Anti-Wear Composition for Lubricants

Abstract

Certain citric esters and amides, and certain mixtures thereof, e.g., mixtures comprising citrate oligomers, exhibit excellent anti-wear activity in lubricants. Many of these compounds or mixtures of compounds also exhibit a high degree of anti-wear synergy in combination with zinc dihydrocarbyldithiophosphates. The compounds of the invention are thus valuable tools that can allow one to reduce the amounts of zinc, and phosphates, that are used in the lubricant without sacrificing anti-wear performance.

Claims

1. A lubricant composition comprising: A) a lubricating oil, and B) 0.2 to 5 wt %, based on the weight of the lubricant composition, of ii) a compound of formula II ##STR00026## iii) a compound of formula III ##STR00027## or iv) a mixture of compounds of formula II and formula III, wherein: n is from 1 to 20, R is C.sub.1-18 alkyl; C.sub.1-18 alkyl substituted by a carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or the heterocycle may be substituted by one or more C.sub.1-12 alkyl or alkyloxy; C.sub.2-18 alkyl interrupted by one or more O, carbonyl, carbonyloxy and/or substituted by OH; C.sub.2-18 alkyl interrupted by one or more O, carbonyl or carbonyloxy and substituted by a carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-12 alkyl or alkyloxy; or a carbocycle comprising 5 to 12 carbon atoms, or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-12 alkyl or alkyloxy; and R is C.sub.2-18 alkylene; C.sub.2-18 alkylene interrupted by one or more O, carbonyl or carbonyloxy and/or substituted by OH, carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-12 alkyl or alkyloxy; or said alkylene, interrupted alkylene or substituted alkylene interrupted by a carbocycle comprising 5 to 12 carbon atoms, or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-12 alkyl or alkyloxy, wherein each R and each R may be the same or different from any other R or R.

2. The lubricant composition according to claim 1 comprising more than one compound of formula III, which differ by having different values of n.

3. The lubricant composition according to claim 1 further comprising i) a compound of formula I: ##STR00028## wherein R is as described for formula II and III, and the wt % of all compounds of formula I, II and III combined is from 0.2 wt % to 5.0 wt % based on the weight of the lubricant composition.

4. The lubricant composition according to claim 1 wherein: n is from 1 to 10, 1 to 5, or 1 to 3; R is C.sub.1-16 alkyl, C.sub.1-12 alkyl or C.sub.1-6 alkyl, said alkyl substituted by a carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 8 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or the heterocycle may be substituted by one or more C.sub.1-8 alkyl or alkyloxy; C.sub.2-16 alkyl, C.sub.2-12 alkyl or C.sub.2-6 alkyl interrupted by one or more O, carbonyl, carbonyloxy and/or substituted by a carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 8 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-8 alkyl or alkyloxy; or a carbocycle comprising 5 to 12 carbon atoms, or a heterocycle comprising 3 to 8 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-8 alkyl or alkyloxy, and R is C.sub.2-16 alkylene, C.sub.2-12 alkylene or C.sub.2-8 alkylene, said alkylene interrupted by one or more O, carbonyl or carbonyloxy and/or substituted by OH, carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-8 alkyl or alkyloxy; or said alkylene, interrupted alkylene or substituted alkylene interrupted by a carbocycle comprising 5 to 12 carbon atoms, or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-8 alkyl or alkyloxy.

5. The lubricant composition according to claim 4 further comprising i) a compound of formula I: ##STR00029## wherein R is as described for formula II and III and the wt % of all compounds of formula I, II and III combined is from 0.2 wt % to 5.0 wt %, based on the weight of the lubricant composition.

6. The lubricant composition according to claim 5, which comprises at least one compound of formula I, at least one compound of formula II, and at least one compound of formula III, wherein n is from 1 to 5; R is C.sub.1-12 alkyl or C.sub.2-12 alkyl interrupted by one or more O, and R is C.sub.2-12 alkylene, or said alkylene interrupted by one or more O.

7. A lubricant composition comprising: A) a lubricating oil, and B) 0.2 to 5 wt %, based on the weight of the lubricant composition, of i) a compound of formula I: ##STR00030## wherein R is a carbocycle comprising 5 to 12 carbon atoms, or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-12 alkyl or alkyloxy; C.sub.1-6 alkyl substituted by a carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or the heterocycle may be substituted by one or more C.sub.1-12 alkyl or alkyloxy; C.sub.6-18 alkyl interrupted by one or more O, carbonyl, or carbonyloxy and/or substituted by OH; or C.sub.6-18 alkyl interrupted by one or more O, carbonyl, or carbonyloxy and substituted by OH, carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-12 alkyl or alkyloxy.

8. A lubricant composition comprising: A) a lubricating oil, and B) 0.2 to 5 wt %, based on the weight of the lubricant composition, of a compound of formula IV: ##STR00031## wherein: R is C.sub.1-18 alkyl; C.sub.1-18 alkyl substituted by a carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or the heterocycle may be substituted by one or more C.sub.1-12 alkyl or alkyloxy; C.sub.2-18 alkyl interrupted by one or more O, carbonyl, carbonyloxy and/or substituted by OH; C.sub.2-18 alkyl interrupted by one or more O, carbonyl or carbonyloxy and substituted by a carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-12 alkyl or alkyloxy; or a carbocycle comprising 5 to 12 carbon atoms, or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-12 alkyl or alkyloxy; L is C.sub.1-12 alkylene or C.sub.2-12 alkylene interrupted by O, carbonyl, carbonyloxy, and G is a nitrogen atom or a group comprising one or more nitrogen atoms.

9. The lubricant composition according to claim 8 wherein G is a nitrogen atom, or a linear or branched primary amine, or a linear, branched, or cyclic polyamine.

