 4-phenylazoaniline. Suitable amines are referenced in U.S. Pat. No. 7,790,661 and are hereby incorporated by reference.

[0401] In embodiments, the compound condensing with the acylated polymer can be represented by the following formulas:

##STR00009##

wherein X is an alkylene group containing about 1 to about 4 carbon atoms; R.sup.2, R.sup.3 and R.sup.4 are hydrocarbyl groups.

##STR00010##

wherein X is an alkylene group containing about 1 to about 4 carbon atoms; R.sup.3 and R.sup.4 are hydrocarbyl groups.

[0402] Alternately, the amine may be an amine having at least 4 aromatic groups and an aldehyde (such as formaldehyde). The aromatic amine may be represented by formula:

##STR00011##

wherein, R.sup.1 is hydrogen or a C.sub.1-5 alkyl group (typically hydrogen); R.sup.2 is hydrogen or a C.sub.1-5 alkyl group (typically hydrogen); U is an aliphatic, alicyclic or aromatic group, optionally with the proviso that when U is aliphatic, the aliphatic group may be linear or branched alkylene group containing 1, 2, 3, 4, or 5, or 1 to 2 carbon atoms; and w is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, such as 0, 1, 2, or 3 or 0 or 1 (typically 0). For further information on such amines see, e.g., US 2017/0073606, page 5 paragraph [0064]-[0070] and European Patent No. 2 401 348.

[0403] Examples of compounds capable of condensing with the acylating agent and further having a tertiary amino group can include but are not limited to: dimethylaminopropylamine, N,N-dimethyl-aminopropy-lamine, N,N-diethyl-aminopropylamine, N,N-dimethyl-ami-noethylamine ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, the isomeric butylenediamines, pentanediamines, hexanediamines, heptanediamines, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetraamine, tetraethylene pentaamine, pentaethylenehexaamine, hexamethylenetetramine, and bis(hexamethylene) triamine, the diaminobenzenes, the diaminopyridines or mixtures thereof. The compounds capable of condensing with the acylating agent and further having a tertiary amino group can further include aminoalkyl substituted heterocyclic compounds such as 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-di-amino-N-methyldipropylamine, 3,3-aminobis(N,N-dimethylpropylamine). Another example of compounds capable of condensing with the acylating agent and having a tertiary amino group include alkanolamines including, but not limited to, triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-di-ethylaminopropanol, N,N-diethylaminobutanol, N,N,N-tris (hydroxyethyl)amine, N,N,N-tris(hydroxymethyl)amine.

[0404] In embodiments, the polymer may be reacted with a polyether aromatic compound. Typically, the polyether aromatic compound will have at least two functional groups, each capable of reacting with a monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester thereof, or mixtures thereof. In embodiments, the polyether aromatic compound is derived from an aromatic compound containing at least one amine group and wherein the poly ether is capable of reacting with a monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester thereof.

[0405] Examples of suitable polyether aromatic amines include compounds having the following structure:

##STR00012##

in which A represents an aromatic aminic moiety wherein the ether groups are linked through at least one amine group on the aromatic moiety; R.sub.1 and R.sub.6 are independently hydrogen, alkyl, alkaryl, aralkyl, or aryl or mixtures thereof; R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are independently hydrogen or alkyl containing from about 1 to about 6 carbon atoms of mixtures thereof; and a and x are independently integers from about 1 to about 50.

[0406] The acylated polymer may be reacted with a polyether amine or polyether polyamine. Typical polyether amine compounds contain at least one ether unit and are chain terminated with at least one amine moiety. The polyether polyamines can be based on polymers derived from C.sub.2-C.sub.6 epoxides such as ethylene oxide, propylene oxide, and butylene oxide. Examples of polyether polyamines are sold under the Jeffamine brand and are commercially available from Huntsman Corporation.

[0407] Amines useful herein for combination with the acylated polymer include one or more of: N-phenyldiamines (such as N-phenyl-1,4-phenylenediamine, N-phenyl-p-phenylenediamine (a.k.a. 4-amino-diphenylamine, ADPA), N-phenyl-1,3-phenylenediamine, N-phenyl-1,2-phenylenediamine), nitroaniline (such as 3-nitroaniline), N-phenylethane-diamine (such as N1-phenylethane-1,2-diamine), N-aminophenylacetamide (such as N-(4-aminophenyl)acetamide), morpholinopropanamine (such as 3-morpholinopropan-1-amine), and aminoethylpiperazine (such as 1-(2-aminoethyl)piperazine).

[0408] In embodiments, the functionalization (such as amination) reactions described herein may take place in diluent (such as base oil or alkane solvent). As a side product, functionalized diluent (such as functionalized base oil) can be produced. It is contemplated that the functionalized diluent (such as functionalized base oil) may comprise reaction product of the acylated diluent (such as acylated base oil) with an amine to form an amide, imide or combination thereof.

[0409] Preferably, the reaction product of the acylated diluent (such as acylated oil) with an amine or alcohol to form an amide, imide, ester, or combination thereof, may be present in a concentrate in an amount of 40 wt % or less, alternately 20 wt % or less, alternately 10 wt % or less, alternately 5 wt % or less, alternately 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably at 0.1 mass % or less, preferably at 0 mass % (such as 0 to 40 mass %, alternately 0.01 to 40 mass %, alternately 0.1 to 20 mass %, alternately to 1 to 10 mass %, alternately 1.5 to 5 mass %), based upon the weight of the concentrate composition.

[0410] Preferably one or more functionalized base oils, such as the reaction product of the acylated diluent (such as acylated base oil) with an amine or alcohol to form an amide, imide, ester, or combination thereof, may be present in the lubricating oil composition at an amount of 0.01 to 40 mass %, alternately 0.1 to 20 mass %, alternately to 1 to 10 mass %, alternately 1.5 to 5 mass %, (such as at 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably at 0.1 mass % or less, preferably at 0 mass %), based upon the weight of the lubricating oil composition.

[0411] In embodiments, the functionalization (such as amination) reactions described herein may take place in solvent-containing media. As a side product, functionalized solvent can be produced. In embodiments, the functionalized solvent may be present in a concentrate composition at 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably at 0.1 mass % or less, preferably at 0 mass %, based upon the weight of the concentrate composition. In embodiments, functionalized solvent may be present in a lubricating oil composition at 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably at 0.1 mass % or less, preferably at 0 mass %, based upon the weight of the lubricating oil composition.

[0412] In embodiments, the acylated base oil/solvent may be removed prior to functionalization.

[0413] The functionalized polymer may be a homopolymer of C.sub.4 or C.sub.5 olefins, such as butadiene and isoprene.

[0414] In embodiments, the functionalized polymer may be a homopolymer of isoprene, or a copolymer of isoprene and less than 5 mol % (such as less than 3 mol %, such as less than 1 mol %, such as less than 0.1 mol %) comonomer.

[0415] The functionalized polymer may comprise or be a copolymer of isoprene and one or more of styrene, methyl-styrene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3 pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene, 2-p-tolyl-1,3-butadiene 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene, and 3,5-decadiene, (optionally the comonomer(s) are present at less than 20 mol %, less than 5 mol %, such as less than 3 mol %, such as less than 1 mol %, such as less than 0.1 mol %)

[0416] In embodiments, the functionalized polymer comprises 10 (such as 9, such as 8, such as 7, such as 6, such as 5, such as 4, such as 3, such as 2, such as 1) wt %, or less, based upon the weight of the functionalized polymer, of styrene monomer.

[0417] In embodiments, styrene repeat units may be absent in the functionalized polymer.

[0418] In embodiments, the functionalized polymer may be a block or tapered block copolymer that does not comprise a styrene block.

[0419] In embodiments, the functionalized polymer may be a block or tapered block copolymer comprising (or consisting of or consisting essentially of) isoprene.

[0420] In embodiments, the functionalized polymer may be a block or tapered block copolymer comprising 50 wt % or more isoprene, based upon the weight of the copolymer.

[0421] In embodiments, the functionalized polymer may be a block or tapered block copolymer comprising (or consisting of or consisting essentially of) C.sub.4-5 conjugated diene, preferably comprising 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) wt % or more C.sub.4-5 conjugated diene, based upon the weight of the copolymer.

[0422] In embodiments, the functionalized polymer may be a copolymer comprising 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) wt % or more isoprene, based upon the weight of the copolymer.

[0423] In embodiments, the functionalized polymer may be a copolymer comprising 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) wt % or more butadiene, based upon the weight of the copolymer.

[0424] In embodiments, the functionalized polymer may be a copolymer comprising 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) wt % or more butadiene and isoprene, based upon the weight of the copolymer.

[0425] In embodiments, the functionalized polymer may be a di-block copolymer comprising at least one block of isoprene homo- or co-polymer.

[0426] Optionally, butadiene repeat units may be absent in the functionalized polymer.

[0427] Optionally, the functionalized polymer may be not homopolyisobutylene.

[0428] Optionally, the functionalized polymer may be not a copolymer of isoprene and butadiene.

[0429] Generally, the polymerized conjugated diene in the functionalized polymer includes monomer units that have been inserted in the growing polymer chain by conjugated addition and non-conjugated addition In embodiments the functionalized polymer contains at least about 50% of by conjugated addition insertions, such as at least about 75% of by conjugated addition insertions, such as about 80% of by conjugated addition insertions, such as from about 85% to about 100% of by conjugated addition insertions, based upon the total number of by conjugated addition and non-conjugated insertions, as measured by .sup.13C NMR.

[0430] The insertion of isoprene most often occurs by 2,1 insertions, 1,4 insertions (trans and cis), and 3,4 insertions of isoprene. (Measurements of the insertion geometry are determined by .sup.1H NMR.) As measured by .sup.1H NMR, the functionalized isoprene polymer contains at least about 50% of 1,4-insertions, such as at least about 75% of 1,4 insertions, such as at least about 80% of 1,4 insertions, such as at least about 90% of 1,4 insertions, such as at least about 95% of 1,4 insertions, such as at least 98% of 1,4 insertions, based upon the total of the 2,1 insertions, 1,4 insertions, and 3,4 insertions of isoprene. For purposes of this disclosure: 1) the phrase 1,4 insertion includes 1,4 and 4,1 insertions, 2) the phrase 2,1 insertion includes 2,1 and 1,2 insertions, and 3) the phrase 3,4 insertion includes 3,4 and 4,3 insertions.

[0431] The functionalized polymer may be homopolymer or copolymer. Optionally, the functionalized polymer comprises a homopolymer or copolymer of isoprene. The copolymer may be a random copolymer, a tapered block copolymer, a star copolymer, or a block copolymer.

[0432] The functionalized polymer may typically have an Mn of 20,000 to 150,000 g/mol, alternately 20,000 to about 150,000 g/mol, alternately 30,000 to about 125,000 g/mol, alternately 35,000 to about 100,000 g/mol, alternately 40,000 to 80,000 g/mol (GPC-PS).

[0433] The polymer prior to functionalization may typically have an Mn/Mw (GPC-PS) of 1.0 to 2, such as 1.1 to 1.5, such as 1.1 to 1.3, such as 1.1 to 1.2. As functionalization occurs, Mw/Mn broadening may occur.

[0434] The functionalized polymer may typically have an Mw/Mn (GPC-PS) of 1 to 3, alternately 1 to 2, alternately greater than 1 to less than 2, alternately 1.05 to 1.9, alternately 1.10 to 1.8, alternately 1.10 to 1.7, alternately 1.12 to 1.6, alternately 1.13 to 1.5, alternately 1.15 to 1.4, alternately 1.15 to 1.3. Alternately, the functionalized polymer may typically have an Mw/Mn of 1 or greater than 1 to less than 2 (such as less than 1.8, such as less than 1.7, such as less than 1.6, such as less than 1.4, such as less than 1.2, such as less than 1.15, such as less than 1.12, such as less than 1.10).

[0435] In embodiments, the functionalized polymer may have a Saponification Number (SAP) of 25 (such as 28, such as 30, such as 32, such as 34) mgKOH/g or more, as determined by ASTM D94.

[0436] In embodiments, the functionalized polymer may contribute 17% or more (such as 20% or more, such as 17 to 40%, such as 20 to 30%) to the Saponification Number of the lubricating oil composition.

[0437] In embodiments, the functionalized polymer may have an average functionality of 1.4 to 20 FG grafts/polymer chain, such as 1.4 to 15 FG grafts/polymer chain, such as 3 to 12.5 FG grafts/polymer chain, such as 4 to 10 FG grafts/polymer chain, as determined by GPC-PS.

[0438] The functionalized polymer may have an average functionality of 15 (such as 14, 13, 12, 11, 10, 9, 8, 7, or 6) or less FG grafts/polymer chain, as determined by GPC-PS.

[0439] The functionalized polymer may have an average functionality of 1 (such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0) or more FG grafts/polymer chain, as determined by GPC-PS.

[0440] The functionalized polymer may have an average functionality from 1 (such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0) to 15 (such as 14, 13, 12,11, 10, 9, 8, 7, or 6) FG grafts/polymer chain, as determined by GPC-PS.

[0441] In embodiments, the functionalized polymer may have an aromatic content of 5% or less, such as 3% or less, such as 1% or less, such as 0%, based upon the weight of the polymer.

[0442] In embodiments, the functionalized polymer may comprise acylated polymers of branched C.sub.4-5 monomers having an Mn of 20,000 to 500,000 g/mol having an Mw/Mn of 2 or less, such as from 1 to 2.0, as determined by GPC-PS.

[0443] In embodiments, the functionalized polymer may have a number average molecular weight (Mn) of 20,000 (such as 25,000, such as 30,000, such as 35,000 such as 40,000) g/mol or more, as determined by GPC-PS.

[0444] In embodiments, the functionalized polymer may have a weight average molecular weight (Mw) of 50,000 (such as 40,000, such as 35,000) g/mol or less, as determined by GPC-PS. In embodiments, the functionalized polymer may have a weight average molecular weight (Mw) of 1000 to 50,000 g/mol, such as 5000 to 40,000 g/mol as determined by GPC-PS.

[0445] In embodiments, the functionalized polymer may have a z average molecular weight (Mz) of 5000 to 150,000 g/mol, such as 10,000 to 150,000 g/mol, such as 15,000 to 70,000 g/mol, such as 20,000 to 150,000 g/mol, alternately 20,000 to about 150,000 g/mol, alternately 30,000 to about 125,000 g/mol, alternately 35,000 to about 100,000 g/mol, alternately 40,000 to 80,000 g/mol, alternately 40,000 to 60,000 g/mol (GPC-PS).

[0446] In embodiments, the functionalized polymer may have a gel content of less than about 5 wt %, less than 3 wt %, less than 2 wt %, less than 1 wt %, less than 0.5 wt %, less than 0.1 wt %, or 0 wt %, where the gel content is measured by determining the amount of material that is extractable from the polymer by using boiling xylene (or cyclohexane) as an extractant. The percent of soluble and insoluble (gel) material in a polymer composition is determined as described herein.

[0447] In embodiments, the functionalized polymer may have a Functionality Distribution (Fd) value of 3.5 or less (such as 3.4 or less, such as from 1 to 3.3, such as from 1.1 to 3.2, such as from 1.2 to 3.0, such as 1.4 to 2.9, as determined by GPC-PS). Functionality Distribution (Fd) value is determined as set out in the Example section below and an average functionality of 1.4 to 20 FG grafts/polymer chain, such as 1.4 to 15 FG grafts/polymer chain, such as 3 to 12.5 FG grafts/polymer chain, such as 4 to 10 FG grafts/polymer chain, as determined by GPC-PS.

