Method of reducing aqueous separation in an emulsion composition suitable for engine fueled by E85 fuel

Abstract

A method for reducing aqueous phase separation of an emulsion comprising ethanol-based fuel and a lubricating oil comprising molybdenum ester amide complex, comprising the step of adding to the lubricating oil a dispersant polyalkyl (meth) acrylate (DPMA) in an amount from about 0.01 to about 0.5% by weight of the lubricating oil, such that the weight ratio of molybdenum to DPMA is about 2.05 or less.

Claims

1. A method for reducing aqueous phase separation of an emulsion comprising alcohol-based fuel, and a lubricating oil comprising molybdenum ester amide complex, comprising the step of adding to the lubricating oil a dispersant polyalkyl (meth) acrylate (DPMA) in an amount from about 0.01 to about 0.5% by weight of the lubricating oil, such that the weight ratio of molybdenum present from the molybdenum ester amide complex to DPMA (Mo:DPMA) is about 2.05 or less.

2. The method of claim 1, wherein aqueous phase separation at ambient temperature and at 0 C. to 10 C. for 24 hours is 0%.

3. The method of claim 1, wherein the molybdenum ester amide complex is prepared by reacting about 1 mole of fatty oil, about 0.1 to 2.5 moles of diethanolamine and a molybdenum source sufficient to yield about 0.1 to 12.0 percent of molybdenum based on the weight of the complex.

4. The method of claim 3, wherein the DPMA comprises (a) 0 to 40% by weight of one or more ethylenically unsaturated ester compounds of the formula (I) ##STR00005## wherein R is hydrogen or methyl, R.sup.1 is a saturated or unsaturated linear or branched alkyl radical having 1 to 5 carbon atoms or a saturated or unsaturated cycloalkyl group having 3 to 5 carbon atoms, R.sup.2 and R.sup.3 are each independently hydrogen or a group of the formula COOR wherein R is hydrogen or a saturated or unsaturated linear or branched alkyl group having 1 to 5 carbon atoms; (b) 10 to 98% by weight, of one or more ethylenically unsaturated ester compounds of the formula (II) ##STR00006## wherein R is hydrogen or methyl, R.sup.4 is a saturated or unsaturated linear or branched alkyl radical having 6 to 15 carbon atoms or a saturated or unsaturated cycloalkyl group having 6 to 15 carbon atoms, R.sup.5 and R.sup.6 are each independently hydrogen or a group of the formula COOR in which R is hydrogen or a saturated or unsaturated linear or branched alkyl group having 6 to 15 carbon atoms; (c) 0 to 30% by weight of one or more ethylenically unsaturated ester compounds of the formula (III) ##STR00007## wherein R is hydrogen or methyl, R.sup.7 is a saturated or unsaturated linear or branched alkyl radical having 16 to 40, carbon atoms or a cycloalkyl group having 16 to 40 carbon atoms, R.sup.8 and R.sup.9 are each independently hydrogen or a group of the formula COOR in which R is hydrogen or a saturated or unsaturated linear or branched alkyl group having 16 to 40 carbon atoms; (d) 0 to 30% by weight of vinyl monomers; (e) 2 to 10% by weight of at least one N-dispersant monomer.

5. The method of claim 1, wherein the alcohol-based fuel is E85 fuel.

6. The method of claim 1, wherein the amount of molybdenum provided from the complex is between about 0.016% and about 0.1024% by weight of the lubricating oil.

7. The method of claim 6, wherein the DPMA is present at less than or equal to about 0.2% by weight of the lubricating oil.

8. The method of claim 7, wherein the DPMA is present at less than or equal to about 0.05% by weight of the lubricating oil.

9. A method for reducing aqueous phase separation of an emulsion comprising alcohol-based fuel, and a lubricating oil comprising molybdenum ester amide complex, comprising the step of adding to the lubricating oil a dispersant polyalkyl (meth) acrylate (DPMA) in an amount from about 0.01 to about 0.5% by weight of the lubricating oil, such that the weight ratio of molybdenum present from the molybdenum ester amide complex to DPMA (Mo:DPMA) is about 2.05 or less, wherein: the DPMA comprises (a) 2.0 to 40% by weight of one or more ethylenically unsaturated ester compounds of the formula (I) ##STR00008## wherein R is hydrogen or methyl, R.sup.1 is a saturated or unsaturated linear or branched alkyl radical having 1 to 5 carbon atoms or a saturated or unsaturated cycloalkyl group having 3 to 5 carbon atoms, R.sup.2 and R.sup.3 are each independently hydrogen or a group of the formula COOR wherein R is hydrogen or a saturated or unsaturated linear or branched alkyl group having 1 to 5 carbon atoms; (b) 10 to 98% by weight, of one or more ethylenically unsaturated ester compounds of the formula (II) ##STR00009## wherein R is hydrogen or methyl, R.sup.4 is a saturated or unsaturated linear or branched alkyl radical having 6 to 15 carbon atoms or a saturated or unsaturated cycloalkyl group having 6 to 15 carbon atoms, R.sup.5 and R.sup.6 are each independently hydrogen or a group of the formula COOR in which R is hydrogen or a saturated or unsaturated linear or branched alkyl group having 6 to 15 carbon atoms; (c) 0 to 30% by weight of one or more ethylenically unsaturated ester compounds of the formula (III) ##STR00010## wherein R is hydrogen or methyl, R.sup.7 is a saturated or unsaturated linear or branched alkyl radical having 16 to 40 carbon atoms or a cycloalkyl group having 16 to 40 carbon atoms, R.sup.8 and R.sup.9 are each independently hydrogen or a group of the formula COOR in which R is hydrogen or a saturated or unsaturated linear or branched alkyl group having 16 to 40 carbon atoms; (d) 0 to 30% by weight of vinyl monomers; (e) 2 to 10% by weight of at least one N-dispersant monomer; the molybdenum ester amide complex is prepared by reacting about 1 mole of fatty oil, about 0.1 to 2.5 moles of diethanolamine and a molybdenum source sufficient to yield about 0.1 to 12.0 percent of molybdenum based on the weight of the complex; and the amount of molybdenum provided from the complex is between about 0.016% and about 0.1024% by weight of the lubricating oil.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The present invention relates to a composition and method for reducing aqueous phase separation of an emulsion composition comprising alcohol based fuel, water and an oil of lubricating viscosity, said lubricating oil comprising a molybdenum ester/amide, wherein said composition and method comprises adding to the lubricating oil an amount of DPMA viscosity index modifier that is effective to reduce aqueous phase separation.