10. A lubricant composition comprising: A) a lubricating oil, and B) 0.2 to 5 wt %, based on the weight of the lubricant composition, of a compound of formula V or VI: ##STR00032## wherein Y is OR or NRR provided that in formula V at least one Y is NRR L is C.sub.1-12 alkylene or C.sub.2-12 alkylene interrupted by O, carbonyl, carbonyloxy R is C.sub.1-18 alkyl; C.sub.1-18 alkyl substituted by a carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or the heterocycle may be substituted by one or more C.sub.1-12 alkyl or alkyloxy; C.sub.2-18 alkyl interrupted by one or more O, carbonyl, carbonyloxy and/or substituted by OH; C.sub.2-18 alkyl interrupted by one or more O, carbonyl or carbonyloxy and substituted by a carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-12 alkyl or alkyloxy; or a carbocycle comprising 5 to 12 carbon atoms, or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-12 alkyl or alkyloxy; and R is H or R, wherein each R and each R may be the same or different from any other R or R.

11. The lubricant composition according to claim 10 comprising as B) 0.2 to 5 wt %, based on the weight of the lubricant composition, of a compound of formula Va or VIa: ##STR00033##

12. The lubricant composition according to claim 1 further comprising ZDDP.

13. The lubricant composition according to claim 12 wherein the citrates and ZDDP are present in a weight ratio of citrate to ZDDP of 3:1 to 1:3.

14. The lubricant composition according to claim 1 wherein the lubricating oil is present at about 90 wt % or more.

15. The lubricant composition according to claim 1 further comprising one or more additional lubricant additive selected from the group consisting of dispersants, detergents, corrosion/rust inhibitors, antioxidants, anti-wear agents, anti-foamants, friction modifiers, seal swell agents, demulsifiers, V.I. improvers and pour point depressants.

16. The lubricant composition according to claim 7 further comprising ZDDP.

17. The lubricant composition according to claim 16 wherein the citrates and ZDDP are present in a weight ratio of citrate to ZDDP of 3:1 to 1:3.

18. The lubricant composition according to claim 7 wherein the lubricating oil is present at about 90 wt % or more.

19. The lubricant composition according to claim 7 further comprising one or more additional lubricant additive selected from the group consisting of dispersants, detergents, corrosion/rust inhibitors, antioxidants, anti-wear agents, anti-foamants, friction modifiers, seal swell agents, demulsifiers, V.I. improvers and pour point depressants.

20. The lubricant composition according to claim 8 further comprising ZDDP.

21. The lubricant composition according to claim 20 wherein the citrates and ZDDP are present in a weight ratio of citrate to ZDDP of 3:1 to 1:3.

22. The lubricant composition according to claim 8 wherein the lubricating oil is present at about 90 wt % or more.

23. The lubricant composition according to claim 8 further comprising one or more additional lubricant additive selected from the group consisting of dispersants, detergents, corrosion/rust inhibitors, antioxidants, anti-wear agents, anti-foam

24. The lubricant composition according to claim 10 further comprising ZDDP.

25. The lubricant composition according to claim 24 wherein the citrates and ZDDP are present in a weight ratio of citrate to ZDDP of 3:1 to 1:3.

26. The lubricant composition according to claim 10 wherein the lubricating oil is present at about 90 wt % or more.

27. The lubricant composition according to claim 10 further comprising one or more additional lubricant additive selected from the group consisting of dispersants, detergents, corrosion/rust inhibitors, antioxidants, anti-wear agents, anti-foamants, friction modifiers, seal swell agents, demulsifiers, V.I. improvers and pour point depressants, friction modifiers, seal swell agents, demulsifiers, V.I. improvers and pour point depressants.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0017] FIG. 1 shows a Liquid Chromatography Mass Spectrometry (LCMS) analysis of an exemplary product reaction mixture obtained by the reaction of citric acid and butane diol and conversion of residual acids to butyl esters in accordance with the present disclosure.

DETAILED DESCRIPTION

[0018] The compounds and compound combinations of the invention exhibit friction reduction activity and anti-wear activity in lubricants. The friction reduction activity is often higher than the activity seen with currently used citrate lubricant additives, and in many embodiments, the anti-wear activity of the compounds of the invention surpasses that of known citric acid derived additives, e.g., citrates, and even ZDDP. In many cases, compounds of the invention show synergy when mixed with ZDDP. The excellent activity of the compounds of the invention allows one to reduce the amount of ZDDP present in automobile and truck lubricants, thereby reducing the zinc and phosphorus content of the lubricants.

[0019] Throughout the present application, a or an means one or more than one unless indicated otherwise.

[0020] Citrate compounds useful in lubricant compositions of the present invention include compounds of formula I, II or III:

##STR00005##

wherein: [0021] n is 1 to 20, e.g., 1 to 10, 1 to 5, or 1 to 3; [0022] R is C.sub.1-15 alkyl; [0023] C.sub.1-18 alkyl substituted by a carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or the heterocycle may be substituted by one or more C.sub.1-12 alkyl or alkyloxy; [0024] C.sub.2-18 alkyl interrupted by one or more O, carbonyl, carbonyloxy and/or substituted by OH; [0025] C.sub.2-18 alkyl interrupted by one or more O, carbonyl or carbonyloxy and substituted by a carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-12 alkyl or alkyloxy; or [0026] a carbocycle comprising 5 to 12 carbon atoms, or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-12 alkyl or alkyloxy; and [0027] R is C.sub.2-18 alkylene; [0028] C.sub.2-18 alkylene interrupted by one or more O, carbonyl or carbonyloxy and/or substituted by OH, a carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-12 alkyl or alkyloxy; or [0029] said alkylene, interrupted alkylene or substituted alkylene interrupted by a carbocycle comprising 5 to 12 carbon atoms, or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-12 alkyl or alkyloxy.