[0448] This disclosure relates to amide, imide, and/or ester functionalized hydrogenated/saturated polymers comprising (consisting essentially of or consisting of) C.sub.4-5 olefins having an Mw/Mn of less than 2, a Functionality Distribution (Fd) value of 3.5 or less (such as 3.4 or less, such as from 1 to 3.3, such as from 1.1 to 3.2, such as from 1.2 to 3.0, such as 1.4 to 2.9, as determined by GPC-PS), and wherein, if the polymer prior to functionalization is a C.sub.4 olefin polymer such as polyisobutylene, polybutadiene, or a copolymer thereof (preferably a polyisobutylene or a copolymer of isobutylene and butadiene), then the C.sub.4 olefin polymer has an Mn of 10,000 g/mol or more (GPC-PS), and if the polymer prior to functionalization is a C.sub.4/C.sub.5 copolymer of isoprene and butadiene, then the Mn of the copolymer is greater than 25,000 Mn (GPC-PS).

[0449] This disclosure also relates to amide, imide, and/or ester functionalized hydrogenated/saturated polymers comprising 90 mol % or more isoprene repeat units, having an Mw/Mn of less than 2, a Functionality Distribution (Fd) value of 3.5 or less (such as 3.4 or less, such as from 1 to 3.3, such as from 1.1 to 3.2, such as from 1.2 to 3.0, such as 1.4 to 2.9, as determined by GPC-PS), and wherein the polymer prior to functionalization has an Mn of 30,000 g/mol or more (GPC-PS).

[0450] This disclosure also relates to amide, imide, and/or ester functionalized hydrogenated/saturated homopolymers of isoprene having an Mw/Mn of less than 2, a Functionality Distribution (Fd) value of 3.5 or less (such as 3.4 or less, such as from 1 to 3.3, such as from 1.1 to 3.2, such as from 1.2 to 3.0, such as 1.4 to 2.9, as determined by GPC-PS), and wherein the polymer prior to functionalization has an Mn of 30,000 g/mol or more (as determined by GPC-PS).

[0451] The lubricating composition according to the present disclosure may further comprise one or more additives such as detergents, friction modifiers, antioxidants, pour point depressants, anti-foam agents, viscosity modifiers, dispersants, corrosion inhibitors, antiwear agents, extreme pressure additives, demulsifiers, seal compatibility agents, seal swell agents, additive diluent base oils, etc. Specific examples of such additives are described in, for example, Kirk-Othmer Encyclopedia of Chemical Technology, third edition, volume 14, pp. 477-526, and several are discussed in further detail below.

C. Detergents

[0452] The lubricating oil compositions and concentrate compositions may comprise one or more metal detergents (such as blends of metal detergents) also referred to as a detergent additive. Metal detergents typically function both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents generally comprise a polar head with a long hydrophobic tail, with the polar head comprising a metal salt of an acidic organic compound. The salts may contain a substantially stoichiometric amount of the metal in which case they are usually described as normal or neutral salts, and would typically have a total base number (TBN as measured by ASTM D2896) of up to 150 mgKOH/g, such as from 0 to 80 (or 5-30) mgKOH/g. A large amount of a metal base may be incorporated by reacting excess metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide). Such detergents, sometimes referred to as overbased, may have a TBN of 100 mgKOH/g or more (such as 200 mgKOH/g or more), and typically will have a TBN of 250 mgKOH/g or more, such as 300 mgKOH/g or more, such as from 200 to 800 mgKOH/g, 225 to 700 mgKOH/g, 250 to 650 mgKOH/g, or 300 to 600 mgKOH/g, such as 150 to 650 mgKOH/g.

[0453] Suitable detergents include, oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali metals (Group 1 metals, e.g., Li, Na, K, Rb) or alkaline earth metals (Group 2 metals, e.g., Be, Mg, Ca, Sr, Ba), particularly, sodium, potassium, lithium, calcium, and magnesium, such as Ca and/or Mg. Furthermore, the detergent may comprise a hybrid detergent comprising any combination of sodium, potassium, lithium, calcium, or magnesium salts of sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates or other oil-soluble carboxylates of a Group 1 and/or 2 metal.

[0454] Preferably, the detergent additive(s) useful in the present disclosure comprises calcium and/or magnesium metal salts. The detergent may be a calcium and/or magnesium carboxylate (e.g., salicylates), sulfonate, or phenate detergent. More preferably, the detergent additives are selected from magnesium salicylate, calcium salicylate, magnesium sulfonate, calcium sulfonate, magnesium phenate, calcium phenate, and hybrid detergents comprising two, three, four, or more of more of these detergents and/or combinations thereof.

[0455] The metal-containing detergent may also include hybrid detergents formed with mixed surfactant systems including phenate and/or sulfonate components, e.g., phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, as described, for example, in U.S. Pat. Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179. Where, for example, a hybrid sulfonate/phenate detergent is employed, the hybrid detergent would be considered equivalent to amounts of distinct phenate and sulfonate detergents introducing like amounts of phenate and sulfonate soaps, respectively.

[0456] The overbased metal-containing detergent maybe sodium salts, calcium salts, magnesium salts, or mixtures thereof of the phenates, sulfur-containing phenates, sulfonates, salixarates, and salicylates. Overbased phenates and salicylates typically have a total base number of 180 to 650 mgKOH/g, such as 200 to 450 TBN mgKOH/g. Overbased sulfonates typically have a total base number of 250 to 600 mgKOH/g, or 300 to 500 mgKOH/g. In embodiments, the sulfonate detergent may be predominantly a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8 as is described in paragraphs [0026] to [0037] of US Patent Application Publication No. 2005/065045 (and granted as U.S. Pat. No. 7,407,919). The overbased detergent may be present at 0 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 0.2 wt % to 8 wt %, or 0.2 wt % to 3 wt %, based upon of the lubricating composition. For example, in a heavy-duty diesel engine, the detergent may be present at 2 wt % to 3 wt % of the lubricating composition. For a passenger car engine, the detergent may be present at 0.2 wt % to 1 wt % of the lubricating composition.

[0457] The detergent additive(s) may comprise one or more magnesium sulfonate detergents. The magnesium detergent may be a neutral salt or an overbased salt. Suitably the magnesium detergent is an overbased magnesium sulfonate having a TBN of from of from 5 to 700 mgKOH/g (ASTM D2896), or from 7 to 600 mgKOH/g, or from 9 to 500 mgKOH/g, or 80 to 650 mgKOH/g, such as 200 to 500 mgKOH/g, such as 240 to 450 mgKOH/g.

[0458] Alternately, the detergent additive(s) is a magnesium salicylate. Suitably the magnesium detergent is a magnesium salicylate having TBN of from 5 to 700 mgKOH/g (ASTM D2896), or from 7 to 600 mgKOH/g, or from 9 to 500 mgKOH/g, 30 to 650 mgKOH/g, such as 50 to 500 mgKOH/g, such as 200 to 500 mgKOH/g, such as 240 to 450 mgKOH/g or alternately of 150 mgKOH/g or less, such as 100 mgKOH/g or less.

[0459] Alternately, the detergent additive(s) is a combination of magnesium salicylate and magnesium sulfonate.

[0460] The magnesium detergent provides the lubricating composition thereof with from 500-4000 ppm of magnesium atoms, suitably from 700-2000 ppm, from 800 to 1500 or from 1000-1200 ppm of magnesium atoms (ASTM D5185).

[0461] The detergent composition may comprise (or consist of) a combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents.

[0462] The detergent may comprise one or more calcium detergents such as calcium carboxylate (e.g., salicylate), sulfonate, or phenate detergent.

[0463] Suitably the calcium detergent has a TBN of from 30 to 1400 mgKOH/g (ASTM D2896), such as 80 to 1200 mgKOH/g, such as 100 to 1000 mgKOH/g, such as 150 to 800 mgKOH/g, such as 200 to 600 mgKOH/g, such as 240 to 550 mgKOH/g, or alternately of 150 mgKOH/g or less, such as 100 mgKOH/g or less, or 200 mgKOH/g or more, or 300 mgKOH/g or more, or 350 mgKOH/g or more. The calcium detergent preferably has a TBN of greater than or equal 500, or 600, or 700, or 800, or 1000, or 1200, or 1300, or 1400 mgKOH/g.

[0464] Suitably, the calcium detergent is a calcium salicylate, sulfonate, or phenate having a TBN of from 30 to 1400 mgKOH/g, 30 to 1200 mgKOH/g (ASTM D2896), such as 50 to 1000 mgKOH/g, such as 200 to 800 mgKOH/g, such as 240 to 600 mgKOH/g or alternately of 150 mgKOH/g or less, such as 100 mgKOH/g or less, or 200 mgKOH/g or more, or 300 mgKOH/g or more, or 350 mgKOH/g or more, or 500 mgKOH/g or more, or 700 mgKOH/g or more, or 900 mgKOH/g or more, or 1100 mgKOH/g or more, or 1300 mgKOH/g or more.

[0465] Calcium detergent is typically present in amount sufficient to provide at least 400 ppm, or at least 500 ppm, or at least 520 ppm, or at least 540 ppm, or at least 560 ppm, or at least 580 ppm, or at least 600 ppm, or at least 650 ppm, or at least 700 ppm, or at least 750 ppm, or at least 800 ppm, or at least 850 ppm, or at least 900 ppm, or at least 1000 ppm, or at least 1100 ppm, or at least 1200 ppm by weight of calcium to the composition (ASTM D5185).

[0466] Suitably the total atomic amount of metal from detergent in the lubrication composition according to all aspects of the disclosure is no more than 5000 ppm, preferably no more than 4000 m and more preferably no more than 2000 ppm (ASTM D5185). The total amount of atomic metal from detergent in the lubrication oil composition according to all aspects of the disclosure is suitably at least 500 ppm, preferably at least 800 ppm and more preferably at least 1000 ppm (ASTM D5185). The total amount of atomic metal from detergent in the lubrication oil composition according to all aspects of the disclosure is suitably from 500 to 5000 ppm, preferably from 500 to 3000 ppm and more preferably from 500 to 2500 ppm (ASTM D5185).

[0467] Sulfonate detergents may be prepared from sulfonic acids which are typically obtained by the sulfonation of alkyl substituted aromatic hydrocarbons, such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl, or their halogen derivatives such as chlorobenzene, chlorotoluene, and chloronaphthalene. The alkylation may be carried out in the presence of a catalyst with alkylating agents having from about 3 to more than 70 carbon atoms. The alkaryl sulfonates usually contain from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms per alkyl substituted aromatic moiety. The oil soluble sulfonates or alkaryl sulfonic acids may be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylate, sulfides, hydrosulfides, nitrates, borates and ethers of the metal. The amount of metal compound is chosen having regard to the desired TBN of the final product, but typically ranges from about 100 to 220 mass (preferably at least 125 mass %) of that stoichiometrically required.

[0468] Metal salts of phenols and sulfurized phenols are prepared by reaction with an appropriate metal compound such as an oxide or hydroxide and neutral or overbased products may be obtained by methods well known in the art. Sulfurized phenols may be prepared by reacting a phenol with sulfur or a sulfur-containing compound such as hydrogen sulfide, sulfur monohalide, or sulfur dihalide, to form products which are generally mixtures of compounds in which 2 or more phenols are bridged by sulfur-containing bridges.

[0469] Carboxylate detergents, e.g., salicylates, can be prepared by reacting an aromatic carboxylic acid (such as a C.sub.5-100, C.sub.9-30, C.sub.14-24 alkyl-substituted hydroxy-benzoic acid) with an appropriate metal compound such as an oxide or hydroxide and neutral or overbased products may be obtained by methods well known in the art. The aromatic moiety of the aromatic carboxylic acid can contain heteroatoms, such as nitrogen and oxygen. Preferably, the moiety contains only carbon atoms; more preferably the moiety contains six or more carbon atoms; for example, benzene is a preferred moiety. The aromatic carboxylic acid may contain one or more aromatic moieties, such as one or more benzene rings, either fused or connected via alkylene bridges.

[0470] Preferred substituents in oil-soluble salicylic acids are alkyl substituents. In alkylsubstituted salicylic acids, the alkyl groups advantageously contain 5 to 100, preferably 9 to 30, especially 14 to 20, carbon atoms. Where there is more than one alkyl group, the average number of carbon atoms in all of the alkyl groups is preferably at least 9 to ensure adequate oil solubility.

[0471] Further, as metal organic and inorganic base salts, which are used as detergents can contribute to the sulfated ash content of a lubricating oil composition, in embodiments of the present disclosure, the amounts of such additives are minimized. In order to maintain a low sulfur level, salicylate detergents can be used and the lubricating composition herein may comprise one or more salicylate detergents (said detergents are preferably used in amounts in the range of 0.05 to 20.0 wt %, more preferably from 1.0 to 10.0 wt % and most preferably in the range of from 2.0 to 5.0 wt %, based on the total weight of the lubricating composition).

[0472] The total sulfated ash content of the lubricating composition herein is typically not greater than 5.0 wt %, alternately at a level of not greater than 3.5 wt % and alternately at a level of not greater than 1.5 wt %, based on the total weight of the lubricating composition as determined by ASTM D874.

[0473] Furthermore, it is useful that each of the detergents, independently, have a TBN (total base number) value in the range of from 10 to 700 mgKOH/g, 10 to 500 mgKOH/g, alternately in the range of from 100 to 650, alternately in the range of from 10 to 500 mgKOH/g, alternately in the range of from 30 to 350 mgKOH/g, and alternately in the range of from 50 to 300 mgKOH/g, as measured by ISO 3771.

[0474] The sulfonate detergents (such as Ca and/or Mg sulfonate detergents) may be present in an amount to deliver 0.1 wt % to 1.5 wt %, or 0.15 to 1.2 wt %, or 0.2 wt % to 0.9 wt % sulfonate soap to the lubricant composition.

[0475] The salicylate detergents (such as Ca and/or Mg salicylate detergents) are present in an amount to deliver 0.3 wt % to 1.4 wt %, or 0.35 wt % to 1.2 wt %, or 0.4 wt % to 1.0 wt % salicylate soap to the lubricant composition.

[0476] The sulfonate soap may be present in an amount 0.2 wt % to 0.8 wt % of the lubricant composition, and the salicylate soap may be present in an amount 0.3 wt % to 1.0 wt % of the lubricant composition.

[0477] The total of all alkaline earth metal detergent soap maybe present in an amount 0.6 wt % to 2.1 wt %, or 0.7 wt % to 1.4 wt % of the lubricant composition.

[0478] Typically, lubricating compositions formulated for use in heavy-duty diesel engines comprise detergents at from about 0.1 to about 10 mass %, alternately from about 0.5 to about 7.5 mass %, alternately from about 1 to about 6.5 mass %, based on the lubricating composition.

[0479] Typically, lubricating compositions formulated for use in a passenger-car engines comprise detergents at from about 0.1 to about 10 mass %, alternately from about 0.5 to about 7.5 mass %, alternately from about 1 to about 6.5 mass %, based on the lubricating composition.

[0480] Typically, lubricating compositions formulated for use in a drive train (e.g., transmissions) comprise detergents at from about 0.1 to about 10 mass %, alternately from about 0.5 to about 7.5 mass %, alternately from about 2 to about 6.5 mass %, based on the lubricating composition.

[0481] Typically, lubricating oil compositions formulated for use in marine or stationary gas engines comprise detergents at from about 0.1 to about 15 mass %, alternately from about 0.5 to about 12 mass %, alternately from about 2 to about 6 mass %, based on the total lubricating oil composition.

D. Friction Modifiers

[0482] A friction modifier is any material or materials that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid-containing such material(s). Friction modifiers, also known as friction reducers, or lubricity agents or oiliness agents, and other such agents that change the ability of base oils, formulated lubricating compositions, concentrate compositions or functional fluids, to modify the coefficient of friction of a lubricated surface may be effectively used in combination with the base oils or lubricating compositions of the present disclosure if desired. Friction modifiers that lower the coefficient of friction are particularly advantageous in combination with the base oils and lubricating compositions of this disclosure.