(2) As used herein, the terms alcohol based fuel or ethanol based fuel refers to any fuel composition containing from about 10 to about 100 percent by weight of ethanol.

(3) Molybdenum Ester/AmidesSulfur & Phosphorus-Free Organomolybdenum.

(4) An organomolybdenum compound is prepared by reacting about 1 mole of fatty oil, about 0.1 to 2.5 moles of diethanolamine and a molybdenum source sufficient to yield about 0.1 to 12.0 percent of molybdenum based on the weight of the complex at elevated temperatures (i.e. greater than room temperature, such as a temperature range of about 70 C. to 160 C. The organomolybdenum component of the invention is prepared by sequentially reacting fatty oil, diethanolamine and a molybdenum source by condensation method described in U.S. Pat. No. 4,889,647, incorporated herein by reference, and commercially available from Vanderbilt Chemicals, LLC. of Norwalk, Conn. as MOLYVAN 855. This compound as used in the present invention contains approximately 8% Mo. The reaction yields a reaction product mixture. The major components are believed to have the structure formulae:

(5) ##STR00001##

(6) wherein R14 represent a fatty oil residue. An embodiment for the present invention are fatty oils which are glyceryl esters of higher fatty acids containing at least 12 carbon atoms and may contain 22 carbon atoms and higher. Such esters are commonly known as vegetable and animal oils. Examples of useful vegetable oils are those derived from coconut, corn, cottonseed, linseed, peanut, soybean and sunflower seed. Similarly, animal fatty oils such as tallow may be used. The source of molybdenum may be oxygen-containing molybdenum compound capable of reacting with the intermediate reaction products of fatty oil and diethanolamine to form an ester type molybdenum complex. The source of molybdenum includes, among others, ammonium molybdates, molybdenum oxides and mixtures thereof.

(7) Other sulfur and phosphorus free organomolybdenum compounds that may be used in the present invention may be prepared by reacting a sulfur and phosphorus free molybdenum source with an organic compound containing amino and/or alcohol groups. Examples of sulfur and phosphorus free molybdenum sources include molybdenum trioxide, ammonium molybdates, sodium molybdates and potassium molybdate. The amino groups may be monoamines, diamines, or polyamines. The alcohol groups may be mono-substituted alcohols, diols or bis-alcohols or polyalcohols. As an example, the reaction of diamines with fatty oils produces a product containing both amino and alcohol group that can react with the sulfur and phosphorus free molybdenum source.

(8) Examples of sulfur- and phosphorus-free organo molybdenum compounds appearing in patents and patent applications include compounds described in U.S. Pat. Nos. 4,259,195; 4,261,843; 4,164,473; 4,266,945; 4,889,647; 5,137,647; 4,692,256; 5,412,130; 6,509,303; and 6,528,463.

(9) Examples of commercially available sulfur and phosphorus free oil soluble molybdenum compounds are available under the trade name SAKURA-LUBE from Asahi Denka Kogyo K.K. and MOLYVAN from Vanderbilt Chemicals, LLC.

(10) In addition to molybdenum esters/amides, the lubricating oil may contain other additives including oxidation inhibitors, detergents, dispersants, viscosity index modifiers, rust inhibitors, anti-wear additives such as molybdenum dithiocarbamates (including Molvyan 822 from Vanderbilt Chemicals, LLC), and pour point depressants.

(11) Oxidation Inhibitor Components

(12) Oxidation inhibitors that may be used include alkylated diphenylamines (ADPAs) and hindered phenolics.