[0030] For example, compounds of formula I, II or III wherein: [0031] R is C.sub.1-16 alkyl, C.sub.1-12 alkyl or C.sub.1-6 alkyl, said alkyl substituted by a carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 8 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or the heterocycle may be substituted by one or more C.sub.1-8 alkyl or alkyloxy; [0032] C.sub.2-16 alkyl, C.sub.2-12 alkyl or C.sub.2-6 alkyl interrupted by one or more O, carbonyl, carbonyloxy and/or substituted by a carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 8 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-8 alkyl or alkyloxy; or [0033] carbocycle comprising 5 to 12 carbon atoms, or a heterocycle comprising 3 to 8 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-8 alkyl or alkyloxy; and [0034] R is C.sub.2-16 alkylene, C.sub.2-12 alkylene or C.sub.2-8 alkylene, said alkylene interrupted by one or more O, carbonyl or carbonyloxy and/or substituted by OH, a carbocycle comprising 5 to 12 carbon atoms or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-8 alkyl or alkyloxy; or [0035] said alkylene, interrupted alkylene or substituted alkylene interrupted by a carbocycle comprising 5 to 12 carbon atoms, or a heterocycle comprising 3 to 11 carbon atoms and one or more heteroatoms selected from O, S and N, wherein the carbocycle or heterocycle may be substituted by C.sub.1-8 alkyl or alkyloxy.

[0036] Alkyl may be linear alkyl or branched alkyl; alkylene may be linear alkylene or branched alkylene. Alkylene refers to a hydrocarbon based chain or group connected to two other groups, also known as an alkyl-diyl. Carbocycle and heterocycle may be aromatic or non-aromatic, monocyclic or polycyclic. Alkyl or alkylene interrupted by O may be an ether, for example, R may be as shown in parentheses:

##STR00006##

or polyether, for example, R may be as shown in parentheses:

##STR00007##

[0037] In some exemplary embodiments:

R is ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, benzyl, norbornane methyl, adamantyl, tetrahydrofurfuryl, triethylene glycol mono-methyl ether, and isomers thereof, such as, isopropyl isobutyl, sec-butyl, tert-butyl, iso-pentyl, tert-pentyl, 2-ethylhexyl, and the like; and
R is ethane diyl; propane 1,2- or 1,3-diyl; butane 1,4-, 1,2 or 1,3 diyl; pentane 1,5 or 1,4 diyl; hexane 1,6-diyl; 2-ethyl hexane 1,6-diyl; and the like.

[0038] Compounds of formula IV can also be used in lubricant compositions of the invention, either on their own or in combination with other citrates or citramides, and with or without synergistic antiwear additives such as ZDDP:

##STR00008##

wherein R is as defined above, x is 2, 3, 4, 5 or 6, typically 2 or 3, L is a linking group, such as, C.sub.1-12 alkylene, C.sub.1-12 alkylene interrupted by O, carbonyl, carbonyloxy, and G is a nitrogen atom or a group comprising one or more nitrogen atoms, such as a linear or branched primary amine or linear, branched or cyclic polyamine. Compounds of formula IV can be prepared in a straightforward manner, e.g.:

##STR00009##

[0039] Further embodiments provide compounds of formula V and VI and lubricant compositions comprising them:

##STR00010##

wherein L and R are as defined above, R is H or R, and Y is OR or NRR provided that in formula V at least one Y is NRR. Generally, in compounds of formula V, two or all three Y groups are NRR, e.g., formula Va, and often in compounds of formula VI, the majority or all Y groups are OR, e.g., formula VIa:

##STR00011##

[0040] Primary amines such as 2-ethylhexylamine, secondary amines such as N-butyl-N-methyl amine, long chain amines such as oleic amine, and mixtures of amines such as tallow amine, have been used to construct many of the amide groups in the formula above. For example, data obtained from lubricant compositions comprising tris(2-ethylhexyl) citramide, tris(N-butyl-N-methyl) citramide, trioleyl citramide, tritallow citramide, tris(hydrogenated tallow) citramide, tritallow citramide, and trioleyl citramide can be found in the Examples.

[0041] A hydroxyalkyl amine can be conveniently used to form the N-L-O linking segment found in formula VI and VIa. For example, bis (2-hydroxypropyl)amine can be used in the preparation of compounds of formula VIa like:

##STR00012##

[0042] Compositions of the invention comprise, for example:

A) a natural or synthetic lubricating oil, and
B) from about 0.25 to about 5 wt %, e.g., about 0.5 to about 5, about 0.5 to about 3, about 0.5 to about 2, about 0.75 to about 1.5 wt %, based on the weight of the lubricant composition, of one or more compounds of formula II, III, IV, V or VI and optionally compounds of formula I, as described above, e.g., a composition comprising at least one compound of formula II and at least one compound of formula III, or a composition comprising at least one compound of formula I, at least one compound of formula II, and at least one compound of formula III.

[0043] A composition comprising:

A) a natural or synthetic lubricating oil, and
B) from about 0.25 to about 5 wt %, e.g., about 0.5 to about 5, about 0.5 to about 3, about 0.5 to about 2, about 0.75 to about 1.5 wt %, based on the weight of the lubricant composition, of one or more compounds of formula I wherein R is a carbocycle or heterocycle, alkyl substituted by carbocycle or heterocycle, or alkyl interrupted by O, such as a polyether; for example, the compound of formula I may be tris benzyl, tris norbornane methyl, tris adamantyl, tris tetrahydrofurfuryl, or tris triethylene glycol mono-methyl ether esters of citric acid, and the like.

[0044] Further embodiments provide lubricant compositions comprising one or more of the citrates or citramides above and ZDDP. Due to the excellent activity of the compounds of the invention, one can use less ZDDP, and thus lower the amount of zinc and phosphorus in a lubricant while maintaining excellent anti-wear and anti-friction properties. In many embodiments, synergistic activity is seen when certain citrates and citramides are blended with ZDDP, i.e., activity of the blend at a load level exceeds the activity of either the citric acid based component, (e.g., citrate or citramide), or the ZDDP at the same load level.