[0483] Illustrative friction modifiers may include, for example, organometallic compounds or materials, or mixtures thereof. Illustrative organometallic friction modifiers useful in the lubricating oil formulations of this disclosure include, for example, tungsten and/or molybdenum compounds, such as molybdenum amine, molybdenum diamine, an organotungstenate, a molybdenum dithiocarbamate, molybdenum dithiophosphates, molybdenum amine complexes, molybdenum carboxylates, and the like, and mixtures thereof. Examples of useful molybdenum-containing compounds may conveniently include molybdenum dithiocarbamates, trinuclear molybdenum compounds, for example, as described in PCT Publication No. WO 98/26030, sulfides of molybdenum and molybdenum dithiophosphate.

[0484] Other known friction modifiers comprise oil-soluble organo-molybdenum compounds. Such organo-molybdenum friction modifiers may also provide antioxidant and antiwear credits to a lubricating oil composition. Examples of such oil-soluble organo-molybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof. Particularly preferred are molybdenum dithiocarbamates, dialkyldithiophosphates, alkyl xanthates and alkylthioxanthates.

[0485] Additionally, the molybdenum compound may be an acidic molybdenum compound. These compounds will react with a basic nitrogen compound as measured by ASTM test D664 or D2896 titration procedure and are typically hexavalent. Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, e.g., hydrogen sodium molybdate, MoOC.sub.14, MoO.sub.2Br2, Mo.sub.2O.sub.3C.sub.16, molybdenum trioxide or similar acidic molybdenum compounds.

[0486] Among the molybdenum compounds useful in the compositions of this disclosure are organo-molybdenum compounds of the formula Mo(ROCS.sub.2).sub.4 and Mo(RSCS.sub.2).sub.4, wherein R is an organo group selected from the group consisting of alkyl, aryl, aralkyl and alkoxyalkyl, generally of from 1 to 30 carbon atoms, and preferably 2 to 12 carbon atoms and most preferably alkyl of 2 to 12 carbon atoms. Especially preferred are the dialkyldithiocarbamates of molybdenum.

[0487] Another group of organo-molybdenum compounds useful in the lubricating compositions of this disclosure are trinuclear molybdenum compounds, especially those of the formula Mo3SkLnQz and mixtures thereof wherein the L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron-donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At least 21 carbon atoms should be present among all the ligand/organo groups, such as at least 25, at least 30, or at least 35, carbon atoms.

[0488] Lubricating oil compositions useful in all aspects of the present disclosure preferably contain at least 10 ppm, or at least 12 ppm, or at least 20 ppm molybdenum. Suitably, lubricating oil compositions useful in all aspects of the present disclosure contain no more than 1000 ppm, no more than 750 ppm, no more than 500 ppm, no more than 350 ppm, or more preferably no more than 200 ppm of molybdenum. Lubricating oil compositions useful in all aspects of the present disclosure preferably contain from 12 to 350 ppm, such as 12 to 500 ppm, or 20 to 200 ppm of molybdenum (measured as atoms of molybdenum).

[0489] For more information or useful friction modifiers containing Mo, please see U.S. Pat. No. 10,829,712 (col 8, ln 58 to col 11, ln 31). Particularly preferred friction modifiers containing Mo of the instant disclosure are dimeric molybdenum dialkyldithiocarbamate (moly dimer), a trimeric molybdenum dialkyldithiocarbamate (moly trimer), or a combination thereof.

[0490] Ashless friction modifiers may be present in the lubricating oil compositions of the present disclosure and are known generally and include esters formed by reacting carboxylic acids and anhydrides with alkanols and amine-based friction modifiers. Other useful friction modifiers generally include a polar terminal group (e.g., carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. Esters of carboxylic acids and anhydrides with alkanols are described in U.S. Pat. No. 4,702,850. Examples of other conventional organic friction modifiers are described by M. Belzer in the Journal of Tribology (1992), Vol. 114, pp. 675-682 and M. Belzer and S. Jahanmir in Lubrication Science (1988), Vol. 1, pp. 3-26. Typically, the total amount of organic ashless friction modifier in a lubricant according to the present disclosure does not exceed 5 mass %, based on the total mass of the lubricating oil composition and preferably does not exceed 2 mass % and more preferably does not exceed 0.5 mass %.

[0491] Illustrative friction modifiers useful in the lubricating compositions described herein include, for example, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof.

[0492] Illustrative alkoxylated fatty acid esters include, for example, polyoxyethylene stearate, fatty acid polyglycol ester, and the like. These can include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isosterate, polyoxypropylene isostearate, polyoxyethylene palmitate, and the like.

[0493] Illustrative alkanolamides include, for example, lauric acid diethylalkanolamide, palmic acid diethylalkanolamide, and the like. These can include oleic acid diethyalkanolamide, stearic acid diethylalkanolamide, oleic acid diethylalkanolamide, polyethoxylated hydrocarbylamides, polypropoxylated hydrocarbylamides, and the like.

[0494] Illustrative polyol fatty acid esters include, for example, glycerol monooleate, saturated mono-, di-, and tri-glyceride esters, glycerol monostearate, and the like. These can include polyol esters, hydroxyl-containing polyol esters, and the like.

[0495] Illustrative borated glycerol fatty acid esters include, for example, borated glycerol monooleate, borated saturated mono-, di-, and tri-glyceride esters, borated glycerol monosterate, and the like. In addition to glycerol polyols, these can include trimethylolpropane, pentaerythritol, sorbitan, and the like. These esters can be polyol monocarboxylate esters, polyol dicarboxylate esters, and on occasion polyoltricarboxylate esters. Preferred can be the glycerol monooleates, glycerol di-oleates, glycerol tri-oleates, glycerol mono-oleates, glycerol di-stearates, and glycerol tri-stearates and the corresponding glycerol mono-palmitates, glycerol di-palmitates, and glycerol tri-palmitates, and the respective isostearates, linoleates, and the like. Ethoxylated, propoxylated, and/or butoxylated fatty acid esters of polyols, especially using glycerol as underlying polyol are useful herein.

[0496] Illustrative fatty alcohol ethers include, for example, stearyl ether, myristyl ether, and the like. Alcohols, including those that have carbon numbers from C.sub.3 to C.sub.50, can be ethoxylated, propoxylated, or butoxylated to form the corresponding fatty alkyl ethers. The underlying alcohol portion can preferably be stearyl, myristyl, C.sub.11-C.sub.13 hydrocarbon, oleyl, isosteryl, and the like.

[0497] Useful concentrations of friction modifiers may range from 0.01 wt % to 5 wt %, or about 001 wt % to about 2.5 wt %, or about 0.05 wt % to about 1.5 wt %, or about 0.051 wt % to about 1 wt %. Concentrations of molybdenum-containing materials are often described in terms of Mo metal concentration. Advantageous concentrations of Mo may range from 12 ppm to 350 ppm or more, and often with a preferred range of 20 to 200 ppm. Friction modifiers of all types may be used alone or in mixtures with the materials of this disclosure. Often mixtures of two or more friction modifiers, or mixtures of friction modifier(s) with alternate surface-active material(s), are also desirable. For example, combinations of Mo-containing compounds with polyol fatty acid esters, such as glycerol mono-oleate are useful herein.

E. Antioxidants

[0498] Antioxidants retard the oxidative degradation of base oils during service. Such degradation may result in deposits on metal surfaces, the presence of sludge, a viscosity increase in a lubricant, and the like. A wide variety of oxidation inhibitors that are useful in lubricating oil compositions. See Lubricants and Related Products, Klamann, Wiley VCH, 1984; U.S. Pat. Nos. 4,798,684 and 5,084,197, for example.

[0499] Useful antioxidants include hindered phenols. These phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are the hindered phenolics, which contain a sterically hindered hydroxyl group, and these include those derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in the o- or p-position to each other. Typical phenolic antioxidants include the hindered phenols substituted with C.sub.6 alkyl groups and the alkylene coupled derivatives of these hindered phenols. Examples of phenolic materials of this type 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol; 2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4-heptyl phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol. Other useful hindered mono-phenolic antioxidants may include, for example, hindered 2,6-di-alkyl-phenolic proprionic ester derivatives. Bis-phenolic antioxidants may also be advantageously used herein. Examples of ortho-coupled phenols include: 2,2-bis(4-heptyl-6-t-butyl-phenol); 2,2-bis(4-octyl-6-t-butyl-phenol); and 2,2-bis(4-dodecyl-6-t-butyl-phenol). Para-coupled bisphenols include, for example, 4,4-bis(2,6-di-t-butyl-phenol) and 4,4-methylene-bis(2,6-di-t-butyl-phenol).

[0500] Effective amounts of one or more catalytic antioxidants may also be used. The catalytic antioxidants comprise an effective amount of a) one or more oil soluble polymetal organic compounds; and effective amounts of b) one or more substituted N,N-diaryl-o-phenylenediamine compounds or c) one or more hindered phenol compounds; or a combination of both b) and c). Catalytic antioxidants useful herein are more fully described in U.S. Pat. No. 8,048,833.

[0501] Non-phenolic oxidation inhibitors, which may be used include aromatic amine antioxidants and these may be used either as such or in combination with phenolics. Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines such as aromatic monoamines of the formula R.sub.8R.sub.9R.sub.10N, where R.sub.8 is an aliphatic, aromatic or substituted aromatic group, R.sub.9 is an aromatic or a substituted aromatic group, and R.sub.10 is H, alkyl, aryl or R.sub.11S(O)XR.sub.12 where R.sub.11 is an alkylene, alkenylene, or aralkylene group, R.sub.12 is an alkyl group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1, or 2. The aliphatic group R.sub.8 may contain from 1 to about 20 carbon atoms, and preferably contains from about 6 to 12 carbon atoms. The aliphatic group is typically a saturated aliphatic group. Preferably, both R.sub.8 and R.sub.9 are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl. Aromatic groups R.sub.8 and R.sub.9 may be joined together with other groups such as S.

[0502] Typical aromatic amines antioxidants have alkyl substituent groups of at least about 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups will not contain more than about 14 carbon atoms. The general types of amine antioxidants useful in the present compositions include diphenylamines, phenyl naphthylamines, phenothiazines, imidodibenzyls and diphenyl phenylene diamines. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used. Particular examples of aromatic amine antioxidants useful in the present disclosure include: p,p-dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine; phenyl-alpha-naphthylamine; and p-octylphenyl-alpha-naphthylamine.

[0503] Sulfur-containing antioxidants are also useful herein. In particular, one or more oil-soluble or oil-dispersible sulfur-containing antioxidant(s) can be used as an antioxidant additive. For example, sulfurized alkyl phenols and alkali or alkaline earth metal salts thereof also are useful antioxidants herein. Suitably, the lubricating oil composition(s) of the present disclosure may include the one or more sulfur-containing antioxidant(s) in an amount to provide the lubricating oil composition with from 0.02 to 0.2, preferably from 0.02 to 0.15, even more preferably 0.02 to 0.1, even more preferably 0.04 to 0.1, mass % sulfur based on the total mass of the lubricating oil composition. Optionally the oil-soluble or oil-dispersible sulfur-containing antioxidant(s) are selected from sulfurized C.sub.4 to C.sub.25 olefin(s), sulfurized aliphatic (C.sub.7 to C.sub.29) hydrocarbyl fatty acid ester(s), ashless sulfurized phenolic antioxidant(s), sulfur-containing organo-molybdenum compound(s), and combinations thereof. For further information on sulfurized materials useful as antioxidants herein, please see U.S. Pat. No. 10,731,101 (col 15, ln 55 to col 22, ln 12).

[0504] Antioxidants useful herein include hindered phenols and/or arylamines. These antioxidants may be used individually by type or in combination with one another.

[0505] Typical antioxidants include: Irganox L67, Irganox L135, Ethanox 4702, Lanxess Additin RC 7110; Ethanox 4782J; Irganox 1135, Irganox 5057, sulfurized lard oil and palm oil fatty acid methyl ester.

[0506] Antioxidant additives may be used in an amount of about 0.01 to 10 (alternately 0.01 to 5, alternately 0.01 to 3 wt %, alternately 1 to 6 wt %, alternately 2 to 5 wt %, alternately 3 to 4 wt %, alternately about 0.03 to 5 wt %, alternately 0.05 to less than 3 wt %, based upon the weight of the lubricating composition.

[0507] Compositions according to the present disclosure may contain an additive having a different enumerated function that also has secondary effects as an antioxidant (for example, phosphorus-containing antiwear agents (such as ZDDP) may also have antioxidant effects). These additives are not included as antioxidants for purposes of determining the amount of antioxidant in a lubricating oil composition or concentrate herein.

F. Pour Point Depressants

[0508] Conventional pour point depressants (also known as lube oil flow improvers) may be added to the compositions of the present disclosure if desired. These pour point depressants may be added to lubricating compositions of the present disclosure to lower the minimum temperature at which the fluid will flow or can be poured. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers. U.S. Pat. Nos. 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655,479; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe useful pour point depressants and/or the preparation thereof. Such additives may be used in an amount of about 0.01 to 5 wt %, preferably about 0.01 to 1.5 wt %, based upon the weight of the lubricating composition.

G. Anti-Foam Agents

[0509] Anti-foam agents may advantageously be added to lubricant compositions described herein. These agents prevent or retard the formation of stable foams. Silicones and/organic polymers are typical anti-foam agents. For example, polysiloxanes, such as silicon oil or polydimethyl siloxane, provide anti-foam properties.

[0510] Anti-foam agents are commercially available and may be used in minor amounts such as 5 wt % or less, 3 wt % or less, 1 wt % or less, 0.1 wt % or less, such as from 5 to wt % to 0.1 ppm such as from 3 wt % to 0.5 ppm, such as from 1 wt % to 10 ppm.

[0511] For example, it may be that the lubricating oil composition comprises an anti-foam agent comprising polyalkyl siloxane, such as a polydialkyl siloxane, for example, wherein the alkyl is a C.sub.1-C.sub.10 alkyl group, e.g., a polydimethylsiloxane (PDMS), also known as a silicone oil. Alternately, the siloxane is a poly(R.sup.3)siloxane, wherein R.sup.3 is one or more same or different linear branched or cyclic hydrocarbyls, such as alkyls or aryls, typically having 1 to 20 carbon atoms. It may be that, for example, the lubricating oil composition comprises a polymeric siloxane compound according to Formula 1 below wherein R.sup.1 and R.sup.2 are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, phenyl, naphthyl, alkyl substituted phenyl, or isomers thereof (such as methyl, phenyl) and n is from 2 to 1000, such as 50 to 450, alternately such as 40 to 100.

[0512] Additionally, or alternatively, it may be that the lubricating oil composition comprises an organo-modified siloxane (OMS), such as a siloxane modified with an organo group such as a polyether (e.g., ethylene-propyleneoxide copolymer), long chain hydrocarbyl (e.g., C.sub.11-C.sub.100 alkyl), or aryl (e.g., C.sub.6-C.sub.14 aryl). It may be that, for example, the lubricating oil composition comprises an organo-modified siloxane compound according to Formula 1, wherein n is from 2 to 2000, such as 50 to 450 (alternately such as 40 to 100), and wherein R.sup.1 and R.sup.2 are the same or different, optionally wherein each of R.sup.1 and R.sup.2 is, independently an organo group, such as an organo group selected from polyether (e.g., ethylene-propyleneoxide copolymer), long chain hydrocarbyl (e.g., C.sub.11-C.sub.100 alkyl), or aryl (e.g., C.sub.6-C.sub.14 aryl). Preferably, one of R.sup.1 and R.sup.2 is CH.sub.3.