(13) Alkylated diphenylamines are widely available antioxidants for lubricants. One possible embodiment of an alkylated diphenylamine for the invention are secondary alkylated diphenylamines such as those described in U.S. Pat. No. 5,840,672, which is hereby incorporated by reference. These secondary alkylated diphenylamines are described by the formula XNHY, wherein X and Y each independently represent a substituted or unsubstituted phenyl group wherein the substituents for the phenyl group include alkyl groups having 1 to 20 carbon atoms, preferably 4-12 carbon atoms, alkylaryl groups, hydroxyl, carboxy and nitro groups and wherein at least one of the phenyl groups is substituted with an alkyl group of 1 to 20 carbon atoms, preferably 4-12 carbon atoms. It is also possible to use commercially available ADPAs including VANLUBE SL (mixed alkylated diphenylamines), DND, NA (mixed alkylated diphenylamines), 81 (p,p-dioctyldiphenylamine) and 961 (mixed octylated and butylated diphenylamines) manufactured by Vanderbilt Chemicals, LLC, Naugalube 640, 680 and 438L manufactured by Chemtura Corporation, Irganox L-57 and L-67 manufactured by BASF Corporation, and Lubrizol 5150A & C manufactured by Lubrizol Corporation. Another possible ADPA for use in the invention is a reaction product of N-phenyl-benzenamine and 2,4,4-trimethylpentene.

(14) Hindered phenolics are also widely available antioxidants for lubricants. A preferred hindered phenol is available from Vanderbilt Chemicals, LLC as Vanlube BHC (Iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate). Other hindered phenols may include orthoalkylated phenolic compounds such as 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 2-tert-butylphenol, 2,6-disopropylphenol, 2-methyl-6-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4-(N,N-dimethylaminomethyl)-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 2-methyl-6-styrylphenol, 2,6-distyryl-4-nonylphenol, 4,4methylyenebis(2,6-di-tert-butylphenol) and their analogs and homologs. Mixtures of two or more such phenolic compounds are also suitable.

(15) Additional sulfur containing antioxidant such as, methylene bis (dibutyldithiocarbamate) and tolutriazole derivative may be used in the lubricating additive compositions. One such supplemental antioxidant component is commercially available under the trade name VANLUBE 996E, manufactured by Vanderbilt Chemicals, LLC.

(16) Viscosity Modifiers

(17) Viscosity modifiers (VM) may be used in the lubricant to impart high and low temperature operability. VM may be used to impart that sole function or may be multifunctional. Multifunctional viscosity modifiers also provide additional functionality for dispersant function. Examples of Viscosity modifiers and dispersant viscosity modifiers are polymethacrylates, polyacrylates, polyolefins, styrene-maleic ester copolymer and similar polymeric substances including homopolymers, copolymers and graft copolymers.

(18) The dispersant polymethacrylate (DPMA) viscosity index modifier used in the present invention as an emulsion stabilizer can be described as follows, and as set forth in WO 2013/182581, the disclosure of which is incorporated herein. In addition to the preferred DPMA compound Viscoplex 6-850 VII, other compounds within this definition would include Viscolex viscosity index improvers 6-054, 6-565, 6-950 and 6-954, all available from Evonik RohMax Additives GmbH of Darmstadt, Germany:

(19) polyalkyl(meth)acrylate(s) comprising monomer units of:

(20) (a) 0 to 40% by weight of one or more ethylenically unsaturated ester compounds of the formula (I)

(21) ##STR00002## wherein R is hydrogen or methyl, R.sup.1 is a saturated or unsaturated linear or branched alkyl radical having 1 to 5 carbon atoms or a saturated or unsaturated cycloalkyl group having 3 to 5 carbon atoms, R.sup.2 and R.sup.3 are each independently hydrogen or a group of the formula COOR wherein R is hydrogen or a saturated or unsaturated linear or branched alkyl group having 1 to 5 carbon atoms; (b) 10 to 98% by weight, preferably 20 to 95% by weight, of one or more ethylenically unsaturated ester compounds of the formula (II)

(22) ##STR00003## wherein R is hydrogen or methyl, R.sup.4 is a saturated or unsaturated linear or branched alkyl radical having 6 to 15 carbon atoms or a saturated or unsaturated cycloalkyl group having 6 to 15 carbon atoms, R.sup.5 and R.sup.6 are each independently hydrogen or a group of the formula COOR in which R is hydrogen or a saturated or unsaturated linear or branched alkyl group having 6 to 15 carbon atoms; (c) 0 to 30% by weight, preferably 5 to 20% by weight, of one or more ethylenically unsaturated ester compounds of the formula (III)

(23) ##STR00004## wherein R is hydrogen or methyl, R.sup.7 is a saturated or unsaturated linear or branched alkyl radical having 16 to 40.sub.1 preferably 16 to 30, carbon atoms or a cycloalkyl group having 16 to 40, preferably 16 to 30, carbon atoms, R.sup.8 and R.sup.9 are each independently hydrogen or a group of the formula COOR in which R is hydrogen or a saturated or unsaturated linear or branched alkyl group having 16 to 40, preferably 16 to 30, carbon atoms; (d) 0 to 30% by weight of vinyl monomers; (e) 2 to 10% by weight of at least one N-dispersant monomer.