[0045] For example, the invention provides a composition comprising;

A) a natural or synthetic lubricating oil, and
B) from about 0.25 to about 5 wt %, e.g., about 0.5 to about 5, about 0.5 to about 3, about 0.5 to about 2, about 0.75 to about 1.5 wt %, based on the weight of the lubricant composition, of one or more compounds of formula I, II, III, IV, V and/or VI and ZDDP in a weight ratio of citric acid based component to ZDDP of 3:1 to 1:3; 2:1 to 1:2; 1.5:1 to 1:1.5; 2:1 to 1:1; 1:1 to 1:2.

[0046] Citrates of formula I can be prepared by any known esterification process. Some embodiments provide lubricant compositions comprising compounds of formula I wherein R is a carbocycle or heterocycle, alkyl substituted by carbocycle or heterocycle, or alkyl interrupted by O, such as a polyether; for example, tris benzyl, tris norbornane methyl, trisadamantyl, tris tetrahydrofurfuryl, or tris triethylene glycol mono-methyl ether esters of citric acid, and the like. Such compounds can be used with or without other citrates, and with or without synergistic anti-wear additives such as ZDDP.

[0047] In one method of preparing compounds of formula II and III, citric acid is reacted with a polyol, such as a diol, often in the presence of an acid catalyst, such as methane sulfonic acid, to obtain a dimer, trimer, various other oligomers, etc., depending on the relative amounts of citric acid and polyol used, followed by standard esterification of the remaining carboxylic acid groups, e.g., reaction with a monohydric alcohol in the presence of an acid, i.e., a two-step method. In an alternate method, citric acid is reacted with an alcohol, such as butanol, and a diol, such as 1,6-hexanediol, together, in the presence of a catalyst, e.g., an acid catalyst, at the same time in the same vessel, i.e., a one-step method.

[0048] Often, depending on the process for the preparation of compounds of formula III, and even when attempting to prepare predominately compounds of formula II, a mixture of compounds of formula III differing in the value for n will be present in varying amounts. For example, when preparing predominately a trimer, i.e., a compound of formula III wherein n=1, it is common for dimers, monomeric compounds, tetramers and pentamers to also be present. In some instances, mixtures such as these are desirable, as mixtures often can exhibit a higher degree of solubility than a single component.

[0049] In one example, FIG. 1 shows a Liquid Chromatography Mass Spectrometry (LCMS) analysis of an exemplary product reaction mixture obtained by the reaction of citric acid and butane diol and conversion of residual acids to butyl esters in accordance with the present disclosure. The top Total Ion Chromatogram (TIC) is that of the whole product mixture with all oligomers. The individual peaks provided in the rows below represent separate HPLC isolated oligomers. The main product oligomers shown include a coupled product or dimer-citrate oligomer (terminal citrate ester represented as (A), and the linker diol as (B), giving A-B-A oligomer), a trimer-citrate oligomer A-B-A-B-A (again citrate terminal esters (A) and added internal ester (A), joined by the diol linker (B)), a tetramer-citrate oligomer designated as A-B-A-B-A-B-A, followed by a pentamer-citrate oligomer A-B-A-B-A-B-A-B-A, and a hexamer-citrate oligomer A-B-A-B-A-B-A-B-A-B-A.

[0050] Many embodiments of the present disclosure make use of the above one step or two step method to generate mixtures of compounds comprising varying amounts of compounds of formula II and formula III having different values for n. Often, these mixtures will also contain compounds of formula I. By varying conditions, one can increase the amount of a desired component, and, if desired, it is possible to separate the mixtures using standard techniques.

[0051] Synergistic activity is seen when certain compounds of the invention are blended with ZDDP, i.e., activity of the blend at a load level exceeds the activity of either the citric acid derivative or the ZDDP at the same load level. For example, as shown in the Examples, lubricant compositions comprising 1 wt % of a 1:1 mixture of ZDDP and select citrates or citrate mixtures comprising a compound of formula II, provide better anti-wear protection than either 1 wt % ZDDP or 1 wt % of the same citrate compound(s).

[0052] Lubricant compositions containing a reference 5W-30 oil without any other antiwear additives, were blended with 1 wt % of citrates of the invention or various industry standards, e.g., 1 wt % ZDDP, triethyl citrate or tributyl citrate, and tested for anti-wear activity using standard 4-ball anti-wear tests ASTM D4172, and a modified ASTM D4172 where 0.615 wt % cumene hydroperoxide (chp) was added to the lubricant to simulate oxidative aging. Another series of tests was run using lubricant compositions containing 0.5 wt % ZDDP and 0.5 wt % inventive citrate additives. Full results can be found in the Examples.

[0053] Several of the inventive compounds exhibited improved performance over the commercial alkyl citrate additives triethyl citrate or tri-n-butyl citrate. For example, bis-trihexylcitrate dioxalate, bis-trioctylcitrate dioxalate, and four higher citrate oligomers, hexane-1,6-diyl bis-dihexyl citrate, ethane-1,2-diyl bisdihexyl citrate, propane-1,2-diyl bisdihexyl citrate, and butane-1,4-diyl bisdihexyl citrate all provided significantly better anti-wear performance than the commercial citrate standards. Among the bis dialkyl citrate diol linked oligomers, the bis-dihexyl citrates appeared to have some advantage over shorter chain esters. 1,2-ethane-diol, 1,2-propane-diol, and 1,4-butane-diol linkers showed some advantage over the 1,6-hexane-diol linked oligomers.