##STR00013##

[0513] Based on the total weight of the lubricant composition, the siloxane according to Formula 1 is incorporated so as to provide about 0.1 to less than about 30 ppm Si, or about 0.1 to about 25 ppm Si, or about 0.1 to about 20 ppm Si, or about 0.1 to about 15 ppm Si, or about 0.1 to about 10 ppm Si. More preferably, it is in the range of about 3-10 ppm Si.

[0514] In embodiments, silicone anti-foam agents useful herein are available from Dow Corning Corporation and Union Carbide Corporation, such as Dow Corning FS-1265 (1000 centistokes), Dow Corning DC-200, and Union Carbide UC-L45. Silicone anti-foamants useful herein include polydimethylsiloxane, phenyl-methyl polysiloxane, linear, cyclic or branched siloxanes, silicone polymers and copolymers, and/organo-silicone copolymers. Also, a siloxane polyether copolymer Anti-foamant available from OSI Specialties, Inc. of Farmington Hills, Michigan and may be substituted or included. One such material is sold as SILWET-L-7220.

[0515] Acrylate polymer anti-foam agent can also be used herein. Typical acrylate anti-foamants include polyacrylate anti-foamant available from Monsanto Polymer Products Co. known as PC-1244. A preferred acrylate polymer anti-foam agent useful herein is PX3841 (i.e., an alkyl acrylate polymer), commercially available from Dorf Ketl, also referred to as Mobilad C402.

[0516] In embodiments, a combination of sililcone anti-foamant and acrylate anti-foamant can be used, such as at a weight ratio of the silicone anti-foamant to the acrylate anti-foamant of from about 5:1 to about 1:5, see, for example, US Patent Application Publication No. 2021/0189283.

H. Viscosity Modifiers

[0517] Viscosity modifiers (also referred to as viscosity index improvers or viscosity improvers) can be included in the lubricating compositions and concentrate compositions described herein. Viscosity modifiers provide lubricants with high and low temperature operability. These additives impart shear stability at elevated temperatures and acceptable viscosity at low temperatures. Suitable viscosity modifiers include high molecular weight hydrocarbons, polyesters, and viscosity modifier dispersants that can function as both a viscosity modifier and a dispersant. Typical molecular weights of these polymers are between about 10,000 to 1,500,000 g/mol, more typically about 20,000 to 1,200,000 g/mol, and even more typically between about 50,000 and 1,000,000 g/mol.

[0518] Examples of suitable viscosity modifiers are linear or star-shaped polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes. Polyisobutylene is a commonly used viscosity modifier. Another suitable viscosity modifier is polymethacrylate (copolymers of various chain length alkyl methacrylates, for example), some formulations of which also serve as pour point depressants. Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (copolymers of various chain length acrylates, for example). Specific examples include styrene-isoprene or styrene-butadiene based polymers of 50,000 to 200,000 g/mol molecular weight.

[0519] Copolymers useful as viscosity modifiers include those commercially available from Chevron Oronite Company LLC under the trade designation PARATONE (such as PARATONE 8921, PARATONE 68231, and PARATONE 8941); from Afton Chemical Corporation under the trade designation HiTEC (such as HiTEC 5850B, and HiTEC5777); and from The Lubrizol Corporation under the trade designation Lubrizol 7067C. Hydrogenated polyisoprene star polymers useful as viscosity modifiers herein include those commercially available from Infineum International Limited, e.g., under the trade designation SV200 and SV600. Hydrogenated diene-styrene block copolymers useful as viscosity modifiers herein are commercially available from Infineum International Limited, e.g., under the trade designation SV 50.

[0520] Polymers useful as viscosity modifiers herein include polymethacrylate or polyacrylate polymers, such as linear polymethacrylate or polyacrylate polymers, such as those available from Evnoik Industries under the trade designation Viscoplex (e.g., Viscoplex 6-954) or star polymers which are available from Lubrizol Corporation under the trade designation Asteric (e.g., Lubrizol 87708 and Lubrizol 87725).

[0521] Vinyl aromatic-containing polymers useful as viscosity modifiers herein may be derived from vinyl aromatic hydrocarbon monomers, such as styrenic monomers, such as styrene. Illustrative vinyl aromatic-containing copolymers useful herein may be represented by the following general formula: A-B wherein A is a polymeric block derived predominantly from vinyl aromatic hydrocarbon monomer (such as styrene), and B is a polymeric block derived predominantly from conjugated diene monomer (such as isoprene).

[0522] Vinyl aromatic-containing polymers useful as viscosity modifiers may have a Kinematic viscosity at 1000 C of 20 cSt or less, such as 15 cSt or less, such as 12 cSt or less, but may be diluted (such as in Group I, II, and/or III basestock) to higher Kinematic viscosities at 100 C., such as to 40 cSt or more, such as 100 cSt or more, such as 1000 cSt or more, such as 1000 to 2000 cSt.).

[0523] Typically, the viscosity modifiers may be used in an amount of about 0.01 to about 10 wt %, such as about 0.1 to about 7 wt %, such as 0.1 to about 4 wt %, such as about 0.2 to about 2 wt %, such as about 0.2 to about 1 wt %, and such as about 0.2 to about 0.5 wt %, based on the total weight of the formulated lubricant composition.

[0524] Viscosity modifiers are typically added as concentrates, in large amounts of diluent oil. The as delivered viscosity modifier typically contains from 20 wt % to 75 wt % of an active polymer for polymethacrylate or polyacrylate polymers, or from 8 wt % to 20 wt % of an active polymer for olefin copolymers, hydrogenated polyisoprene star polymers, or hydrogenated diene-styrene block copolymers, in the as delivered polymer concentrate.

L. Dispersants

[0525] During engine operation, oil-insoluble oxidation byproducts are produced. Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces. Dispersants used in the formulation of the lubricating compositions herein may be ashless or ash-forming in nature. Preferably, the dispersant is ashless. So called ashless dispersants are organic materials that form substantially no ash upon combustion. For example, non-metal-containing or borated metal-free dispersants are considered ashless. In contrast, metal-containing detergents tend to form ash upon combustion.

[0526] Dispersants useful herein typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain. The polar group typically contains at least one element of nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain 40 to 500, such as 50 to 400 carbon atoms.

Dispersants of (Poly)Alkenylsuccinic Derivatives

[0527] A particularly useful class of dispersants includes the (poly)alkenylsuccinic derivatives, typically produced by the reaction of a long chain hydrocarbyl-substituted succinic compound, usually a hydrocarbyl-substituted succinic anhydride, with a polyhydroxy or polyamino compound. The long chain hydrocarbyl group constituting the oleophilic portion of the molecule which confers solubility in the oil, is often a polyisobutylene group (typically the long chain hydrocarbyl group, such as a polyisobutylene group, has an Mn of 400 to 3000 g/mol, such as 450 to 2500 g/mol). Many examples of this type of dispersant are well known commercially and in the literature. Exemplary US Patents describing such dispersants include U.S. Pat. Nos. 3,172,892; 3,2145,707; 3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012; 3,630,904; 3,632,511; 3,787,374 and 4,234,435. Other types of dispersants are described in U.S. Pat. Nos. 3,036,003; 3,200,107; 3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574; 3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; 5,705,458. A further description of dispersants useful herein may be found, for example, in European Patent Applications Nos. 0 471 071 and 0 451 380, to which reference is made for this purpose.

[0528] Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants. In particular, succinimide, succinate esters, or succinate ester amides prepared by the reaction of a hydrocarbon-substituted succinic acid or anhydride compound (typically having at least 25 carbon atoms, such as 28 to 400 carbon atoms, in the hydrocarbon substituent), with at least one equivalent of a polyhydroxy or polyamino compound (such as an alkylene amine) are particularly useful herein. Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives may have a number average molecular weight of at least 400 g/mol, such as at least 900 g/mol, such as at least 1500 g/mol, such as from 400 to 4000 g/mol, such as from 800 to 3000, such as from 2000 to 2800 g/mol, such from about 2100 to 2500 g/mol, and such as from about 2200 to about 2400 g/mol.

[0529] Succinimides, which are particularly useful herein, are formed by the condensation reaction between: 1) hydrocarbyl-substituted succinic anhydrides, such as polyisobutylene succinic anhydride (PIBSA); and 2) polyamine (PAM). Examples of suitable polyamines include: polyhydrocarbyl polyamines, polyalkylene polyamines, hydroxy-substituted polyamines, polyoxyalkylene polyamines, and combinations thereof. Examples of polyamines include tetraethylene pentamine, pentaethylene hexamine, tetraethylenepentamine (TEPA), pentaethylenehaxamine (PEHA), N-phenyl-p-phenylenediamine (ADPA), and other polyamines having an average of 5, 6, 7, 8, or 9 nitrogen atoms per molecule. Mixtures where the average number of nitrogen atoms per polyamine molecule is greater than 7 are commonly called heavy polyamines or H-PAMs and may be commercially available under trade names such as HPA and HPA-X from Dow Chemical, E-100 from Huntsman Chemical, et al. Examples of hydroxy-substituted polyamines include N-hydroxyalkyl-alkylene polyamines such as N-(2-hydroxyethyl)ethylene diamine, N-(2-hydroxyethyl)piperazine, and/or N-hydroxyalkylated alkylene diamines of the type described, for example, in U.S. Pat. No. 4,873,009. Examples of polyoxyalkylene polyamines include polyoxyethylene and/or polyoxypropylene diamines and triamines (as well as co-oligomers thereof) having an average Mn from about 200 to about 5000 g/mol. Products of this type are commercially available under the tradename Jeffamine. Representative examples of useful succinimides are shown in U.S. Pat. Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; 3,652,616; 3,948,800; and 6,821,307; and CA Patent No. 1,094,044.

[0530] The dispersants may comprise one or more, optionally borated, higher molecular weight (Mn 1600 g/mol or more, such as 1800 to 3000 g/mol) succinimides and one or more, optionally borated, lower molecular weight (Mn less than 1600 g/mol) succinimides, where the higher molecular weight may be 1600 to 3000 g/mol, such as 1700 to 2800 g/mol, such as 1800 to 2500 g/mol, such as 1850 to 2300 g/mol; and the lower molecular weight may be 600 to less than 1600 g/mol, such as 650 to 1500 g/mol, such as 700 to 1400 g/mol, such as 800 to 1300 g/mol, such as 850 to 1200 g/mol such as 900 to 1150 g/mol, such as 900 to 1000.0 g/mol, such as about 950 g/mol. The higher molecular weight succinimide dispersant may be present in the lubricating composition in an amount of from 0.5 to 10 wt %, or from 0.8 to 6 wt %, or from 1.0 to 5 wt %, or from 1.5 to 5 wt %, or from 1.5 to 4.0 wt %; and the lower molecular weight succinimides dispersant may be present in the lubricating composition in an amount of from 1 to 5 wt %, or from 1.5 to 4.8 wt %, or from 1.8 to 4.6 wt %, or from 1.9 to 4.6 wt %, or at 2 wt % or more, such as 2 to 5 wt %. The lower molecular weight succinimides may differ from the higher molecular weight succinimides, by 500 g/mol or more, such as by 750 g/mol or more, such as by 1000 g/mol or more, such as by 1200 g/mol or more, such as by 500 to 3000 g/mol, such as by 750 to 2000 g/mol, such as by 1000 to 1500 g/mol.

[0531] Succinate esters useful as dispersants include those formed by the condensation reaction between hydrocarbyl-substituted succinic anhydrides and alcohols or polyols. For example, the condensation product of a hydrocarbyl-substituted succinic anhydride and pentaerythritol is a useful dispersant.

[0532] Succinate ester amides useful herein are formed by a condensation reaction between hydrocarbyl-substituted succinic anhydrides and alkanol amines. Suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines, and polyalkenylpolyamines such as polyethylene polyamines and/or propoxylated hexamethylenediamine. Representative examples are shown in U.S. Pat. No. 4,426,305.

[0533] Hydrocarbyl-substituted succinic anhydrides (such as PIBSA) esters of hydrocarbyl bridged aryloxy alcohols are also useful as dispersants herein. For information on such dispersants, please see U.S. Pat. No. 7,485,603, particularly, col 2, In 65 to col 6, In 22 and col 23, In 40 to col 26, In 46. In particular, PIBSA esters of methylene-bridged naphthyloxy ethanol (i.e., 2-hydroxyethyl-1-naphthol ether (or hydroxy-terminated ethylene oxide oligomer ether of naphthol) are useful herein.

[0534] The molecular weight of the hydrocarbyl-substituted succinic anhydrides used in the preceding paragraphs will typically range from 350 to 4000 g/mol, such as 400 to 3000 g/mol, such as 450 to 2800 g/mol, such as 800 to 2500 g/mol. The above (poly)alkenylsuccinic derivatives can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid.

[0535] The dispersants may be present in the lubricant in an amount 0.1 mass % to 20 mass % of the composition, such as 0.2 to 15 mass %, such as 0.25 to 10 mass %, such as 0.3 to 5 mass %, such as 1.0 mass % to 3.0 mass %, of the lubricating oil composition.

[0536] The above (poly)alkenylsuccinic derivatives, can also be post reacted with boron compounds such as boric acid, borate esters or highly borated dispersants, to form borated dispersants generally having from about 0.1 to about 5 moles of boron per mole of dispersant reaction product.

[0537] Dispersants useful herein include borated succinimides, including those derivatives from mono-succinimides, bis-succinimides, and/or mixtures of mono- and bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polyisobutylene having an Mn of from about 300 to about 5000 g/mol, or from about 500 to about 3000 g/mol, or about 1000 to about 2000 g/mol, or a mixture of such hydrocarbylene groups, often with high terminal vinylic groups.

[0538] The boron-containing dispersant may be present at 0.01 wt % to 20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 0.5 wt % to 8 wt %, or 1.0 wt % to 6.5 wt %, or 0.5 wt % to 2.2 wt % of the lubricating composition.

[0539] The boron-containing dispersant may be present in an amount to deliver boron to the composition at 15 ppm to 2000 ppm, or 25 ppm to 1000 ppm, or 40 ppm to 600 ppm, or 80 ppm to 350 ppm.

[0540] The borated dispersant may be used in combination with non-borated dispersant and may be the same or different compound as the non-borated dispersant. In one embodiment, the lubricating composition may include one or more boron-containing dispersants and one or more non-borated dispersants, wherein the total amount of dispersant may be 0.01 wt % to 20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 0.5 wt % to 8 wt %, or 1.0 wt % to 6.5 wt %, or 0.5 wt % to 2.2 wt % of the lubricating composition and wherein the ratio of borated dispersant to non-boroated dispersant may be 1:10 to 10:1 (weight:weight) or 1:5 to 3:1 or 1:3 to 2:1.

[0541] The dispersant may comprise one or more borated or unborated poly(alkenyl)succinimides, where the polyalkyenyl is derived from polyisobutylene and the imide is derived from a polyamine (PIBSA-PAM).

[0542] The dispersant may comprise one or more PIBSA-PAMs, where the PIB is derived from polyisobutylene having an Mn of from 600 to 5000, such as from 700 to 4000, such as from 800 to 3000, such as from 900 to 2500 g/mol and the polyamine is derived from hydrocarbyl-substituted polyamines, such as tetraethylene pentamine, pentaethylene hexamine, tetraethylenepentamine (TEPA), pentaethylenehaxamine (PEHA), N-phenyl-p-phenylenediamine (ADPA), and other polyamines having an average of 5, 6, 7, 8, or 9 nitrogen atoms per molecule). The dispersant may be borated, typically at levels of up to 4 mass % such as from 1 to 3 mass %. The dispersant may comprise one or more borated and one or more non-borated PIBSA-PAM's. The dispersant may comprise one or more borated PIBSA-PAM's derived from a PIB having an Mn of 700 to 1800 g/mol (such as 800 to 1500 g/mol) and one or more non-borated PIBSA-PAM's derived from a PIB having an Mn of more than 1800 to 5000 g/mol (such as 2000 to 3000 g/mol). The dispersant may comprise one or more non-borated PIBSA-PAM's derived from a PIB having an Mn of 700 to 1800 g/mol (such as 800 to 1500 g/mol) and one or more borated PIBSA-PAM's derived from a PIB having an Mn of more than 1800 to 5000 g/mol (such as 2000 to 3000 g/mol).