(24) The DPMA used in the present invention is an emulsion stabilizer at significantly lower treat rate than when the compound is normally used as viscosity index modifier. It is believed to contain about 3.4 wt. % methyl methacrylate monomer, about 0.9 wt. % N-vinyl pyrolidone as the nitrogen-containing monomer, and the balance longer chain alkyl methacrylate monomers, in particular, lauryl methacrylate, MW 214,000. Commercially available dispersant DPMA Viscoplex 6-850, product of Evonik Rohmax USA Inc. was used.

(25) Base Oil Component

(26) A suitable base blend is any partially formulated engine oil consisting of one or more base oils, dispersants, detergent, antiwear, VI improver, antioxidants and any other additives such that when combined with the inventive composition constitutes a fully formulated motor oil for any gasoline, diesel, natural gas, bio-fuel powered vehicle. Base oils suitable for use in formulating the compositions, additives and concentrates described herein may be selected from any of the synthetic or natural oils or mixtures thereof. The synthetic base oils includes alkyl esters of dicarboxylic acids, polyglycols and alcohols, poly-alpha olefins, including polybutenes, alkyl benzenes, organic esters of phosphoric acids, polysilicone oils and alkylene oxide polymers, interpolymers, copolymers and derivatives thereof where the terminal hydroxyl group have been modified by esterification, etherification and the like.

(27) Natural base oil include animal oils and vegetable oils (e.g. castor oil, lard oil) liquid petroleum oils and hydro-refined, solvent treated or acid treated mineral lubricating oils of paraffinic, naphthenic and mixed paraffinic naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils. The base oils typically have viscosity of about 2.5 to about 15 cSt and preferably about 2.5 to about 11 cSt at 100 C.

(28) Detergent Components

(29) The lubricating composition may also include detergents. Detergents as used herein are preferably metal salts of organic acids. The organic portion of the detergent is preferably sulfonate, carboxylate, phenates, and salicylates. The metal portion of the detergent is preferably an alkali or alkaline earth metal. Preferred metals are sodium, calcium, potassium and magnesium. Preferably the detergents are overbased, meaning that there is a stoichiometric excess of metal over that needed to form neutral metal salts.

(30) Dispersant Components

(31) The lubricating composition may also include dispersants. Dispersants may include, but are not limited to, a soluble polymeric hydrocarbon backbone having functional groups capable of associating with particles to be dispersed. Typically, amide, amine, alcohol or ester moieties attached to the polymeric backbone via bridging groups. Dispersants may be selected from ashless succinimide dispersants, amine dispersants, Mannich dispersants, Koch dispersants and polyalkylene succinimide dispersants.

(32) Antiwear Components

(33) Zinc dialkyl dithiophosphates (ZDDPs) may also be used in the lubricating oil additive compositions. ZDDPs have good antiwear and antioxidant properties and have been used as wear protection for the critical components of engines. Many patents address the manufacture and use of ZDDPs including U.S. Pat. Nos. 4,904,401; 4,957,649, and 6,114,288. Non limiting general ZDDP types are primary and secondary ZDDPs, and mixtures of primary and secondary ZDDPs. Additional supplemental antiwear components may be used in the lubricating oil additive composition. This includes, but not limited to, borate esters, ashless dithiocarbamates and metal dithiocarbamates.

(34) Other Components

(35) Rust inhibitors selected from the group consisting of metal sulfonate based such as calcium dinonyl naphthalene sulfonate, DMTD based rust inhibitors such as 2,5-Dimercapto-1,3,4-Thiadiazole Alkyl Polycarboxylate may be used.

(36) Pour point depressants are particularly important to improve low temperature qualities of a lubricating oil. Pour point depressants contained in the additive composition may be selected from polymethacrylates, vinyl acetate or maleate copolymer, styrene maleate copolymer.

EXAMPLES

(37) The following examples are illustrative of this invention and its beneficial properties. In these examples, as well as throughout this application, all parts and percentages are by weight of the total lubricating composition, unless otherwise indicated. Lubricating compositions according to the present disclosure were formulated as shown in Tables 1-4. Each example was subjected to the E85 Emulsion Screener Test, in which a mixture of 10% E85 fuel, 10% water and 80% test oil is blended by Waring blender or equivalent for 1 minute at room temperature and the resulting emulsion is placed in a graduated cylinder and kept at ambient temperature at between 0 C. to 10 C. for 24 hours. The desired result [PASS] of the emulsion test is to have no aqueous separation (0%) and at least 85% emulsion remaining.