[0054] In one comparison, oligomers of bis-dihexyl citrate formed in one step from citric acid and a mixture of 1,6-hexane-diol and n-hexanol provided better anti-wear performance than a similar mixture of compounds formed in two steps, first reacting citric acid with 1,6-hexane diol followed by reaction with n-hexanol. In another comparison, 2-ethyl hexyl citrate dioxalate underperformed the hexyl counterparts bis-trihexyl citrate dioxalate and bis-trioctylcitrate dioxalate. It appears possible that gains in solubility due to the branching of the 2-ethyl hexyl derivative may be offset by the same branching interfering with the compound organizing on the surface.

[0055] Significant synergy was observed when ZDDP was blended with either hexane-1,6-diyl bis-dihexyl citrate, ethane-1,2-diyl bisdihexyl citrate, or propane-1,2-diyl bisdihexyl citrate, either in the presence or absence of chp, e.g.:

TABLE-US-00001 Wear, mm, no chp, Wear, mm, chp, 0.5 wt % sample/ 0.5 wt % sample/ Sample 0.5 wt % ZDDP 0.5 wt % ZDDP STD, no additive 0.598 0.740 ZDDP 0.441 0.476 Hexane-1,6-diyl, 0.335 0.386 bisdihexyl citrate 1 -step Ethane-1,2-diyl 0.308 0.379 bisdihexyl citrate Propane-1,2-diyl 0.325 0.349 bisdihexyl citrate

[0056] Commercial lubricant formulations typically contain a variety of other additives, for example, dispersants, detergents, corrosion/rust inhibitors, antioxidants, anti-wear agents, anti-foamants, friction modifiers, seal swell agents, demulsifiers, V.I. improvers, pour point depressants, and the like. A sampling of these additives can be found in, for example, U.S. Pat. Nos. 5,498,809 and 7,696,136, the relevant portions of each disclosure are incorporated herein by reference, although the practitioner is well aware that this comprises only a partial list of available lubricant additives. It is also well known that one additive may be capable of providing or improving more than one property, e.g., an anti-wear agent may also function as an anti-fatigue and/or an extreme pressure additive.

[0057] The lubricant compositions of the invention will often contain any number of these additives. Thus, final lubricant compositions of the invention will generally contain a combination of additives along with the inventive citrates, in a combined concentration ranging from about 0.5 to about 30 weight percent, e.g., from about 0.5 to about 10 weight percent based on the total weight of the oil composition. For example, the combined additives may be present from about 1 to about 5 weight percent. Oil concentrates of the additives can contain from about 30 to about 75 weight percent additives.

[0058] Given the ubiquitous presence of additives in a lubricant formulation, the amount of lubricating oil present in the inventive composition is not specified above, but in most embodiments, except additive concentrates, the lubricating oil is a majority component, i.e., present in more than 50 wt % based on the weight of the composition, for example, 60 wt % or more, 70 wt % or more, 80 wt % or more, 90 wt % or more, or 95 wt % or more.

[0059] The natural or synthetic lubricating oil of the invention can be any suitable oil of lubricating viscosity. For example, a lubricating oil base stock is any natural or synthetic lubricating oil base stock fraction having a kinematic viscosity at 100 C. of about 2 to about 200 cSt, about 3 to about 150 cSt, and often about 3 to about 100 cSt. The lubricating oil base stock can be derived from natural lubricating oils, synthetic lubricating oils, or mixtures thereof. Suitable lubricating oil base stocks include, for example, petroleum oils, mineral oils, and oils derived from coal or shale petroleum based oils, animal oils, such as lard oil, vegetable oils (e.g., canola oils, castor oils, sunflower oils) and synthetic oils.

[0060] Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils, such as polymerized and interpolymerized olefins, gas-to-liquids prepared by Fischer-Tropsch technology, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs, homologs, and the like. Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers, and derivatives thereof, wherein the terminal hydroxyl groups have been modified by esterification, etherification, etc. Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids with a variety of alcohols. Esters useful as synthetic oils also include those made from monocarboxylic acids or diacids and polyols and polyol ethers. Other esters useful as synthetic oils include those made from copolymers of alphaolefins and dicarboxylic acids which are esterified with short or medium chain length alcohols.

[0061] Silicon-based oils, such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils, comprise another useful class of synthetic lubricating oils. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, poly alphaolefins, and the like.

[0062] The lubricating oil may be derived from unrefined, refined, re-refined oils, or mixtures thereof. Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar and bitumen) without further purification or treatment. Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment. Refined oils are similar to unrefined oils, except that refined oils have been treated in one or more purification steps to improve one or more properties. Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, percolation, and the like, all of which are well-known to those skilled in the art. Re-refined oils are obtained by treating refined oils in processes similar to those used to obtain the refined oils. These re-refined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.

[0063] Lubricating oil base stocks derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforesaid natural and/or synthetic base stocks. Such wax isomerate oil is produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst. Natural waxes are typically the slack waxes recovered by the solvent dewaxing of mineral oils; synthetic waxes are typically the waxes produced by the Fischer-Tropsch process. The resulting isomerate product is typically subjected to solvent dewaxing and fractionation to recover various fractions having a specific viscosity range. Wax isomerate is also characterized by possessing very high viscosity indices, generally having a V.I. of at least 130, preferably at least 135 or higher and, following dewaxing, a pour point of about 20 C. or lower.

[0064] The friction modifying mixture of metal based friction modifier and hydroxy carboxylic ester or amide of the invention can be added to the lubricating oil directly as a combination or as individual components. The mixture can be added by itself or along with other common additives. A concentrate containing the mixture may also be prepared and added to the lubricating oil. It is also possible to add the friction modifying mixture to a preformulated lubricating oil which already contains all or most of the other formulation components.

[0065] The lubricating oil compositions of the invention can be used in a variety of applications, for example, crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, gas engine lubricants, turbine lubricants, automatic transmission fluids, gear lubricants, compressor lubricants, metal-working lubricants, hydraulic fluids, and other lubricating oil and grease compositions.

[0066] Further non-limiting disclosure is provided in the Examples that follow.