[0543] The dispersant may comprise PIBSA derived from a PIB having an Mn of 700 to 5000 g/mol (such as 800 to 3000 g/mol) and one or more borated or non-borated PIBSA-PAM's derived from a PIB having an Mn of 700 to 5000 g/mol.

[0544] The dispersant may comprise PIBSA derived from a PIB having an Mn of 700 to 5000 g/mol (such as 800 to 3000 g/mol) and one or more borated PIBSA-PAM's derived from a PIB having an Mn of 700 to 1800 g/mol (such as 800 to 1500 g/mol) and one or more non-borated PIBSA-PAM's derived from a PIB having an Mn of more than 1800 to 5000 g/mol (such as 2000 to 3000 g/mol). The dispersant may comprise PIBSA derived from a PIB having an Mn of 700 to 5000 g/mol (such as 800 to 3000 g/mol) one or more non-borated PIBSA-PAM's derived from a PIB having an Mn of 700 to 1800 g/mol (such as 800 to 1500 g/mol) and one or more borated PIBSA-PAM's derived from a PIB having an Mn of more than 1800 to 5000 g/mol (such as 2000 to 3000 g/mol).

[0545] The dispersant may comprise one or more borated or non-borated PIBSA-PAM's and one or more PIBSA-esters of hydrocarbyl bridged aryloxy alcohols.

[0546] The dispersant may comprise one or more borated and one or more non-borated PIBSA-PAM's.

[0547] The dispersant may comprise one or more, optionally borated, higher molecular weight (Mn 1600 g/mol or more, such as 1800 to 3000 g/mol) PIBSA-PAM's and one or more, optionally borated, lower molecular weight (Mn less than 1600 g/mol) PIBSA-PAM's, where the higher molecular weight may be 1600 to 3000 g/mol, such as 1700 to 2800 g/mol, such as 1800 to 2500 g/mol, such as 1850 to 2300 g/mol; and the lower molecular weight may be 600 to less than 1600 g/mol, such as 650 to 1500 g/mol, such as 700 to 1400 g/mol, such as 800 to 1300 g/mol, such as 850 to 1200 g/mol, such as 900 to 1100 g/mol, such as 900 to 1000.0 g/mol, such as about 950 g/mol. The higher molecular weight PIBSA-PAM dispersant may be present in the lubricating composition in an amount of from 0.5 to 10 wt %, or from 0.8 to 6 wt %, or from 1.0 to 5 wt %, or from 1.5 to 5 wt % or from 1.5 to 4.0 wt %; and the lower molecular weight PIBSA-PAM dispersant may be present in the lubricating composition in an amount of from 1 to 5 wt %, or from 1.5 to 4.8 wt %, or from 1.8 to 4.6 wt %, or from 1.9 to 4.6 wt %, or at 2 wt % or more, such as 2 to 5 wt %.

[0548] In one preferred form, the dispersant may comprise one or more, optionally borated, higher molecular weight (Mn 1600 g/mol or more) PIBSA-PAM's and one or more, optionally borated, lower molecular weight (Mn less than 1600 g/mol) PIBSA-PAM's, where the higher molecular weight PIBSA-PAM's are included in the lubricating oil composition at less than or equal to 2.5 wt %, or less than or equal to 1.5 wt %, or less than or equal to 0.5 wt %, or 0.0 wt %. In the preferred form wherein the dispersant comprises one or more, optionally borated, higher molecular weight (Mn 1600 g/mol or more) PIBSA-PAM's and one or more, optionally borated, lower molecular weight (Mn less than 1600 g/mol) PIBSA-PAM's, the treat level of the combination of the higher molecular weight PIBSA-PAM's and the lower molecular weight PIBSA-PAM's may range for 1.0 to 6.0 wt %, or 1.5 to 5.5 wt %, or 2.0 to 5.0 wt %, or 2.5 to 4.5 wt %, or 3.0 to 4.0 wt %.

Dispersants of Mannich Bases

[0549] Mannich base dispersants useful herein are typically made from the reaction of an amine component, a hydroxy aromatic compound (substituted or unsubstituted, such as alkyl substituted), such as alkylphenols, and an aldehyde, such as formaldehyde. See U.S. Pat. Nos. 4,767,551 and 10,899,986. Process aids and catalysts, such as oleic acid and sulfonic acids, can also be part of the reaction mixture. Representative examples are shown in U.S. Pat. Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; 3,803,039; 4,231,759; 9,938,479; 7,491,248; and 10,899,986, and PCT Publication No. WO 01/42399.

Dispersants of Polymethacrylate or Polyacrylate Derivatives

[0550] Polymethacrylate or polyacrylate derivatives are another class of dispersants useful herein. These dispersants are typically prepared by reacting a nitrogen-containing monomer and a methacrylic or acrylic acid esters containing 5-25 carbon atoms in the ester group. Representative examples are shown in U.S. Pat. Nos. 2,100,993, and 6,323,164. Polymethacrylate and polyacrylate dispersants are typically lower molecular weights.

[0551] The lubricating composition of the disclosure typically comprises dispersant at 0.1 mass % to 20 mass % of the composition, such as 0.2 to 15 mass %, such as 0.25 to 10 mass %, such as 0.3 to 5 mass %, such as 2.0 mass % to 4.0 mass % of the lubricating oil composition. Alternately the dispersant may be present at 0.1 wt % to 5 wt %, or 0.01 wt % to 4 wt % of the lubricating composition.

[0552] For further information on dispersants useful herein, please see U.S. Pat. No. 10,829,712, col 13, ln 36 to col 16, ln 67 and U.S. Pat. No. 7,485,603, col 2, ln 65 to col 6, ln 22, col 8, ln 25 to col 14, ln 53, and col 23, ln 40 to col 26, ln 46.

[0553] Compositions according to the present disclosure may contain an additive having a different enumerated function that also has secondary effects as a dispersant (for example, Component B Functionalized Polymer described above, may also have dispersant effects). These additives are not included as dispersants for purposes of determining the amount of dispersant in a lubricating oil composition or concentrate herein.

J. Corrosion Inhibitors/Anti-Rust Agents

[0554] Corrosion inhibitors may be used to reduce the corrosion of metals and are often alternatively referred to as metal deactivators or metal passivators. Some corrosion inhibitors may alternatively be characterized as antioxidants.

[0555] Suitable corrosion inhibitors may include nitrogen and/or sulfur-containing heterocyclic compounds such as triazoles (e.g., benzotriazoles), substituted thiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines and derivatives of any one or more thereof. A particular corrosion inhibitor is a benzotriazole represented by the structure:

##STR00014##

wherein R.sup.8 is absent (hydrogen) or is a C.sub.1 to C.sub.20 hydrocarbyl or substituted hydrocarbyl group which may be linear or branched, saturated or unsaturated. It may contain ring structures that are alkyl or aromatic in nature and/or contain heteroatoms such as N, O, or S. Examples of suitable compounds may include benzotriazole, alkyl-substituted benzotriazoles (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl substituted benzotriazole, alkylaryl- or arylalkyl-substituted benzotriazoles, and the like, as well as combinations thereof. For instance, the triazole may comprise or be a benzotriazole and/or an alkylbenzotriazole in which the alkyl group contains from 1 to about 20 carbon atoms or from 1 to about 8 carbon atoms. Non-limiting examples of such corrosion inhibitors may comprise or be benzotriazole, tolyltriazole, and/or optionally, substituted benzotriazoles such as Irgamet 39, which is commercially available from BASF of Ludwigshafen, Germany. A preferred corrosion inhibitor may comprise or be benzotriazole and/or tolyltriazole.

[0556] Additionally, or alternatively, the corrosion inhibitor may include one or more substituted thiadiazoles represented by the structure:

##STR00015##

wherein R.sub.15 and R.sub.16 are independently hydrogen or a hydrocarbon group, which group may be aliphatic or aromatic, including cyclic, alicyclic, aralkyl, aryl and alkaryl, and wherein each w is independently 1, 2, 3, 4, 5, or 6 (preferably 2, 3, or 4, such as 2). These substituted thiadiazoles are derived from the 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecule. Many derivatives of DMTD have been described in the art, and any such compounds may be included in the fluid used in the present disclosure. For example, U.S. Pat. Nos. 2,719,125; 2,719,126; and 3,087,937; describe the preparation of various 2, 5-bis-(hydrocarbon dithio)-1,3,4-thiadiazoles.

[0557] Further, additionally or alternatively, the corrosion inhibitor may include one or more other derivatives of DMTD, such as a carboxylic ester in which R.sub.15 and R.sub.16 may be joined to the sulfide sulfur atom through a carbonyl group. Preparation of these thioester-containing DMTD derivatives is described, for example, in U.S. Pat. No. 2,760,933. DMTD derivatives produced by condensation of DMTD with alpha-halogenated aliphatic carboxylic acids having at least 10 carbon atoms are described, for example, in U.S. Pat. No. 2,836,564. This process produces DMTD derivatives wherein R.sub.15 and R.sub.16 are HOOCCH(R.sub.19)(R.sub.19 being a hydrocarbyl group). DMTD derivatives further produced by amidation or esterification of these terminal carboxylic acid groups may also be useful.

[0558] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles is described, for example, in U.S. Pat. No. 3,663,561.

[0559] A class of DMTD derivatives may include mixtures of a 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole and a 2,5-bis-hydrocarbyldithio-1,3,4-thiadiazole. Such mixtures may be sold under the tradename HiTEC 4313 and are commercially available from Afton Chemical Company.

[0560] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles is described, for example, in U.S. Pat. No. 3,663,561.

[0561] A class of DMTD derivatives may include mixtures of a 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole and a 2,5-bis-hydrocarbyldithio-1,3,4-thiadiazole. Such mixtures may be sold under the tradename HiTEC 4313 and are commercially available from Afton Chemical Company.

[0562] Still further, additionally or alternatively, the corrosion inhibitor may include a trifunctional borate having the structure, B(OR.sub.46).sub.3, in which each R.sub.46 may be the same or different. As the borate may typically be desirably compatible with the non-aqueous medium of the composition, each R.sub.46 may, in particular, comprise or be a hydrocarbyl C.sub.1-C.sub.8 moiety. For compositions in which the non-aqueous medium comprises or is a lubricating oil basestock, for example, better compatibility can typically be achieved when the hydrocarbyl moieties are each at least C.sub.4. Non-limiting examples of such corrosion inhibitors thus include, but are not limited to, triethylborate, tripropylborates such as triisopropylborate, tributylborates such as tri-tert-butylborate, tripentylborates, trihexylborates, trioctylborates such as tri-(2-ethylhexyl)borate, monohexyl dibutylborate, and the like, as well as combinations thereof.

[0563] When used, a corrosion inhibitor may comprise a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, or a combination thereof.

[0564] When desired, corrosion inhibitors can be used in any effective amount, but, when used, may typically be used in amounts from about 0.001 wt % to 5.0 wt %, based on the weight of the composition, e.g., from 0.005 wt % to 3.0 wt % or from 0.01 wt % to 1.0 wt %. Alternately, such additives may be used in an amount of about 0.01 to 5 wt %, preferably about 0.01 to 1.5 wt %, based upon the weight of the lubricating composition.

[0565] In some embodiments, 3,4-oxypyridinone-containing compositions may contain substantially no (e.g., 0, or less than 0.001 wt %, 0.0005 wt % or less, not intentionally added, and/or absolutely no) triazoles, benzotriazoles, substituted thiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines, derivatives thereof, combinations thereof, or all corrosion inhibitors.

[0566] Compositions according to the present disclosure may contain an additive having a different enumerated function that also has secondary effects as a corrosion inhibitor (for example, Component B Functionalized Polymer described above, may also have corrosion inhibitor effects). These additives are not included as corrosion inhibitor for purposes of determining the amount of corrosion inhibitor in a lubricating oil composition or concentrate herein.

K. Antiwear Agents

[0567] The lubricating oil compositions and concentrate compositions of the present disclosure can contain one or more antiwear agents that can reduce friction and excessive wear. Any antiwear agent known by a person of ordinary skill in the art may be used in the lubricating oil composition. Non-limiting examples of suitable antiwear agents include zinc dithiophosphate, metal (e.g., Pb, Sb, Mo, and the like) salts of dithiophosphates, metal (e.g., Zn, Pb, Sb, Mo, and the like) salts of dithiocarbamates, metal (e.g., Zn, Pb, Sb, and the like) salts of fatty acids, boron compounds, phosphate esters, phosphite esters, amine salts of phosphoric acid esters or thiophosphoric acid esters, reaction products of dicyclopentadiene and thiophosphoric acids and combinations thereof. The amount of the antiwear agent may vary from about 0.01 wt % to about 5 wt %, from about 0.05 wt % to about 3 wt %, or from about 0.1 wt % to about 1 wt %, based on the total weight of the lubricating oil composition.

[0568] In embodiments, the antiwear agent is or comprises a dihydrocarbyl dithiophosphate metal salt, such as zinc dialkyl dithiophosphate compounds. The metal of the dihydrocarbyl dithiophosphate metal salt may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel, or copper. In some embodiments, the metal is zinc. In other embodiments, the alkyl group of the dihydrocarbyl dithiophosphate metal salt has from about 3 to about 22 carbon atoms, from about 3 to about 18 carbon atoms, from about 3 to about 12 carbon atoms, or from about 3 to about 8 carbon atoms. In further embodiments, the alkyl group is linear or branched.

[0569] Useful antiwear agents also include substituted or unsubstituted thiophosphoric acids, and salts thereof include zinc-containing compounds such as zinc dithiophosphate compounds selected from zinc dialkyl-, diaryl- and/or alkylaryl-dithiophosphates.

[0570] A metal alkylthiophosphate and more particularly a metal dialkyl dithio phosphate in which the metal constituent is zinc, or zinc dialkyl dithio phosphate (ZDDP) can be a useful component of the lubricating compositions of this disclosure. ZDDP can be derived from primary alcohols, secondary alcohols or mixtures thereof. ZDDP compounds generally are of the formula Zn[SP(S)(OR.sub.1)(OR.sub.2)].sub.2 where R.sub.1 and R.sub.2 are C.sub.1-C.sub.18 alkyl groups, preferably C.sub.2-C.sub.12 alkyl groups. These alkyl groups may be straight chain or branched. Alcohols used in the ZDDP can be 2-propanol, butanol, secondary butanol, pentanols, hexanols such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethyl hexanol, alkylated phenols, and the like. Mixtures of secondary alcohols or of primary and secondary alcohol can be used. Alkyl aryl groups may also be used. Useful zinc dithiophosphates include secondary zinc dithiophosphates such as those available from The Lubrizol Corporation under the trade designations LZ 677A, LZ 1095 and LZ1371, from Chevron Oronite under the trade designation OLOA 262 and from Afton Chemical under the trade designation HiTEC 7169.

[0571] In embodiments, the zinc compound can be a zinc dithiocarbamate complex, such as the zinc dithiocarbamates represented by the formula:

##STR00016##

where each R.sub.1 is independently a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 10 carbon atoms, n is 0, 1, or 2, L is a ligand that saturates the coordination sphere of zinc, and x is 0, 1, 2, 3, or 4. In certain embodiments, the ligand, L, is selected from the group consisting of water, hydroxide, ammonia, amino, amido, alkylthiolate, halide, and combinations thereof.