Example 1

(38) In Table 1, the base blend is prepared by combining mineral oil, over based detergent, dispersant, pour point depressant, metal dialkyldithiophosphate and mixtures of hindered phenolics and alkylated diphenylamines. The base blend is then further formulated as described in Examples 1A through 1D. Example 1A is a control and contains no friction modifier. Example 1B is prepared by blending molybdenum dithiocarbamate with example 1A. Example 1C is prepared by blending molybdenum ester/amide (MOLYVAN 855) to example 1A. Example 1D is prepared by blending a combination of molybdenum dithiocarbamate and molybdenum ester/amide to example 1A. In example 1C, the total amount of molybdenum from the molybdenum ester/amide is 160 ppm. In Example 1D, the total amount of molybdenum from the molybdenum ester/amide is 80 ppm. As can be seen from the results mentioned in Table 1, Examples 1A and 1B performed acceptably and maintain emulsion stability with no separation of aqueous phase, while examples 1C and 1D failed to maintain stable emulsion and resulted in separation of an aqueous phase. These results indicate that the presence of molybdenum ester/amide adversely affects the emulsion stability of E85 fuel, water and lubricating composition, resulting in aqueous phase separation (while also demonstrating that it is the structure of the molybdenum ester amide itself, rather than molybdenum per se as represented by molybdenum dithiocarbamate as in Example 1B). In the previously mentioned study reported by Patel et al., it was indicated that the use of VI modifier in the high amounts tested results in an avoidance of aqueous phase separation, regardless of the type of viscosity index modifier. However, the present data indicates that this is not true for a lubricating formulation that contains molybdenum ester/amide in the presence of olefin copolymer, one of the VI modifiers discussed by Patel. As seen in Table 2, the presence of the VI modifier olefin copolymer alone, even at a high rate of 7 wt. %, cannot prevent the molybdenum ester amide from causing aqueous phase separation. In contrast, it is surprisingly seen that the dispersant PMA VI modifier, Viscoplex 6-850, does prevent aqueous phase separation in the presence of molybdenum ester amide. What is even more unexpected, however, is that this effect can be achieved at significantly lower rates of the Viscoplex dispersant PMA than is suggested by Patel.

(39) TABLE-US-00001 TABLE 1 Components (wt. %) Examples 1A 1B 1C 1D 1 Base Blend* 87.38 87.38 87.38 87.38 2 VI modifier - Olefin Coplymer 7 7 7 7 3 Friction Modifier - Molybdenum 0.2 0.1 Ester/Amide 4 Friction Modifier - Molybdenum 0.31 0.155 Dithiocarbamate 5 Diluent Oil** 5.62 5.31 5.42 5.365 6 Total 100 100 100 100 7 0 C. to 10 C. Oil 0 0 88 87 Separation (%) 8 0 C. to 10 C. Aqueous 0 0 12 13 Separation (%) 9 0 C. to 10 C. Emulsion (%) 100 100 0 0 10 Ambient ( C.) Oil Separation (%) 10 10 88 86 12 Ambient ( C.) Aqueous 0 0 12 14 Separation (%) 13 Ambient ( C.) Emulsion (%) 90 90 0 0 *Base blend is mineral oil including over based detergent, dispersant and pour point depressant, Metal dialkyldithiophosphate and Mixture of Hindered Phenol and Alkylated Diphenylamine **Diluent is mineral oil without additives to bring the total to 100%

(40) TABLE-US-00002 TABLE 2 Components (wt. %) Examples 2A 2B 1 Base Blend* 88.48 88.48 2 VI Modifier - Olefin Coplomer 7 3 VI Modifier - Viscoplex 6-850 7 Dispersant polymethacrylate 4 Friction Modifier - Molybdenum 0.2 0.2 Ester/Amide 5 Friction Modifier - Molybdenum 0.163 0.163 Dithiocarbamate 6 Diluent Oil** 4.257 5.02 7 Total 100 100 8 0 C. to 10 C. Oil Separation (%) 91 0 9 0 C. to 10 C. Aqueous Separations (%) 9 0 10 0 C. to 10 C. Emulsion (%) 0 100 11 Ambient ( C.) Oil Separation (%) 94 0 12 Ambient ( C.) Aqueous Separation (%) 6 0 13 Ambient ( C.) Emulsion (%) 0 100 *Base blend is mineral oil including over based detergent, dispersant and pour point depressant, Metal dialkyldithiophosphate, Mixture of Hindered Phenol and Alkylated Diphenylamine, Calcium Dinonyl Naphthalene Sulfonate, Organo borate ester, 2,5-Dimercapto-1,3,4-Thiadiazole Alkyl Polycarboxylate, Methylene Bis (dibutyledithiocarbamate) and tolutriazole derivative **Diluent is mineral oil without additives to bring the total to 100%

(41) TABLE-US-00003 TABLE 3 Examples 3A 3B 3C 3D 3E 1 Base Blend* 94.78 94.78 94.78 94.78 94.78 2 Aristonate S-4000 Low Molecular Wt. Alkyl 0.2 Aryl Sulfonate 3 Aristonate C-5000 Neutral Calcium Sulfonate 0.2 4 Calcium alkylaryl sulfonate 0.2 5 VI Modifier-Viscoplex 6-850 Dispersant 0.2 polymethacrylate 6 Diluent Oil** 5.22 5.02 5.02 5.02 5.42 7 Total 100 100 100 100 100 8 0 C. to 10 C. Oil Separation (%) 89 89 89 88 30 9 0 C. to 10 C. Aqueous Separation (%) 11 11 11 12 0 10 0 C. to 10 C. Emulsion (%) 0 0 0 0 70 11 Ambient ( C.) Oil Separation (%) 89 90 89 89 0 12 Ambient ( C.) Aqueous Separation (%) 11 10 11 11 0 13 Ambient ( C.) Emulsion (%) 0 0 0 0 100 *Base blend is mineral oil including over based detergent, dispersant and pour point depressant, Olefin Copolymer, Metal dialkyldithiophosphate, Mixture of Hindered Phenol and Alkylated Diphenylamine, Molybdenum Ester/Amide, Calcium Dinonyl Naphthalene Sulfonate **Diluent is mineral oil without additives to bring the total to 100%