EXAMPLES

[0067] Compounds, typically mixtures of compounds of the following formula, wherein x is a number of from 1 to 20 and R and R are as described above, are prepared according to general procedures A or B.

##STR00013##

General Procedure 1

[0068] A) To a mixture of citric acid, diol and toluene is added a catalytic amount of methanesulfonic or other acid, the flask is equipped with a Dean-Stark trap and condenser, flushed with N.sub.2, then heated to reflux with stirring. The reaction can be followed by any standard means. When judged complete, the reaction is cooled to ambient temperature, washed with saturated sodium bicarbonate and brine, the organic layer is dried over anhydrous sodium sulfate, filtered, and typically heated to 60 C. under vacuum, to yield the final product, typically as a mixture comprising dimers, trimers and higher oligomers of different chain lengths.
B) The product from A is combined with an alcohol, e.g., a mono-hydroxy alkyl, toluene, and a catalytic amount of methanesulfonic or other acid, the flask is equipped with a Dean-Stark trap and condenser, flushed with N.sub.2, then heated to reflux with stirring. When judged complete, the reaction is cooled to ambient temperature, washed with saturated sodium bicarbonate and brine, the organic layer is dried over anhydrous sodium sulfate, filtered, and typically heated to 60 C. under vacuum, to yield the final product.

General Procedure 2

[0069] To a mixture of citric acid, diol, mono-hydroxy alkyl and toluene is added a catalytic amount of methanesulfonic or other acid, the flask is equipped with a Dean-Stark trap and condenser, flushed with N.sub.2, then heated to reflux with stirring. The reaction can be followed by any standard means. When judged complete, the reaction is then cooled to ambient temperature, washed with saturated sodium bicarbonate and brine, the organic layer is dried over anhydrous sodium sulfate, filtered, and typically heated to 60 C. under vacuum, to yield the final product, typically as a mixture comprising dimers, trimers and higher oligomers of different chain lengths.

[0070] Citrate products of the invention were prepared using the following pairs of diols and mono-hydroxy alkyl using the process of General Procedure 1 or General Procedure 2. Some of the pairs were used to prepared citrate products following each of the General Procedures. For example, products were prepared using the mixture of Ex 10, i.e., 1, 6-hexane diol and hexanol according to General Procedure 1, and a separate product mixture was prepared from 1, 6-hexane diol and hexanol according to General Procedure 2.

TABLE-US-00002 EX Diol mono-Hydroxyl Alkyl 1 1,2-Ethane diol Hexanol 2 1,2-Propane diol Hexanol 3 1,4-Butane diol Ethanol 4 1,4-Butane diol Hexanol 5 1,6-Hexane diol Butanol 6 1,2-Proane diol Butanol 7 1,4-Butane diol Butanol 8 1,6-Hexane diol Hexanol 9 1,4-Butane diol 2-Ethylhexanol 10 1,6-Hexane diol iso-Pentanol

Example 11Tris(Tetrahydrofurfuryl) Citrate

[0071] ##STR00014##

[0072] Citric acid (8.0 g, 42 mmol) and tetrahydrofurfuryl alcohol (14.9 g, 146 mmol) were weighed into a flask, toluene (80 ml) and methanesulfonic acid (0.10 ml, 1.5 mmol) were added, the flask was equipped with a Dean-Stark trap and condenser, the flask was flushed with N.sub.2, then heated to reflux with stirring for 6.5 h. The reaction mixture was cooled to ambient temperature, washed with saturated sodium bicarbonate, and brine. The organic layer was dried over anhydrous sodium sulfate, filtered, and heated to 60 C. for 1.5 h under vacuum (0.5 torr) to provide the final product as a yellow oil (9.5 g).

Example 12Mixed Ethyl-Tetrahydrofurfuryl Citrate

[0073] Triethyl citrate (12.01 g, 43.47 mmol) and tetrahydrofurfuryl alcohol (15.03 g, 147.2 mmol) were weighed into a 3 neck flask equipped with a condenser with distillate collection flask, vacuum attachment, and N.sub.2 inlet. The system was flushed with N.sub.2, heated to 65 C. and sodium methoxide (0.50 ml of a 25 wt % MeOH solution, 2.2 mmol) was added. The temperature was increased to 85 C. and the reaction mixture was stirred for 12 h under vacuum (200 torr). Additional sodium methoxide (0.30 ml of a 25 wt % MeOH solution, 1.3 mmol) was added and the reaction was continued for an additional 11 h, after which the reaction mixture was cooled to ambient temperature, diluted with toluene (30 ml), and washed with saturated sodium bicarbonate and brine. The organic layer was dried over anhydrous sodium sulfate and filtered leaving a solution that was placed under vacuum to remove volatile components to provide the product as an amber oil (12 g).

Example 13Tris(1-Adamantyl) Citrate

[0074] ##STR00015##

[0075] Citric acid (2.00 g, 10.4 mmol), 1-adamantanol (4.94 g, 32.4 mmol), and p-toluenesulfonic acid monohydrate (0.197 g, 1.04 mmol) and toluene (70 ml) were added to a flask that was equipped with a Dean Stark trap and condenser, then flushed with N.sub.2, and heated to reflux with stirring for 76 h, after which the reaction mixture was cooled to ambient temperature, washed with 2 M aqueous NaOH, water, and brine. The organic layer was dried over anhydrous sodium sulfate and filtered to provide a solution which was placed under vacuum to remove volatile components and provide a yellow solid crude product. Unreacted 1-adamantanol was removed from the crude product by sublimation under vacuum (50 mtorr) at temperatures increasing from 120 C. to 165 C. for 5 h to provide the final product as a yellow solid (1.59 g).