[0572] The antiwear additives, such as ZDDP and/or the zinc carbamates, are typically used in amounts of from about 0.08 wt % to about 1.2 wt %, preferably from about 0.5 wt % to about 1.0 wt %, and more preferably from about 0.6 wt % to about 0.8 wt %, based on the total weight of the lubricating composition, although more or less can often be used advantageously. Preferably, the antiwear additive is ZDDP, preferably a secondary ZDDP, and is present in an amount of from about 0.6 to 1.0 wt % of the total weight of the lubricating composition. The lubricating oil compositions of the instant disclosure preferably include one or more ZDDPs at a treat level to deliver less than or equal to 1200 ppm, or 1000 ppm, or 800 ppm, or 600 ppm, or 400 ppm, or 200 ppm, or 0 ppm by weight of phosphorous to the composition.

[0573] Antiwear additives useful herein also include boron-containing compounds, such as borate esters, borated fatty amines, borated epoxides, alkali metal (or mixed alkali metal or alkaline earth metal) borates and borated overbased metal salts.

[0574] Compositions according to the present disclosure may contain an additive having a different enumerated function that also has secondary effects as an antiwear agent (for example, Component B Functionalized Polymer described above, may also have antiwear effects). These additives are not included as antiwear agents for purposes of determining the amount of antiwear agents in a lubricating oil composition or concentrate herein.

L. Demulsifiers

[0575] Demulsifiers useful herein include those described in U.S. Pat. No. 10,829,712 (col 20, In 34-40). Typically, a small amount of a demulsifying component may be used herein. A preferred demulsifying component is described in European Patent No. 330 522. It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol. Such additives may be used in an amount of about 0.001 to 5 wt %, preferably about 0.01 to 2 wt %.

M. Seal Compatibility Agents and Seal Swell Agents

[0576] Other optional additives include seal compatibility agents such as organic phosphates, aromatic esters, aromatic hydrocarbons, esters (butylbenzyl phthalate, for example), and polybutenyl succinic anhydride. Such additives may be used in an amount of about 0.001 to 5 wt %, preferably about 0.01 to 2 wt %. In embodiments the seal compatibility agents are sea swell agents, such as PIBSA (polyisobutenyl succinic anhydride).

N. Extreme Pressure Agents

[0577] The lubricating oil compositions and concentrate compositions of the present disclosure can contain one or more extreme pressure agents that can prevent sliding metal surfaces from seizing under conditions of extreme pressure. Any extreme pressure agent known by a person of ordinary skill in the art may be used in the lubricating oil composition. Generally, the extreme pressure agent is a compound that can combine chemically with a metal to form a surface film that prevents the welding of asperities in opposing metal surfaces under high loads. Non-limiting examples of suitable extreme pressure agents include sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins, dihydrocarbyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acid esters and monounsaturated olefins, co-sulfurized blends of fatty acid, fatty acid ester and alpha-olefin, functionally substituted dihydrocarbyl polysulfides, thia-aldehydes, thia-ketones, epithio compounds, sulfur-containing acetal derivatives, co-sulfurized blends of terpene and acyclic olefins, and poly sulfide olefin products, amine salts of phosphoric acid esters or thiophosphoric acid esters, and combinations thereof. The amount of the extreme pressure agent may vary from about 0.01 wt % to about 5 wt %, from about 0.05 wt % to about 3 wt %, or from about 0.1 wt % to about 1 wt %, based on the total weight of the lubricating oil composition.

O. Non-Basestock Unsaturated Hydrocarbons

[0578] The lubricating oil compositions and concentrate compositions of the present disclosure can contain one or more unsaturated hydrocarbons. These unsaturated hydrocarbons are distinct from any baseoils (lubricating oil basestocks of Group I, II, III, IV and/or V) and/or viscosity modifiers that may be present in the compositions and always have at least one (and typically only one, in the case of linear alpha-olefins, or LAOs) unsaturation per molecule. Without being bound by theory, the unsaturation(s) may provide an antioxidation functionality and/or a sulfur-trapping functionality that may supplement and/or replace one or more antioxidant additives and/or one or more corrosion inhibitor additives, but unsaturated hydrocarbons (LAOs) will typically not provide the only antioxidant nor the only corrosion inhibition functionality in lubrication oil compositions. Non-limiting examples of unsaturated hydrocarbons can include one or more unsaturated C.sub.12-C.sub.60 hydrocarbons (such as C.sub.12-C.sub.48 hydrocarbons, C.sub.12-C.sub.36 hydrocarbons, C.sub.12-C.sub.30 hydrocarbons, or C.sub.12-C.sub.24 hydrocarbons). When only one unsaturation is present, the unsaturated hydrocarbons may be termed linear alpha-olefins (LAOs). Other non-limiting examples of unsaturated hydrocarbons can include oligomers/polymers of polyisobutylenes that have retained (or been post-polymerization modified to exhibit) a (near-) terminal unsaturation, and/or blends thereof. When present, unsaturated hydrocarbons (LAOs) may be present from 0.01 to 5 wt % (in particular, 0.1 to 3 mass %, alternately 0.1 to 1.5 mass %), based on total weight of the lubricating oil composition.

[0579] When lubricating oil compositions contain one or more of the additives discussed above, the additive(s) are typically blended into the composition in an amount sufficient for it to perform its intended function. Typical amounts of such additives useful in the present disclosure, especially for use in crankcase lubricants, are shown in the Table below.

[0580] It is noted that many of the additives are shipped from the additive manufacturer as a concentrate, containing one or more additives together, with a certain amount of base oil or other diluents. Accordingly, the weight amounts in the table below, as well as other amounts mentioned herein, are directed to the amount of active ingredient (that is the non-diluent portion of the ingredient). The weight percent (mass %) indicated below is based on the total weight of the lubricating oil composition.

Typical Amounts of Lubricating Oil Components

TABLE-US-00001 A (mass B (mass C (mass Additive Formulations % a.i.) % a.i.) % a.i.) Dispersant 0.1-20 0.5-10 1-6 Detergents 0.1-20 0.2-10 0.3-9 Corrosion Inhibitor 0-7 0.01-5 0.05-1.5 and/or Anti-rust Overbased Ca detergent 0.1-10 0.2-5 0.3-4.5 Overbased Mg detergent 0.1-10 0.2-5 0.4-4.5 High MW PIBSA-PAM 0-20 0.5-8 1 to 4 Low MW PIBSA-PAM 0.1-20 0.5-10 1-6 Antioxidant 0.01-10 0.1-5 0.1-4 Pour Point Depressant 0-8 0.005-5 0.01-1.5 Anti-foaming Agent 0-1 0.001-0.5 0.005-0.15 Functionalized Polymer 0.01-10 0.1-5 0.5-2 Friction Modifier 0-2 0.1-1 0.2-0.5 Antiwear Agent 0.01-10 0.1-5 0.5-3 Viscosity Modifier 0-15 0.1-10 0.25-3 Seal Swell Agents 0-10 0.01-5 0.1-2 Extreme Pressure Agents 0-10 0.01-5 0.1-3 Unsaturated Hydrocarbons 0-10 0.01-5 0.1-3 (LAOs) Base stock Balance Balance Balance (such as 50 to 95%)

[0581] The foregoing additives are typically commercially available materials. These additives may be added independently, but are usually pre-combined in packages, which can be obtained from suppliers of lubricant oil additives. Additive packages with a variety of ingredients, proportions and characteristics are available and selection of the appropriate package will take the use of the ultimate composition into account.

Uses

[0582] The lubricating compositions disclosed herein may be used to lubricate mechanical hybrid engine components, e.g., spark-ignited or compression-ignited, two- or four-stroke reciprocating hybrid engines, by adding the lubricant thereto. Typically, they are crankcase lubricants, such as passenger car motor oils or heavy-duty engine lubricants. In particular, the lubricating compositions disclosed herein are suitably used in the lubrication of the crankcase of a compression-ignited, internal combustion hybrid engine, such as a passenger car engine.

[0583] In particular, the lubricating compositions disclosed herein are suitably used in the lubrication of the crankcase of a spark-ignited hybrid internal combustion engine. In embodiments, the lubricating oils disclosed herein are used in spark-assisted high compression gasoline fueled hybrid internal combustion engines.

[0584] The lubricating compositions described herein are particularly suitable for gasoline fueled hybrid internal combustion engines that are prone to piston-liner wear from a long duration of operation, hence the invention might also extend engine lifetime.