(42) As can be seen from the lubrication composition mentioned in Table 3, Example 3A is the lubrication composition prepared by blending mineral oil, detergent, dispersant, pour point depressant, olefin copolymer as VI modifier, metal dialkyldithiophosphate, mixture of hindered phenol and alkylated diphenylamine, molybdenum ester/amide and calcium dinonyl naphthalene sulfonate. Results indicated that lubricant composition shown in example 3A failed to maintain emulsion and separate aqueous phase. Various different methods were tested to stabilize the E85 fuel, water and lubricating oil emulsion which includes the use of different emulsifiers such as low molecular weight alkyl aryl sulfonate, neutral calcium sulfonate, and calcium alkylaryl sulfonate at 0.2 wt. % treat rate as shown in Table 3 as Example 3B, 3C and 3D respectively. Examples 3B, 3C and 3D failed to maintain emulsion stability. Surprisingly, we have discovered that use of dispersant PMA at 0.2 wt. % treat rate (Example 3E) helps to maintain emulsion stability as well as protects against aqueous phase separation. Dispersant PMA is typically used at 4.0-7.0 wt. % treat rate as a viscosity index modifier. However, the present invention demonstrates the use of low levels of dispersant PMA as an emulsifier for a lubrication composition in the presence of E85 fuel and water.

(43) TABLE-US-00004 TABLE 4 Component (wt. %) Examples 4A 4B 4C 4D 4E 4F 1 Base Blend* 88.48 88.48 88.48 88.48 88.48 88.48 2 VI Improver-Olefin Copolymer 7.00 7.00 7.00 7.00 7.00 7.00 3 Molybdenum Ester/Amide, 0.2 0.2 0.2 0.2 0.2 0.2 4 VI Improver-Viscoplex 6-850 Dispersant polymethacrylate 0.05 0.025 0.01 5 Viscoplex 3-200 Non-dispersant polymethacrylate 0.05 6 Viscoplex 1-333 Non-dispersant 0.05 polymethacrylate 7 Diluent Oil** 4.42 4.37 4.395 4.41 4.37 4.37 8 Total 100 100 100 100 100 100 9 0 C. to 10 C. Oil Separation (%) 88 20 30 30 86 86 10 0 C. to 10 C. Aqueous Separations (%) 12 0 0 0 14 14 11 0 C. to 10 C. Emulsion (%) 0 80 70 70 0 0 12 Ambient ( C.) Oil Separation (%) 87 65 74 70 85 85 13 Ambient ( C.) Aqueous Separation (%) 13 0 0 0 15 15 14 Ambient ( C.) Emulsion (%) 0 35 26 30 0 0 *Base blend is mineral oil including over based detergent, dispersant and pour point depressant, Metal dialkyldithiophosphate, Mixture of Hindered Phenol and Alkylated Diphenylamine, Molybdenum Ester/Amide, Calcium Dinonyl Naphthalene Sulfonate, Organo borate ester, 2,5-Dimercapto-1,3,4-Thiadiazole Alkyl Polycarboxylate, Methylene Bis (dibutyledithiocarbamate) and tolutriazole derivative **Diluent is mineral oil without additives to bring the total to 100%

(44) Table 4 further exemplifies the use of dispersant PMA as a unique method to reduce aqueous phase separation in an emulsion composition comprising E85 fuel, water and lubricating oil. Example 4A is a complicated lubrication composition that includes base blend, olefin copolymer as VI improver, metal dialkyldithiophosphate, mixture of hindered phenol and alkylated diphenylamine as antioxidant, molybdenum ester/amide as friction modifiers, calcium dinonyl naphthalene sulfonate as rust inhibitors, 2,5-Dimercapto-1,3,4-Thiadiazole Alkyl Polycarboxylate as metal deactivator, organo borate ester as supplemental antiwear and methylene Bis(dibutyledithiocarbamate) and tolutriazole derivative as supplemental antioxidant. Example 4A failed to reduce aqueous phase separation in an emulsion with E85 fuel and water. Examples 4B, 4C and 4D are prepared by blending dispersant PMA at 0.05 wt. %, 0.025 wt. % and 0.01 wt. % to example 4A, respectively. Example 4B, 4C and 4D demonstrate the use of dispersant PMA as a method that can effectively reduce aqueous phase separation at significantly lower treat rates. In contrast, non-dispersant PMA, as in examples 4E and 4F, was blended to example 4A at 0.05 wt. % and was ineffective in preventing aqueous separation. This further highlights that it is dispersant PMA in particular, as opposed to other PMA (such as non-dispersant), olefin copolymer, or other known emulsion stabilizers, which is particularly effective in dealing with emulsion instability caused by molybdenum ester amide.

(45) TABLE-US-00005 TABLE 5 Component (wt. %) Examples 5A 5B 5C 5D 5E 1 Base Blend* 87.38 87.38 87.38 87.38 87.38 2 VII-Olefin Copolymer 7 7 7 7 7 3 Molybdenum Ester/Amide 0.2 0.2 0.2 0.2 0.2 4 VII-Viscoplex 6-850 Dispersant PMA 0.01 0.025 0.05 0.2 0.5 5 Diluent Oil** 5.41 5.395 5.37 5.22 4.92 6 Total 100 100 100 100 100 7 0 C. to 10 C. Emulsion Separation (%) 75 78 80 60 86 8 0 C. to 10 C. Aqueous Separation (%) 0 0 0 0 0 9 0 C. to 10 C. Oil Separation (%) 25 22 20 40 14 10 Ambient( C.) Emulsion Separation (%) 75 80 82 0 98 11 Ambient( C.) Aqueous Separation (%) 0 0 0 0 0 12 Ambient ( C.) Oil Separation (%) 25 20 18 100 02 *Base blend is mineral oil including over based detergent, dispersant and pour point depressant, Metal dialkyldithiophosphate, Mixture of Hindered Phenol and Alkylated Diphenylamine, **Diluent is mineral oil without additives to bring the total to 100%

(46) TABLE-US-00006 TABLE 6 Components (wt. %) Examples 6A 6B 6C 6D 6E 1 Base Blend* 87.38 87.38 87.38 87.38 87.38 2 VII-Olefin Copolymer 7 7 7 7 7 3 Molybdenum Ester/ 0.4 0.4 0.4 0.4 0.4 Amide 4 VII-Viscoplex 6-850 0.01 0.025 0.05 0.2 0.5 Dispersant PMA 5 Diluent Oil** 5.21 5.195 5.17 5.02 4.72 6 Total 100 100 100 100 100 7 0 C. to 10 0 22 57 62 87 C. Emulsion Separation (%) 8 0 C. to 10 C. 13 0 0 0 0 Aqueous Separation (%) 9 0 C. to 10 C. Oil 87 78 43 38 13 Separation (%) 10 Ambient ( C.) 0 100 100 100 100 Emulsion Separation (%) 11 Ambient ( C.) 13 0 0 0 0 Aqueous Separation (%) 12 Ambient ( C.) Oil 87 0 0 0 0 Separation (%) *Base blend is mineral oil including over based detergent, dispersant and pour point depressant, Metal dialkyldithiophosphate, Mixture of Hindered Phenol and Alkylated Diphenylamine, **Diluent is mineral oil without additives to bring the total to 100%

(47) TABLE-US-00007 TABLE 7 Components (wt. %) Examples 7A 7B 7C 7D 7E 7F 1 Base Blend* 87.38 87.38 87.38 87.38 87.38 87.38 2 VII-Olefin Copolymer 7 7 7 7 7 7 3 Molybdenum Ester/Amide 0.641 0.641 0.641 0.641 0.641 0.641 4 VII-Viscoplex 6- 850 Dispersant PMA 0.01 0.025 0.03 0.05 0.2 0.5 5 Diluent Oil** 4.969 4.954 4.949 4.929 4.779 4.479 6 Total 100 100 100 100 100 100 7 0 C. to 10 C. Emulsion Separation (%) 0 25 25 10 75 76 8 0 C. to 10 C. Aqueous Separation (%) 11 0 0 0 0 0 9 0 C. to 10 C. Oil Separation (%) 89 75 75 90 25 24 10 Ambient ( C. ) Emulsion Separation (%) 0 23 23 10 100 100 11 Ambient ( C. ) Aqueous Separation (%) 11 0 0 0 0 0 12 Ambient ( C. ) Oil Separation (%) 89 77 77 90 0 0 *Base blend is mineral oil including over based detergent, dispersant and pour point depressant, Metal dialkyldithiophosphate, Mixture of Hindered Phenol and Alkylated Diphenylamine, **Diluent is mineral oil without additives to bring the total to 100%

(48) TABLE-US-00008 TABLE 8 Components (wt. %) Examples 8A 8B 8C 8D 8E 1 Base Blend* 87.38 87.38 87.38 87.38 87.38 2 VII-Olefin Copolymer 7 7 7 7 7 3 Molybdenum Ester/Amide 1.28 1.28 1.28 1.28 1.28 4 VII-Viscoplex 6-850 Dispersant PMA 0.01 0.025 0.05 0.2 0.5 5 Diluent Oil** 4.328 4.315 4.29 4.14 3.84 6 Total 100 100 100 100 100 7 0 C. to 10 C. Emulsion Separation (%) 0 0 10 76 86 8 0 C. to 10 C. Aqueous Separation (%) 13 13 0 0 0 9 0 C. to 10 C. Oil Separation (%) 87 87 90 24 14 10 Ambient( C.) Emulsion Separation (%) 0 0 10 98 100 11 Ambient( C.) Aqueous Separation (%) 13 13 0 0 0 12 Ambient ( C.) Oil Separation (%) 87 87 90 02 0 *Base blend is mineral oil including over based detergent, dispersant and pour point depressant, Metal dialkyldithiophosphate, Mixture of Hindered Phenol and Alkylated Diphenylamine, **Diluent is mineral oil without additives to bring the total to 100%

(49) Tables 5-8 extend the use of dispersant PMA as a method to reduce aqueous phase separation in an emulsion composition comprising E85, water and lubricating oil at higher molybdenum content. The examples demonstrate that the use of dispersant PMA can effectively reduce aqueous phase separation at significantly lower treat rate. In reviewing the data as a whole in Table 9, it is seen that there is a clear effectiveness of the dispersant PMA to prevent aqueous separation, regardless of the amount of Mo present from the molybdenum ester amide, so long as the ratio of Mo:DPMA is less than or equal to about 2.05, for amounts DPMA up to about 0.5% of the lubricating composition.