Example 14Tris(2-Adamantyl) Citrate

[0076] ##STR00016##

[0077] Citric acid (2.00 g, 10.4 mmol), 2-adamantanol (4.90 g, 32.2 mmol), toluene (60 ml), and methanesulfonic acid (0.09 ml, 1 mmol) were added to a flask that was equipped with a Dean-Stark trap and condenser, then flushed with N.sub.2, then heated to reflux with stirring for 70 h. The reaction mixture was cooled to ambient temperature, washed with saturated sodium bicarbonate and brine, the organic layer was dried over anhydrous sodium sulfate, filtered, and then heated to 60 C. for 2 h under vacuum (0.5 torr) to provide a white solid crude product. Unreacted 2-adamantanol was removed from the crude product by sublimation under vacuum (50 mtorr) at 145 C. for 6 h to provide the final product as a white solid (4.08 g).

Example 15Tris(2-Norbornanemethyl)Citrate

[0078] ##STR00017##

[0079] Citric acid (4.0 g, 21 mmol) and 2-norbornanemethanol (mixture of endo and exo, 9.7 g, 77 ml, 0.8 mmol), toluene (60 ml) and methanesulfonic acid (0.10 ml, 1.5 mmol) were added to a flask that was equipped with a Dean-Stark trap and condenser, then flushed with N.sub.2, and heated to reflux with stirring for 70 h, after which the reaction mixture was cooled to ambient temperature, washed with saturated sodium bicarbonate and brine. The organic layer was dried over anhydrous sodium sulfate, filtered, and then heated to 60 C. for 2 h under vacuum (0.5 torr) to yield the final product as an amber oil.

Example 16Tris(Triethylene Glycol Monomethyl Ether) Citrate

[0080] ##STR00018##

[0081] Citric acid (8.0 g, 42 mmol) and triethylene glycol monomethyl ether (23.0 g. 140 mmol) toluene (60 ml) and methanesulfonic acid (0.10 ml, 1.5 mmol) were added to a flask that was equipped with a Dean-Stark trap and condenser, then flushed with N.sub.2, and heated to reflux with stirring for 17 h, after which the reaction mixture was cooled to ambient temperature and washed with saturated sodium bicarbonate and brine. The resulting sodium bicarbonate solutions were then washed with ethyl acetate. The ethyl acetate washings were dried over anhydrous sodium sulfate, filtered, and then heated to 60 C. for 2 h under vacuum (0.5 torr) to yield the final product as a clear colorless liquid (11 g).

Example 17Tribenzyl Citrate

[0082] ##STR00019##

[0083] Citric acid (4.00 g, 20.8 mmol) and benzyl alcohol (6.78 g, 62.7 mmol), toluene (60 ml) and methanesulfonic acid (0.10 ml, 1.5 mmol) were added to a flask that was equipped with a Dean-Stark trap and condenser. The flask was flushed with N.sub.2, heated to reflux with stirring for 26 h, after which the reaction mixture was cooled to ambient temperature, diluted with toluene (50 ml), and washed with saturated sodium bicarbonate, water, and brine. The organic layer was dried over anhydrous sodium sulfate, filtered, then heated to 60 C. for 2 h under vacuum (0.5 torr) to provide the crude product as a yellow liquid. The crude product was purified by silica column chromatography using hexanes/ethyl acetate (5:1 to 3:1) mobile phase to provide the final product as a clear colorless liquid (5.5 g).

Example 181,4-Bis(Ethyl-2-Diethylcitrate)Piperazine

[0084] ##STR00020##

[0085] 1,4-Bis(2-hydroxyethyl)piperazine (2.03 g, 11.7 mmol) and triethyl citrate (26.02 g, 94.19 mmol) were added to a flask equipped with a thermocouple, N.sub.2 supply, and rubber stopper. The mixture was stirred and N.sub.2 was bubbled through the liquid reaction mixture for 20 min while the mixture was heated to 70 C. Sodium methoxide (0.525 ml of a 25 wt. % MeOH solution, 2.30 mmol) was added dropwise causing a color change from colorless to dark yellow. The rubber stopper was removed and distillation head was attached along with a condenser, vacuum adapter and receiving flask. Vacuum was slowly applied (approx. 100 torr) while heating at 85 and stirring for 5 h, after which the reaction mixture was cooled to ambient temperature, diluted with ethyl acetate, and washed with H.sub.2O and brine. The organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated to a volume of 50 ml. The crude product was purified by silica column chromatography using ethyl acetate/methanol (neat ethyl acetate to 3:1 mixture) mobile phase to provide the final product as an amber oil (3.9 g).

Example 191,4-Bis(Ethyl-2-Dibutylcitrate)Piperazine

[0086] ##STR00021##

[0087] 1,4-Bis(2-hydroxyethyl)piperazine (1.92 g, 11.0 mmol) and tributyl citrate (31.53 g, 87.48 mmol) were added to a 3 neck flask equipped with a condenser, distillate collection flask, vacuum attachment, and N.sub.2 inlet. The system was flushed with N.sub.2 and sodium methoxide (0.510 ml of a 25 wt. % MeOH solution, 2.23 mmol) was added. The temperature was increased to 85 C., the reaction mixture was stirred for 7 h under vacuum (approx. 0.1 torr), additional sodium methoxide (0.125 ml of a 25 wt. % MeOH solution, 0.547 mmol) was added and the reaction was continued for an additional 5 h. The reaction mixture was then cooled to ambient temperature, diluted with ethyl acetate, and washed with H.sub.2O and brine. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated to a volume of 70 ml. The crude product was purified by silica column chromatography using ethyl acetate mobile phase to provide the final product as an amber oil (1.7 g).

Example 20Tris(Ethyl-2-Dibutylcitrate)Amine

[0088] ##STR00022##

[0089] Triethylamine (1.64 g, 11.0 mmol) and tributyl citrate (31.97 g, 88.71 mmol) were added to a 3 neck flask equipped with a thermocouple, N.sub.2 supply, and rubber stopper. The mixture was stirred and heated to 70 C. while N.sub.2 was bubbled through the liquid reaction mixture for 1 h. Sodium methoxide (0.500 ml of a 25 wt % MeOH solution. 2.19 mmol) was then added dropwise, the rubber stopper was removed, a distillation head, condenser, vacuum adapter and receiving flask were attached and vacuum was slowly applied (approx. 0.3 torr) while heating at 80 C. and stirring for 3 h. The reaction mixture was then cooled to ambient temperature, diluted with ethyl acetate, washed twice with a 15/2 H.sub.2O/brine mixture, followed by washing with brine. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated to a volume of 80 ml. The crude product was purified by silica column chromatography using hexanes/ethyl acetate (1:1) mobile phase to provide the final product as a yellow oil (0.65 g).

Example 21Performance Tests

[0090] Lubricant compositions comprising a reference 5W-30 oil without any other anti-wear additives, and containing 1 wt % of additives of the invention were tested for anti-wear activity using standard 4-ball anti-wear tests ASTM D4172, and modified ASTM D4172 procedure where 0.615% cumene hydroperoxide (chp) was added to the lubricant to simulate oxidative aging. The results were compared to those obtained using 1 wt % ZDDP, triethyl citrate or tributyl citrate. Another series of tests used lubricant compositions containing 0.5 wt % ZDDP and 0.5 wt % citrate additives. The results are shown in the tables below:

TABLE-US-00003 Wear, mm, Wear, mm, no chp, Wear, mm, Wear, mm, chp, no chp, 1 wt % 0.5 wt % sample/ chp 1 wt % 0.5 wt % sample/ Sample sample 0.5 wt % ZDDP sample 0.5 wt % ZDDP STD 0.598 0.740 ZDDP 0.441 0.441 0.476 0.476 NL 810 (Triethyl citrate) 0.500 0.601 NL 812 (Tributyl citrate) 0.468 0.428 0.578 0.500 Tri-hexyl citrate 0.460 0.375 0.560 0.445 Bis-trihexyl citrate 0.381 0.503 dioxalate Bis-trioctyl citrate dioxalate 0.385 0.506 Bis-triethyl citrate dioxalate 0.458 0.542 Bis-tri-2-ethylhexyl citrate 0.427 0.535 dioxalate Butane-1,4-diyl bisdiethyl 0.452 0.537 citrate Hexane-1,6-diyl bisdihexyl 0.456 0.560 citrate (2-step) Hexane-1,6-diyl bisdihexyl 0.398 0.335 0.502 0.386 citrate (1-step) Ethane-1,2-diyl bisdihexyl 0.415 0.308 0.487 0.379 citrate Propane-1,2-diyl bisdihexyl 0.425 0.325 0.500 0.349 citrate Butane-1,2-diyl bisdihexyl 0.426 0.517 citrate

TABLE-US-00004 Wear, mm, Wear, mm, Wear, mm, chp, no chp 1 wt % chp, 1 wt % 0.5 wt % sample/ Sample sample sample 0.5 wt % ZDDP STD 0.573 0.540 0.540 STD + 0.5% ZDDP 0.446 0.604 0.604 ZDDP 0.446 0.491 0.491 Tributyl citrate 0.468 0.578 0.502 mixed Ethvl-tetrahydrofurfuryl- 0.430 0.560 0.475 citrate Tris(tetrahydrofurfuryl) citrate 0.413 0.531 0.465 Tris(1-adamantyl) citrate 0.455 0.544 0.556 Tris(2-adamantyl) citrate 0.466 0.581 0.537 Tris(2-norbornanemethyl) citrate 0.478 0.583 0.526 Tris(triethvleneqlvcol mono- 0.421 0.557 0.559 methvl ether) citrate Tribenzvl citrate. 0.557 0.518 0.513 1,4-Bis(ethyl-2-diethyl citrate) 0.472 piperazine 1,4-Bis(ethyl-2-dibutyl citrate) 0.473 0.557 0.482 piperazine Tris(ethyl-2-dibutyl citrate) amine 0.500 0.572 0.461

[0091] The following series of citric acid derivatives, amides and ester, were tested for anti-wear activity as above.

##STR00023##

[0092] Di-hexylhydroxy ethyl citrate, may contain minor amounts of Dihydroxethyl hexyl citrate,

##STR00024##

TABLE-US-00005 Wear, mm, Wear, mm, no chp, Wear, mm, Wear, mm, chp, no chp, 1 wt % 0.5 wt % sample/ chp, 1 wt % 0.5 wt % sample/ Sample sample 0.5 wt % ZDDP sample 0.5 wt % ZDDP STD 0.584 0.684 ZDDP 0.488 0.488 0.529 0.529 Mixed 2- 0.466 0.373 0.680 0.459 ethylhexylamide- ethylester- citrate Tris(2-ethylhexyl) 0.447 0.415 0.630 0.652 citramide Tris(hydrogenated 0.418 0.407 0.637 0.501 tallow) citramide Tritallow citramide 0.427 0.436 0.841 0.637 Trioleyl citramide 0.502 0.478 0.710 0.534 Di-hexylhydroxy ethyl 0.527 0.374 0.593 0.415 citrate

[0093] Tri (N-butyl-N-methyl) citramide was tested separately at 1 wt % in a different commercial 5W-30 motor oil that was fully formulated except that it contained no anti-wear additives.

##STR00025##

TABLE-US-00006 Wear, mm, no chp, Wear, mm, chp, Sample 1 wt % sample 1 wt % sample 5W-30 w/o Anti-Wear STD 0.736 0.798 Tris(N-butyl-N-methyl) 0.328 0.576 citramide

[0094] Although particular embodiments of the present invention have been illustrated and described, this description is not meant to be construed in a limiting sense. Various changes and modifications may be made without departing from the principle and scope of the present invention, which is defined by the appended claims.