[0585] This invention further relates to: [0586] 1. A lubricating oil composition for hybrid engines comprising or resulting from the admixing of: [0587] a) an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof; [0588] b) one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more); [0589] c) optionally one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.5 to 12.0 wt. % of the lubricating oil composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is from 1.5 to 9.0 wt. % of the lubricating oil composition; and [0590] d) an overbased calcium salicylate detergent, an overbased magnesium salicylate detergent, an overbased mixed calcium and magnesium salicylate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and delivers at least 5 mmol of total soap to the lubricating oil composition; [0591] wherein the lubricating oil composition has a total sulfated ash of less than or equal to 1.2 wt. %, a kinematic viscosity at 100 C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.4 wt. %; and [0592] wherein the lubricating oil composition results in a passing emulsion dispersion and stability performance at the four test conditions in the Emulsion Stability test (modified ASTM D7563: a) 10%/10% E85/water-24 h; b) 10%/10% E85/water-72 h; c) 15%/15% E85/water-24 h; and d) 15%/15% E85/water-72 h. [0593] 2. The composition of paragraph 1, wherein the lubricating oil composition results in a rating of at least 2 for emulsion corrosion resistance in the emulsion corrosion test. [0594] 3. The composition of paragraph 1, wherein the lubricating oil composition results in a rating of at least 2 for bearing wear in the journal bearing wear test. [0595] 4. The composition of paragraph 1, wherein the lubricating oil composition further comprises one or more zinc dialkyl dithiophosphate (ZDDP) compounds; and wherein the treat level of the one or more ZDDP compounds is from 0.4 wt. % to 2.0 wt. % of the lubricating oil composition. [0596] 5. The composition of paragraph 4, wherein the hydrocarbyl group of the zinc hydrocarbyl dithiophosphate is derived from one or more primary alcohols, one or more secondary alcohols or a combination of primary and secondary alcohols. [0597] 6. The composition of paragraph 4, wherein the one or more zinc dialkyldithiophosphates (ZDDP) include greater than or equal to 85 wt. % secondary alcohols and less than or equal to 15 wt. % primary alcohols. [0598] 7. The composition of paragraph 1, wherein the lubricating oil composition further comprises a functionalized polymer at from 0.01 to 20 wt. % based upon the total weight of the lubricating oil composition, wherein the functionalized polymer comprises a partially or fully saturated olefin homopolymer or copolymer backbone and at least one functional group, having: [0599] i) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization, [0600] ii) where the functional group is derived from an acylating agent and a compound containing amino and/or hydroxyl groups (including but not limited to where the polymer is functionalized with an acylating agent and subsequently reacted with a compound containing amino and/or hydroxyl groups), and [0601] iii) wherein the homopolymer or copolymer backbone is derived from monomers selected from the group consisting of C.sub.2 to C.sub.30 linear alpha olefins, and C.sub.4 to C.sub.20 conjugated dienes. [0602] 8. The composition of paragraph 7, wherein the functionalized polymer is at from 0.3 to 5 wt. % based upon the total weight of the lubricating oil composition, and the functionalized polymer comprises an amide, imide, and/or ester functionalized partially or fully saturated polymer comprising C.sub.4-5 olefins having: [0603] i) an Mw/Mn of less than 2, [0604] ii) a Functionality Distribution (Fd) value of 3.5 or less, and [0605] iii) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization, provided that, if the polymer prior to functionalization is a copolymer of isoprene and butadiene, then the Mn of the copolymer is greater than 25,000 g/mol (GPC-PS). [0606] 9. The composition of paragraph 1, further including one or more corrosion inhibitors, rust inhibitors or combinations thereof at a treat rate of greater than or equal to 0.02 wt. % of the lubricating oil composition. [0607] 10. The composition of paragraph 9, wherein the one or more corrosion and/or rust inhibitors are selected from the group consisting of a non-ionic fatty alcohol ethoxylate, a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, a primary amine, a substituted carboxylic acid functional group, a substituted ester functional group, a substituted anhydride functional group, or a combination thereof. [0608] 11. The composition of paragraph 1, wherein the composition provides for substantially no aqueous separation of lubricating oil emulsions including the lubricating oil composition and up to 15 wt. % water at 0 C. and 25 C. in the Emulsion stability test (modified ASTM D7563). [0609] 12. The composition of paragraph 1, wherein the higher molecular weight PIBSA-PAM is borated, the optional lower molecular weight PIBSA-PAM is borated or a combination thereof, and is/are included at a treat level to deliver from 20 ppm to 1000 ppm by weight of boron to the composition; and or wherein the one or more, optionally borated, higher molecular weight PIBSA-PAM dispersant is from 2.0 to 6.0 wt. % of the composition. [0610] 13. The composition of paragraph 1, wherein the oil of lubricating viscosity is at from 60 wt. % to 95 wt. % of the composition, comprises a Group II base oil, a Group III base oil, a Group IV base oil or combinations thereof, and is substantially free of Group I base oil. [0611] 14. The composition of paragraph 1, wherein the detergent includes a combination of an overbased calcium salicylate detergent and an overbased magnesium salicylate detergent. [0612] 15. The composition of paragraph 14, wherein the soap level is greater than or equal to 0.5 wt. % of the overall composition. [0613] 16. The composition of paragraph 1, further including one or more of the following components: one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more anti-foaming agents; one or more viscosity modifiers; one or more dispersants other than the higher molecular weight PIBSA-PAM and the lower molecular weight PIBSA-PAM; one or more inhibitors, one or more antirust agents; one or more seal swell agents; and/or one or more other anti-wear agents. [0614] 17. The composition of paragraph 16, wherein the one or more antioxidants includes one or more phenolic antioxidants, one or more sulfur based antioxidants, one or more aminic antioxidants or a combination thereof, and wherein the one or more antioxidants comprise from 1.0 to 6.0 wt. % of the composition. [0615] 18. The composition of paragraph 16, wherein the one or more friction modifier includes a dimeric molybdenum dialkyldithiocarbamate (moly dimer), a trimeric molybdenum dialkyldithiocarbamate (moly trimer), or a combination thereof at a treat level to deliver from 12 ppm to 1000 ppm by weight of molybdenum to the composition. [0616] 19. The composition of paragraph 16, wherein the one or more friction modifier includes an organic friction modifier selected from the group consisting of alkylated succinic anhydrides, alkylated succinic acids, alkylated carboxylic acids, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, and combinations thereof, wherein the organic friction modifier comprises from 0.01 to 5.0 wt. % of the composition. [0617] 20. The composition of paragraph 16, wherein the one or more pour point depressants include polymethacrylate, polyacrylate or a combination thereof, and wherein the one or more pour point depressants comprise from 0.01 to 5.0 wt. % of the composition. [0618] 21. The composition of paragraph 1, wherein the lubricating oil composition is used as a passenger vehicle lubricant (PVL) or a commercial vehicle lubricant (CVL). [0619] 22. A method of lubricating a hybrid engine comprising supplying to the engine a lubricating oil composition of paragraph 1. [0620] 23. A lubricating oil composition for hybrid engines comprising or resulting from the admixing of: [0621] a) an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof; [0622] b) one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more); [0623] c) optionally one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 (preferably 1.5) to 12.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is from 1.0 (preferably 1.5) to 9.0 wt. % of the composition; [0624] d) an overbased calcium sulfonate detergent, an overbased magnesium sulfonate detergent, an overbased mixed calcium and magnesium sulfonate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and delivers less than or equal to 5 mmol of total soap to the composition; and [0625] e) one or more organic friction modifier at from 0.01 to 2.0 wt. % of the composition; [0626] wherein the lubricating oil composition has a total sulfated ash of less than or equal to 1.2 wt. %, a kinematic viscosity at 100 C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.4 wt. %; and [0627] wherein the lubricating oil composition results in a rating of at least 2 for emulsion corrosion resistance in the emulsion corrosion test. [0628] 24. The composition of paragraph 23, wherein the lubricating oil composition results in a rating of at least 2 for bearing wear in the journal bearing wear test. [0629] 26. The composition of paragraph 23, wherein the lubricating oil composition further comprises one or more zinc dialkyl dithiophosphate (ZDDP) compounds; and wherein the treat level of the one or more ZDDP compounds is from 0.4 wt. % to 2.0 wt. % of the lubricating oil composition. [0630] 27. The composition of paragraph 26, wherein the hydrocarbyl group of the zinc hydrocarbyl dithiophosphate is derived from one or more primary alcohols, one or more secondary alcohols or a combination of primary and secondary alcohols. [0631] 28. The composition of paragraph 26, wherein the one or more zinc dialkyldithiophosphates (ZDDP) include greater than or equal to 85 wt. % secondary alcohols and less than or equal to 15 wt. % primary alcohols. [0632] 29. The composition of paragraph 23, wherein the lubricating oil composition further comprises a functionalized polymer at from 0.01 to 20 wt. % based upon the total weight of the lubricating oil composition, wherein the functionalized polymer comprises a partially or fully saturated olefin homopolymer or copolymer backbone and at least one functional group, having: [0633] i) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization, [0634] ii) where the functional group is derived from an acylating agent and a compound containing amino and/or hydroxyl groups (including but not limited to where the polymer is functionalized with an acylating agent and subsequently reacted with a compound containing amino and/or hydroxyl groups), and [0635] iii) wherein the homopolymer or copolymer backbone is derived from monomers selected from the group consisting of C.sub.2 to C.sub.30 linear alpha olefins, and C.sub.4 to C.sub.20 conjugated dienes. [0636] 30. The composition of paragraph 29, wherein the functionalized polymer is at from 0.3 to 5 wt. % based upon the total weight of the lubricating oil composition and the functionalized polymer comprises an amide, imide, and/or ester functionalized partially or fully saturated polymer comprising C.sub.4-5 olefins having: [0637] i) an Mw/Mn of less than 2, [0638] ii) a Functionality Distribution (Fd) value of 3.5 or less, and [0639] iii) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization, provided that, if the polymer prior to functionalization is a copolymer of isoprene and butadiene, then the Mn of the copolymer is greater than 25,000 g/mol (GPC-PS). [0640] 31. The composition of paragraph 23, further including one or more corrosion inhibitors, rust inhibitors or combinations thereof at a treat rate of greater than or equal to 0.02 wt. % of the lubricating oil composition. [0641] 32. The composition of paragraph 31, wherein the one or more corrosion and/or rust inhibitors are selected from the group consisting of a non-ionic fatty alcohol ethoxylate, a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, a primary amine, a substituted carboxylic acid functional group, a substituted ester functional group, a substituted anhydride functional group, or a combination thereof. [0642] 33. The composition of paragraph 23, wherein the composition provides for substantially no aqueous separation of lubricating oil emulsions including the lubricating oil composition and up to 15 wt. % water at 0 C. and 25 C. in the Emulsion Stability test (modified ASTM D7563). [0643] 34. The composition of paragraph 23, wherein the higher molecular weight PIBSA-PAM is borated, the optional lower molecular weight PIBSA-PAM is borated or a combination thereof, and is/are included at a treat level to deliver from 20 ppm to 600 ppm by weight of boron to the composition. [0644] 35. The composition paragraph 23, wherein the one or more, optionally borated, higher molecular weight PIBSA-PAM dispersant is from 2.0 to 4.5 wt. % of the composition. [0645] 36. The composition of paragraph 23, wherein the oil of lubricating viscosity is at from 60 wt. % to 95 wt. % of the composition, comprises a Group II base oil, a Group III base oil, a Group IV base oil or combinations thereof, and is substantially free of Group I base oil. [0646] 37. The composition of paragraph 23, wherein the detergent includes a combination of an overbased calcium salicylate detergent and an overbased magnesium salicylate detergent. [0647] 38. The composition of paragraph 23, further including one or more of the following components: one or more other friction modifiers; one or more antioxidants; one or more pour point depressants; one or more anti-foaming agents; one or more viscosity modifiers; one or more dispersants other than the higher molecular weight PIBSA-PAM and the lower molecular weight PIBSA-PAM; one or more inhibitors, one or more antirust agents; one or more seal swell agents; and/or one or more other anti-wear agents. [0648] 39. The composition of paragraph 38, wherein the one or more antioxidants includes one or more phenolic antioxidants, one or more sulfur based antioxidants, one or more aminic antioxidants or a combination thereof, and wherein the one or more antioxidants comprise from 1.0 to 6.0 wt. % of the composition. [0649] 40. The composition of paragraph 38, wherein the one or more other friction modifier includes a dimeric molybdenum dialkyldithiocarbamate (moly dimer), a trimeric molybdenum dialkyldithiocarbamate (moly trimer), or a combination thereof at a treat level to deliver from 12 ppm to 1000 ppm by weight of molybdenum to the composition. [0650] 41. The composition of paragraph 23, wherein the one or more organic friction modifier is selected from the group consisting of alkylated succinic anhydrides, alkylated succinic acids, alkylated carboxylic acids, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, and combinations thereof. [0651] 42. The composition of paragraph 38, wherein the one or more pour point depressants include polymethacrylate, polyacrylate or a combination thereof, and wherein the one or more pour point depressants comprise from 0.01 to 5.0 wt. % of the composition. [0652] 43. The composition of paragraph 23, wherein the lubricating oil composition is used as a passenger vehicle lubricant (PVL) or a commercial vehicle lubricant (CVL). [0653] 44. A method of lubricating a hybrid engine comprising supplying to the engine a lubricating oil composition of paragraph 23. [0654] 45. A concentrate comprising or resulting from the admixing of: [0655] from 1 to less than or equal to 50 wt. % of one or more base oils; [0656] from 2 to 40 wt. % of an overbased calcium salicylate detergent, an overbased magnesium salicylate detergent, an overbased mixed calcium and magnesium salicylate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500; and [0657] from 2 to 40 wt. % of one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more), and one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol). [0658] 46. The concentrate of paragraph 45, further including from 2 to 20 wt. % of one or more zinc hydrocarbyl diphosphate compounds, wherein the one or more zinc hydrocarbyl diphosphate compounds include hydrocarbyl groups derived from one or more primary alcohols, one or more secondary alcohols or a combination of primary and secondary alcohols. [0659] 47. The concentrate of paragraph 45, further including from 0.10 to 10 wt. % of one or more corrosion inhibitors, rust inhibitors or combinations thereof selected from the group consisting of a non-ionic fatty alcohol ethoxylate, a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, a primary amine, a substituted carboxylic acid functional group, a substituted ester functional group, a substituted anhydride functional group or a combination thereof. [0660] 48. The concentrate of paragraph 45, further including from 1 to 30 wt. %, such as 2 to 20 wt. %, based upon the weight of the concentrate, of one or more functionalized polymers, wherein the one or more functionalized polymers comprise a partially or fully saturated olefin homopolymer or copolymer backbone and at least one functional group, having: [0661] i) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization, [0662] ii) where the functional group is derived from an acylating agent and a compound containing amino and/or hydroxyl groups (including but not limited to where the polymer is functionalized with an acylating agent and subsequently reacted with a compound containing amino and/or hydroxyl groups), and, [0663] iii) wherein the homopolymer or copolymer backbone is derived from monomers selected from the group consisting of C2 to C30 linear alpha olefins, and C4 to C20 conjugated dienes; [0664] 49. The concentrate of paragraph 45, further comprising combining the concentrate with a base oil to form a lubricating oil composition comprising: [0665] a) an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof; [0666] b) one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more); [0667] c) optionally one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 to 12.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is from 1.0 to 9.0 wt. % of the composition; and [0668] d) an overbased calcium salicylate detergent, an overbased magnesium salicylate detergent, an overbased mixed calcium and magnesium salicylate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and delivers at least 5 mmol of total soap to the composition; [0669] wherein the lubricating oil composition has a total sulfated ash of less than or equal to 1.2 wt. %, a kinematic viscosity at 100 C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.4 wt. %; and [0670] wherein the lubricating oil composition results in a passing emulsion stability performance at all 4 test conditions in the Emulsion Stability test (modified ASTM D7563). [0671] 50. A concentrate comprising or resulting from the admixing of: [0672] from 1 to less than or equal to 50 wt. % of one or more base oils; [0673] from 2 to 40 wt. % of an overbased calcium sulfonate detergent, an overbased magnesium sulfonate detergent, an overbased mixed calcium and magnesium sulfonate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500; [0674] from 2 to 40 wt. % of one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more), and one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol); and from 0.5 to 10 wt. % of one or more organic friction modifier. [0675] 51. The concentrate of paragraph 50, further including from 2 to 20 wt. % of one or more zinc hydrocarbyl diphosphate compounds, wherein the one or more zinc hydrocarbyl diphosphate compounds include hydrocarbyl groups derived from one or more primary alcohols, one or more secondary alcohols or a combination of primary and secondary alcohols. [0676] 52. The concentrate of paragraph 50, further including from 0.10 to 10 wt. % of one or more corrosion inhibitors, rust inhibitors or combinations thereof selected from the group consisting of a non-ionic fatty alcohol ethoxylate, a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, a primary amine, a substituted carboxylic acid functional group, a substituted ester functional group, a substituted anhydride functional group or a combination thereof. [0677] 53. The concentrate of paragraph 50, further including from 1 to 30 wt. %, such as 2 to 20 wt. %, based upon the weight of the concentrate, of one or more functionalized polymers, wherein the one or more functionalized polymers comprise a partially or fully saturated olefin homopolymer or copolymer backbone and at least one functional group, having: [0678] i) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization, [0679] ii) where the functional group is derived from an acylating agent and a compound containing amino and/or hydroxyl groups (including but not limited to where the polymer is functionalized with an acylating agent and subsequently reacted with a compound containing amino and/or hydroxyl groups), and, [0680] iii) wherein the homopolymer or copolymer backbone is derived from monomers selected from the group consisting of C2 to C30 linear alpha olefins, and C4 to C20 conjugated dienes; [0681] 54. The concentrate of paragraph 50, further comprising combining the concentrate with a base oil to form a lubricating oil composition comprising: [0682] a) an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof; [0683] b) one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more), [0684] c) optionally one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 (preferably 1.5) to 12.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is from 1.0 to 9.0 wt. % of the composition; [0685] d) an overbased calcium sulfonate detergent, an overbased magnesium sulfonate detergent, an overbased mixed calcium and magnesium sulfonate detergent or a combination thereof, wherein the detergent has a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and delivers less than or equal to 5 mmol of total soap to the composition; and [0686] e) one or more organic friction modifier at from 0.01 to 2.0 wt. % of the composition; [0687] wherein the lubricating oil composition has a total sulfated ash of less than or equal to 1.2 wt. %, a kinematic viscosity at 100 C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.4 wt. %; and [0688] wherein the lubricating oil composition results in a rating of at least 2 for emulsion corrosion resistance in the emulsion corrosion test. [0689] 55. A method of evaluating a lubricating oil composition for ranking performance of the lubricating oil composition in a hybrid engine comprising the steps of: [0690] i) selecting a lubricating oil composition for bench scale testing; [0691] ii) testing the composition for emulsion dispersion and stability performance in the Emulsion Stability test (modified ASTM D7563) to determine its score from 0 to 3; [0692] iii) testing the composition for emulsion corrosion resistance in the emulsion corrosion test to determine its score from 0 to 3; [0693] iv) testing the composition for journal bearing wear in the journal bearing wear test to determine the change in the depth of the bearing pre-test and post-test in average maximum wear and assigning a wear result from 1 to 3; and [0694] v) combining test results from steps ii), iii) and iv) above to provide an overall performance rating for ranking the performance of the lubricating oil composition in a hybrid engine.

[0695] The following non-limiting examples are provided to illustrate the disclosure.

EXPERIMENTAL

[0696] All molecular weights are number average molecular weights (Mn) reported in g/mol, as determined by gel permeation chromatography using polystyrene standards, unless otherwise noted. A.I., a.i., and ai are wt % active ingredient, unless otherwise indicated.

Testing Procedures

[0697] Sulfated ash (SASH) content is measured by ASTM D874.

[0698] Phosphorus, Calcium, Zinc, Boron, Molybdenum, Magnesium, Sulfur and Silicon content are measured by ASTM D5185 and ASTM D4951, in event of conflict ASTM D5185 shall control.

[0699] KV100 is Kinematic viscosity measured at 1000 C according to ASTM D445-19a.

[0700] KV40 is Kinematic viscosity measured at 400 C according to ASTM D445-19a.

[0701] Total Base Number (TBN) is measured by ASTM D2896.

[0702] Total Acid Number (TAN) is measured by ASTM D664.

[0703] Nitrogen level test ASTM D5762 measures nitrogen level in a lubricating oil composition.

[0704] The moments of molecular weight (Mw, Mn, Mz) are determined by Gel Permeation Chromatography (GPC-PS) using polystyrene standards (Acquity APC Polystyrene High MW Calibration Kit, 266-1,760,000 Da) as described in US2024/0141156A1, page 35, paragraph [0579]et. seq.

[0705] High Temperature High Shear Viscosity, (HTHS or HTHS150) measures the high temperature high shear viscosity of the lubricating oil and is determined at 150 C. according to ASTM D4683 and is reported in cPs.