(50) TABLE-US-00009 TABLE 9 0 C. to 10 C. Aqueous MOLYVAN Mo DPMA Mo/ Separations 855 (wt. %) (wt. %) (wt. %) DPMA (%) 5A 0.2 0.016 0.01 1.6 Pass 5B 0.2 0.016 0.025 0.64 Pass 5C 0.2 0.016 0.05 0.32 Pass 5D 0.2 0.016 0.2 0.08 Pass 5E 0.2 0.016 0.5 0.032 Pass 6A 0.4 0.032 0.01 3.2 Fail 6B 0.4 0.032 0.025 1.28 Pass 6C 0.4 0.032 0.05 0.64 Pass 6D 0.4 0.032 0.2 0.16 Pass 6E 0.4 0.032 0.5 0.064 Pass 7A 0.641 0.0512 0.01 5.12 Fail 7B 0.641 0.0512 0.025 2.048 Pass 7C 0.641 0.0512 0.03 1.71 Pass 7D 0.641 0.0512 0.05 1.024 Pass 7E 0.641 0.0512 0.2 0.256 Pass 7F 0.641 0.0512 0.5 0.1024 Pass 8A 1.28 0.1024 0.01 10.24 Fail 8B 1.28 0.1024 0.025 4.096 Fail 8C 1.28 0.1024 0.05 2.048 Pass 8D 1.28 0.1024 0.2 0.512 Pass 8E 1.28 0.1024 0.5 0.2048 Pass

(51) Table 10 shows that even among different types of dispersant PMA, the particular claimed DPMA such as Evonik Viscoplex 6-850 is surprisingly superior to other dispersant PMA. While Afton HiTEC 5710, which is outside the DPMA definition as set forth in the present disclosure, is effective in preventing aqueous separation at very low amounts of Mo (0.016 wt. %), once higher amounts of Mo are provided, even increasing the amount of the Afton dispersant PMA will not cure the emulsion stability issue.

(52) TABLE-US-00010 TABLE 10 Components (wt. %) Examples 10A 10B 10C 10D 10E 10F 10G 1 Base Blend* 87.38 85 85 85 85 85 85 2 Olefin Copolymer 7 7 7 7 7 7 7 3 Molybdenum Ester/Amide 0.2 0.2 0.2 0.4 0.641 1.28 0.641 4 VII-Dispersant PMA (Afton 0.01 0.025 0.05 0.01 0.01 0.01 0.025 Hitech 5710) 5 Diluent Oil** 5.41 5.395 5.37 5.21 4.969 4.33 4.954 6 Total 100 100 100 100 100 100 100 7 0 C. to 10 C. Emulsion Separation (%) 100 100 100 0 0 0 0 8 0 C. to 10 C. Oil Separation (%) 0 0 0 85 87 86 87 9 0 C. to 10 C. Aqueous Separation (%) 0 0 0 15 13 14 13 10 Ambient ( C.) Emulsion Separation (%) 23 22 25 0 0 0 0 11 Ambient ( C.) Oil Separation (%) 77 78 75 87 86 85 87 12 Ambient ( C.) Aqueous Separation (%) 0 0 0 13 14 15 13 Components (wt. %) Examples 10H 10I 10J 10K 10L 10M 10N 1 Base Blend* 85 85 85 85 85 85 85 2 Olefin Copolymer 7 7 7 7 7 7 7 3 Molybdenum Ester/Amide 1.28 0.641 1.28 0.641 1.28 0.641 1.28 4 VII-Dispersant PMA (Afton 0.025 0.05 0.05 0.1 0.1 0.2 0.2 Hitech 5710) 5 Diluent Oil** 4.315 4.929 4.29 4.879 4.24 4.779 4.14 6 Total 100 100 100 100 100 100 100 7 0 C. to 10 C. Emulsion Separation (%) 0 0 0 0 0 0 0 8 0 C. to 10 C. Oil Separation (%) 86 85 87 85 84 85 87 9 0 C. to 10 C. Aqueous Separation (%) 14 15 13 15 16 15 13 10 Ambient ( C.) Emulsion Separation (%) 0 0 0 0 0 0 0 11 Ambient ( C.) Oil Separation (%) 86 85 87 86 87 80 87 12 Ambient ( C.) Aqueous Separation (%) 14 15 13 14 13 20 13 *Base blend is mineral oil including over based detergent, dispersant and pour point depressant, Metal dialkyldithiophosphate, Mixture of Hindered Phenol and Alkylated Diphenylamine, **Diluent is mineral oil without additives to bring the total to 100%