[0706] Emulsion Corrosion Test measures the corrosion-mitigating performance of an oil when emulsified with water, according to the following method: [0707] a. An emulsion of candidate oil (85%) and deionized water (15%) is prepared using a high-shear homogenizer and decanted into a sample bag of greater size than the steel specimen (150750.8 mm, degreased, stainless steel 1.0330, roughness of Ra 1.5-1.7 m, from Rocholl Gmbh). [0708] b. The steel specimen plate is submerged in the oil/water emulsion in the sample bag, agitated for 1.5 to 2 minutes, then removed, allowed to drip dry in air for 24 hours, and then placed in humidity chamber at 40 C. and 98-100% Relative Humidity (RH) for 168 hours. [0709] c. The steel specimen plate is removed from the humidity chamber and visually rated on a score of 0 to 3:

[00001]$i.0=\mathrm{coverage}\mathrm{of}>50\%\mathrm{of}\mathrm{the}\mathrm{specimen}\mathrm{plate}\mathrm{with}\mathrm{rust}$$\mathrm{ii}.1=\mathrm{significant}\mathrm{rust}\mathrm{patches}\mathrm{that}\mathrm{cover}$$\mathrm{between}10\%\mathrm{and}50\%\mathrm{of}\mathrm{the}\mathrm{specimen}\mathrm{plate}$$\mathrm{iii}.2=a\mathrm{large}\mathrm{quantity}\left(>10\right)\mathrm{of}\mathrm{rust}\mathrm{spots}\mathrm{that}\mathrm{cover}<10\%\mathrm{of}\mathrm{the}\mathrm{specimen}\mathrm{plate}$$\mathrm{iv}.3=\mathrm{visually}\mathrm{clean}\mathrm{plate}\mathrm{with}\mathrm{negligible}\mathrm{or}\mathrm{trace}\mathrm{corrosion}.$

[0710] Emulsion Stability Test measures the emulsifying performance of an oil when blended with water and fuel, according to the following modifications of the ASTM D7563: [0711] a. The 10% water/10% Ed85 fuel/80% oil ratio of ASTM D7563 is used, at 25 C., with measurements of the water, emulsion and oil layers taken at 24 hours and at 72 hours [0712] b. A 15% water/15% Ed85 fuel/70% oil ratio is used, at 25 C., with measurements of the water, emulsion and oil layers taken at 24 hours and at 72 hours [0713] c. The measurements of the water, emulsion and oil layers under different conditions and times are combined to give an overall score of 0 to 3:

[00002]$i.a\mathrm{visible}\mathrm{water}\mathrm{layer}\mathrm{in}\mathrm{the}\mathrm{ASTM}D7563\mathrm{condition}$$\left(10\%\mathrm{water}/10\%\mathrm{Ed}85\mathrm{fuel}/80\%\mathrm{oil}\right)\mathrm{at}25C.\mathrm{for}24\mathrm{hours}.$$\mathrm{ii}.1=a\mathrm{visible}\mathrm{water}\mathrm{layer}\mathrm{in}\mathrm{any}\mathrm{or}\mathrm{all}\mathrm{of}\mathrm{the}\mathrm{other}\mathrm{three}\mathrm{conditions}$$1.\left(10\%\mathrm{water}/10\%\mathrm{Ed}85\mathrm{fuel}/80\%\mathrm{oil}\right)\mathrm{at}25C.\mathrm{for}72\mathrm{hours}.$$2.\left(15\%\mathrm{water}/15\%\mathrm{Ed}85\mathrm{fuel}/70\%\mathrm{oil}\right)\mathrm{at}25C.\mathrm{for}24\mathrm{hours}.$$3.\left(15\%\mathrm{water}/15\%\mathrm{Ed}85\mathrm{fuel}/70\%\mathrm{oil}\right)\mathrm{at}25C.\mathrm{for}72\mathrm{hours}.$$\mathrm{iii}.2=\mathrm{no}\mathrm{visible}\mathrm{water}\mathrm{layers}\mathrm{in}\mathrm{any}\mathrm{condition},$$\mathrm{but}a\mathrm{visible}\mathrm{oil}\mathrm{layer}\mathrm{in}\mathrm{either}\mathrm{of}\mathrm{the}$$72\mathrm{hour}\mathrm{conditions}\mathrm{of}\mathrm{greater}\mathrm{that}20\%\mathrm{oil}.$$\mathrm{iv}.3=\mathrm{no}\mathrm{visible}\mathrm{water}\mathrm{layers}\mathrm{in}\mathrm{any}\mathrm{condition}\mathrm{and}\mathrm{no}\mathrm{visible}\mathrm{oil}\mathrm{layer}$$\mathrm{in}\mathrm{either}\mathrm{of}\mathrm{the}72\mathrm{hour}\mathrm{conditions}\mathrm{of}\mathrm{greater}\mathrm{than}20\%\mathrm{oil}.$

[0714] Journal Bearing Wear Test measures the wear performance of an oil in a journal bearing rig using the TE-92 start/stop test method, which includes a test rig and test procedure for measuring the journal bearing wear as measured by maximum average wear in microns. The test procedure is included in the following journal article, which is herein incorporated by reference in its entirety for the Journal Bearing Wear Test method: Summer, F., Grin, F., & Ravenhill, E. R. 15 (2020). Friction and Wear Performance of Various Polymer Coatings for Journal Bearings under Stop Start Sliding. Lubricants, 8.2020(1), (https://doi.org/10.3390/lubricants8010001). In this journal article, it is stated that [t]he test strategy started with an initial period at a slower sliding speed at room temperature to facilitate mild running in. Thereafter, the oil was heated during still-stand to an oil bath temperature of 120 C. before stop start sliding was performed 20 up to a maximum speed of 500 rpm. The speed ramps were conducted as quickly as possible to mimic engine stop starts. A total ramp duration from 0 to 1.2 m/s and vice versa lasts 8 s. The test duration varied according to the number of stop start ramps. Using the TE-92 start/stop test method with a polymeric trimetal, the test is run for 20,000 cycles. The bearing material was a polymeric bearing from Kolbenschmidt bearings with PAI resin top layer, aluminium interlayer and steel backing. The test proceeds as follows: [0715] 1) The set of polymer bearing shells are photographed and measured using loss of local bearing wall thickness, micrometry and gravimetric methodology to create a depth profile map across the bearing in two directions. [0716] 2) A journal bearing wear rig is set up with a set of polymer bearing shells loaded into two opposing bearing holders pressed against a central shaft of machined hardened crankshaft steel having diameters of 50 mm. [0717] 3) The rig is charged with oil, so that the oil covers the bearings, and the oil is heated to 120 C. [0718] 4) A test cycle is run where the speed is ramped from 0 rpm until 500 rpm over 5 to 10 seconds. This cycle is repeated until 20,000 iterations have taken place. [0719] 5) At the end of the test, the specimens are removed from the bearing holders and the pre-test measurement is repeated. The average change in depth profile from the un-used specimens is calculated and scored according to:

[00003]$1=\mathrm{catastophic}\mathrm{wear},\mathrm{change}\mathrm{in}\mathrm{depth}\mathrm{of}\mathrm{greater}\mathrm{than}9.\mathrm{microns}$$2=\mathrm{significant}\mathrm{wear},\mathrm{change}\mathrm{in}\mathrm{depth}\mathrm{of}$$\mathrm{between}7.\mathrm{and}9.\mathrm{microns}\left(\mathrm{inclusive}\right)$$3=\mathrm{acceptable}\mathrm{wear},\mathrm{change}\mathrm{in}\mathrm{depth}\mathrm{of}\mathrm{less}\mathrm{than}7.\mathrm{microns}$

Overall Performance Rating

[0720] The overall performance rating is obtained by adding scores from the Emulsion Stability Test, the Emulsion Corrosion Test, and the Journal Bearing Wear Test then dividing by 3 to provide the overall performance rating for ranking the performance of the lubricating oil composition in a hybrid engine.

Materials

Component Chart

TABLE-US-00002 Additional Lubricating Oil Components Description Borated LMW Dispersant Polyisobutylene succinimide having 1 to 3 mass % boron, based upon a PIB having an Mn of about 900 to less than 1000.0 g/mol in oil, ai ~40-50 PMNE PIBSA ester of hydrocarbyl-bridged naphthyloxy alcohol in oil diluted to about 40% ai. prepared in a manner similar to Example 1 of U.S. 2009/0203559. HMW Dispersant Polyisobutylene succinimide based upon a PIB having an Mn of about 2000-2300 g/mol in oil, ai ~45-60 LMW Dispersant Polyisobutylene succinimide based upon a PIB having an Mn of about 900-1050 g/mol in oil, ai ~45-55 Calcium sulfonate Calcium sulfonate detergent having a TBN of approximately 300 mgKOH/g (on an as diluted basis) in oil, ai ~55 Magnesium sulfonate magnesium sulfonate detergent having a TBN of approximately 400 mgKOH/g (on an as diluted basis) in oil, ai ~57 Mg Salicylate Magnesium salicylate detergent, TBN ~340, ai ~55 Ca Salicylate Calcium salicylate detergent, TBN ~225, ai ~70 OFM 1 glycerol mono-oleate organic ester OFM 2 Tallow Esters of Triethanol Amine; OFM 3 Octadecenyl Succinic Anhydride ZDDP Zinc dialkyl dithiophosphate in oil, where the alkyl groups are derived from 1 and 2 alcohols Mo FM Friction Modifier- Trimeric Mo dialkyldithiocarbamate compound in oil, ~45 ai DPA AO Alkylated diphenylamine antioxidant Phenolic AO Phenolic Antioxidant - C.sub.8 hindered phenol PIBSA Polyisobutylene succinate having an Mn of approximately 2000- 2300 g/mol in oil, ai ~70-75 Anti-foamant Polydimethylsiloxane Lube oil flow improver (LOFI) Fumarate-Vinyl Acetate copolymer in oil, ai ~43 VM-1 Hydrogenated styrene-diene block star viscosity modifier VM-2 Hydrogenated styrene-diene copolymer EP copol VM Ethylene-propylene copolymer viscosity modifier (shear stability index ~25)

EXAMPLES

Example 1

[0721] Inventive and comparative lubricating oil compositions were prepared per the formulation table shown in Table 1 below. The inventive lubricating oils compositions are according to one embodiment (Option A) of the invention. The inventive lubricating oil compositions yielded significantly better performance in the emulsion corrosion test as the comparative example. The inventive lubricating oil compositions also exhibited better performance in the emulsion stability test than the comparative example. The inventors have discovered the importance of detergent selection: carboxylate preferred over sulfonate, and total mmol of soap of greater than 5.0 in the lubricating oil composition for unexpectedly and surprisingly improving the emulsion corrosion resistance in a hybrid engine.

TABLE-US-00003 TABLE 1 Option A Inventive Comparative Inventive Comparative Inventive Formulation Formulation Formulation Formulation Formulation 7 8 1 2 3 5W-40 5W-40 0W-20 0W-20 0W-20 LMW Dispersant 0 0 0.60 0.00 0.00 Borated LMW 0.54 0.54 0.44 0.45 0.55 Dispersant HMW Dispersant 5.20 1.00 5.75 5.07 6.00 PMNE 0.00 0.00 0.50 0.00 0.00 Mg Salicylate 0.00 0.00 0.80 0.00 0.60 Ca Salicylate 2.69 2.69 1.37 0.00 1.40 Ca Sulfonate 0.00 0.00 0.00 1.15 0.00 Mg Sulfonate 0.00 0.00 0.00 0.43 0.00 Other 12.97 15.97 11.00 7.6 10.60 components* OFM 1 0.00 0.00 0.00 0.00 0.60 Gp III Base Oil, 4 78.60 79.80 79.54 85.30 80.25 cSt TOTAL 100.00 100.00 100.00 100.00 100.00 *other LOFI; VM-2; LOFI; VM-2; LOFI; VM-1; LOFI; VM-2; VM-1; components PIBSA; Anti- PIBSA; Anti- Mo FM; Mo FM; PIBSA; Anti- foamant; foamant; PIBSA; Anti- PIBSA; Anti- foamant; DPA AO; DPA AO; foamant; foamant; DPA AO; ZDDP ZDDP DPA AO; DPA AO; Phenolic AO; ZDDP ZDDP ZDDP; #Combined with PAO (6 cSt) SASH wt % 0.78 0.78 0.78 0.77 0.79 P wt % 0.080 0.080 0.078 0.075 0.078 S wt % 0.25 0.24 0.19 0.23 0.18 Mg ppm 10 10 600 390 450 Ca ppm 1800 1800 1100 1330 1300 B ppm 70 70 100 100 72 Mo ppm 80 48 Total Soap mmol 16.7 16.7 12.4 3.3 10.7 Emulsion 3 3 3 0 3 Corrosion Score Emulsion Clear Pass - Clear Fail - Clear Pass - Clear Pass - Clear Pass - Stability 100% 15% 100% 91% 100% 10%/10% emulsion Aqueous emulsion emulsion, emulsion E85/water; 24 h 9% oil Emulsion Clear Pass - Clear Fail - Clear Pass - Clear Pass - Clear Pass - Stability 100% 22% 100% 95% 100% 15%/15% emulsion Aqueous emulsion emulsion, emulsion E85/water; 24 h 5% oil Emulsion n.d. n.d. Clear Pass - Borderline - Clear Pass - Stability 99% 75% 100% 10%/10% emulsion, emulsion, emulsion E85/water; 72 h 1% oil 25% oil Emulsion n.d. n.d. Clear Pass - Borderline - Clear Pass - Stability 99% 84% 100% 15%/15% emulsion, emulsion, emulsion E85/water; 72 h 1% oil 16% oil Emulsion 3 (predicted) 0 (predicted) 3 2 3 Stability Score Bearing Wear n.d. n.d. 6.17 9.11 3.66 polymer wear (average wear depth in micrometers) Bearing Wear n.d. n.d. 3 1 3 Score n.d.not done

Example 2

[0722] Inventive and comparative lubricating oil compositions were prepared as shown in Table 2 below. The inventive lubricating oils compositions are according to another embodiment (Option B) of the invention. The inventive lubricating oil composition yielded significantly better performance in the emulsion corrosion test as compared to the comparative examples. The inventors discovered the importance of organic friction modifier (OFM) selection, which provided surprising and unexpectedly improved performance on emulsion corrosion resistance in a hybrid engine.

TABLE-US-00004 TABLE 2 Option B Inventive Comparative Comparative Comparative Comparative Formulation Formulation Formulation Formulation Formulation 4 5 6 2 8 LMW 0.00 0.00 0.00 0.00 0.60 Dispersant Borated LMW 0.25 0.54 0.54 0.45 0.44 Dispersant HMW 2.90 5.20 5.20 5.07 5.75 Dispersant PMNE 0.00 0.00 0.00 0.00 0.50 Ca Salicylate 0.00 0.00 0.55 0.00 0.00 Ca Sulfonate 0.99 1.58 0.00 1.15 2.75 Mg Sulfonate 0.49 0.00 0.00 0.43 0.66 Other 9.65 11.20 11.70 7.60 11.00 Components* OFM 2 0.35 0.00 0.00 0.00 0.00 OFM 3 0.25 0.00 0.00 0.00 0.00 Gp III BaseOil, 85.12 81.47 82.01 85.31 78.30 4/6 cSt TOTAL 100.00 100.00 100.00 100.00 100.00 SASH wt % 0.72 0.78 0.23 0.77 0.76 P wt % 0.071 0.08 0.08 0.075 0.077 S wt % 0.186 0.26 0.26 0.23 0.26 Mg ppm 450 390 602 Ca ppm 1150 1840 126 1330 1112 B ppm 57 70 70 100 57 Mo 82 48 84 Total Soap 3.1 3.3 2.4 3.3 12.7 mmol Emulsion 3 0 0 0 1 Corrosion Score *other LOFI; EP- LOFI; VM-2; LOFI; VM-2; LOFI; VM-2; LOFI; VM-1; components Copol VM; Mo PIBSA; Anti- PIBSA; Anti- Mo FM; Mo FM; FM; PIBSA; foamant; DPA foamant; DPA PIBSA; Anti- PIBSA; Anti- Anti-foamant; AO; ZDDP AO; ZDDP foamant; DPA foamant; DPA DPA AO; AO; ZDDP AO; ZDDP ZDDP

Example 3

[0723] Inventive and comparative lubricating oil compositions according to Tables 1 and 2 above were prepared and tested for performance as shown in Table 3 below. The compositions were subjected to 3 different sets of bench tests, each providing a score between 0 and 3 (or 1 and 3 in the instance of the bearing wear test). The inventors intended that the average of these tests would provide a way of screening lubricating oil compositions for performance in a hybrid engine. The results in Table 3 show that the inventors have successfully discovered a testing methodology for a quick and low cost assessment of the oil performance against 3 main failure modes of hybrid (PHEV or HEV) engines, which enables the identification and selection of inventive lubricating oil compositions for hybrid ICE applications.

TABLE-US-00005 TABLE 3 Formu- Formu- Formu- Formu- lation lation lation lation 1 2 3 4 Emulsion Corrosion Score 3 0 3 3 Emulsion Stability Score 3 2 3 0 Bearing Wear Score 3 1 3 3 Overall performance 3 1 3 2 rating* *(Total of three scores divided by 3)

[0724] Applicants have attempted to disclose all embodiments and applications of the disclosed subject matter that could be reasonably foreseen. However, there may be unforeseeable, insubstantial modifications that remain as equivalents. While the present invention has been described in conjunction with specific, exemplary embodiments thereof, it is evident that many alterations, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description without departing from the spirit or scope of the present disclosure. Accordingly, the present disclosure is intended to embrace all such alterations, modifications, and variations of the above detailed description.

[0725] All patents, test procedures, and other documents cited herein, including priority documents, are fully incorporated by reference to the extent such disclosure is not inconsistent with this invention and for all jurisdictions in which such incorporation is permitted.

[0726] When numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated.