CA2627866A1

CA2627866A1 - Lubricating oil composition containing alkali metal borates with improved frictional properties

Info

Publication number: CA2627866A1
Application number: CA002627866A
Authority: CA
Inventors: Michael J. Haire; Kurt J. Schuemans; Marc J. De Weerdt
Original assignee: Chevron USA Inc; Chevron Oronite Co LLC
Current assignee: Chevron USA Inc; Chevron Oronite Co LLC
Priority date: 2007-04-30
Filing date: 2008-04-01
Publication date: 2008-10-30
Also published as: EP1988146A2; SG147382A1; US20080269085A1; EP1988146A3; JP2008274276A

Abstract

A lubricating oil composition with improved frictional and wear performance, especially when the ratio of polysulfides is controlled, wherein said composition comprises a major amount of an oil of lubricating viscosity, at least one alkali metal borate; at least one dihydrocarbyl polysulfide component comprising a mixture of sulfides and having at least 30%
dihydrocarbyl tetrasulfide or higher sulfides; at least one non-acidic phosphorus component comprised of a trihydrocarbyl phosphite; at least one dihydrocarbyl dithiophosphate; and a phosphorus component comprising a dihydrocarbyl phosphite component is disclosed.

Description

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I LUBRICATING OIL COMPOSITION CONTAINING

FIELD OF THE INVENTION

7 The present invention relates to lubricants generally and, more specifically, to 8 lubricants for automotive gears.

BACKGROUND OF THE INVENTION

12 The use of dispersed alkali metal borates in lubricant formulations is well 13 known. The patent literature has taught the combination of an alkali metal 14 borate with sulfur compounds and particular phosphorus compounds. See for example, U.S. Patent Nos. 4,717,490; 4,472,288; and patents cited therein.
16 These prior art formulations suffered from shortened shelf life compared to 17 other commercially available lubricants which do not use solid dispersions of 18 borate. Published U.S. Patent Application No. US20060252656, filed May 4, 19 2005, teaches how to overcome this shortcoming by the judicious use of non-acidic phosphorus compounds. Patent Application No. US20060252656 also 21 teaches how to maintain and improve load carrying ability by carefully 22 balancing the ratio of tetrasulfide : trisulfide : disulfide in the lubricating 23 composition.

SUMMARY OF THE INVENTION

27 The present invention provides a lubricating composition comprising an oil of 28 lubricating viscosity having dispersed therein a minor amount of a mixture of:
29 (a) a hydrated alkali metal borate component; (b) a dihydrocarbyl polysulfide component comprising a mixture including less than 64.5 wt.% dihydrocarbyl 31 trisulfide, greater than 5.5 wt.% dihydrocarbyl disulfide, and at least 30 wt.%
32 dihydrocarbyl tetrasulfide or higher polysulfides; (c) a non-acidic phosphorus 33 component comprising a trihydrocarbyl phosphite component, at least 90 .

1 wt.% of which has the formula (RO)3 P, where R is a hydrocarbyl of 4 to 24 2 carbon atoms and (d) a dihydrocarbyl dithiophosphate derivative. Optionally, 3 a dihydrocarbyl hydrogen phosphite component, at least 90 wt.% of which has 4 the formula (RO)2 POH, where R is a hydrocarbyl of 4 to 24 carbon atoms, may also be used in the lubricant composition.

9 Figures 1-5 are graphs of breakaway torque vs. gear shifting cylces of the composition of the present invention and of comparative lubricating oil 11 compositions. Figure 1 is a graph depicting a flat slope and an acceptable 12 break-away torque. Figure 2 is a graph depicting a negative slope with the 13 breakaway torque gradually moving away from an acceptable range. Figure 3 14 is a graph depicting a flat slope but a break-away torque which is too low.
Figure 4 is a graph depicting an undesirable negative slope in which the 16 breakaway torque never quite reaches the desired torque of 2.0 Nm. Figure 5 17 is a graph depicting a typical commercial oil which also has a negative slope.

3 The present invention is directed to a gear oil additive package, a lubricating 4 oil composition, a method of making the gear oil additive package, and a method of making the lubricating oil composition.

7 The Additive Package 9 The gear oil additive package of the present invention is an oil-soluble additive composition. The gear oil additive package may be used in a gear 11 lubricating oil. The additive package of the present invention comprises (1) at 12 least one hydrated alkali metal borate component; (2) at least one 13 dihydrocarbyl polysulfide component comprising a mixture including less than 14 about 64.5 wt% dihydrocarbyl trisulfide, greater than about 5.5 wt%
dihydrocarbyl disulfide, and at least about 30.0 wt% dihydrocarbyl tetrasulfide 16 or higher polysulfides; (3) at least one non-acidic phosphorus component 17 comprising a trihydrocarbyl phosphite component, at least 90 wt% of which 18 has the formula (RO)3 P, wherein R is hydrocarbyl group having 4 to 24 19 carbon atoms; and (4) at least one dihydrocarbyl dithiophosphate. The term "non-acidic" refers to the phosphorus contained in the component and is not 21 meant to limit the acidic or non-acidic hydrocarbyl groups attached to 22 phosphorus. This base mix may be combined with base oil a dialkyl 23 phosphite, foam inhibitors, viscosity modifiers, metal deactivators, and 24 optional detergents, dispersants, and oxidation inhibitors to form a complete lubricant formulation.

27 Hydrated Alkali-Metal Borates 29 The first additive component employed in the lubricating oil composition of the present invention is a hydrated particulate alkali metal borate. Hydrated 31 particulate alkali metal borates are well known in the art and are available 32 commercially. Representative patents disclosing suitable borates and 1 methods of manufacture include: U.S. Patent Nos. 3,313,727; 3,819,521;
2 3,853,772; 3,907,601; 3,997,454; 4,089,790; and 6,534,450.

4 The hydrated alkali metal borates can be represented by the following formula:

7 M20.mB2O3.nH2O

9 where M is an alkali metal of atomic number in the range 11 to 19, e.g., sodium or potassium; m is a number from 2.5 to 4.5 (both whole and 11 fractional); and n is a number from 1.0 to 4.8. Preferred are the hydrated 12 potassium borates, particularly the hydrated potassium triborate 13 microparticies having a potassium-to-boron ratio of about 1:2.75 to 1:3.25.
14 The hydrated borate particles generally have a mean particle size of less than 1 micron.

17 Dihydrocarbyl Polysulfides 19 The dihydrocarbyl polysulfide component employed in the present invention comprises a mixture which contains less than about 64.5 wt.%, and preferably 21 no more than about 60.0 wt.% dihydrocarbyl trisulfide, greater than about 5.5 22 wt.% dihydrocarbyl disulfide, and preferably greater than about 6.0 wt% and 23 at least about 30.0 wt.% and preferably at least 40 wt.% dihydrocarbyl 24 tetrasulfide or higher polysulfides. Preferably, the dihydrocarbyl polysulfide mixture contains predominantly dihydrocarbyl tetrasulfide and higher 26 polysulfides. The term "polysulfide" as used herein may also include minor 27 amounts of dihydrocarbyl monosulfides, also referred to as monosulfide or 28 sulfide. Generally, the monosulfide is present in relatively small amounts of 29 less than about 1 wt.% of the total sulfur-containing compounds present.
Typically, monosulfides may be present in amounts ranging from about 31 0.3 wt.% to about 0.4 wt.%. The monosulfides are preferably less than about 32 0.4 wt.% and more preferably less than about 0.3 wt.%.

1 The term "hydrocarbyl" includes hydrocarbon, as well as substantially 2 hydrocarbon groups. "Substantially hydrocarbon" describes groups which 3 contain heteroatom substituents that do not substantially alter the 4 predominantly hydrocarbon nature of the substituent. Non-limiting examples of hydrocarbyl groups include the following: (1) hydrocarbon substituents, 6 i.e., aliphatic (e.g., alkyl or alkenyl) and alicyclic (e.g., cycloalkyl, 7 cycloalkenyl, etc.) substituents, aromatic-, aliphatic-, and alicyclic-substituted 8 aromatic substituents and also includes cyclic substituents wherein the ring is 9 completed through another portion of the molecule (that is, for example, any two indicated substituents may together form an alicyclic radical);
11 (2) substituted hydrocarbon substituents, i.e., those substituents containing 12 non-hydrocarbon groups which do not substantially alter the predominantly 13 hydrocarbon nature of the substituent and which includes groups such as, 14 e.g., halo (especially chloro and fluoro), hydroxy, mercapto, nitro, nitroso, and sulfoxy; (3) heteroatom substituents, i.e., substituents which will contain an 16 atom other than carbon in a ring or chain otherwise composed of carbon 17 atoms (e.g., alkoxy or alkylthio). Suitable heteroatoms include, for example, 18 sulfur, oxygen, nitrogen, and such substituents containing one or more 19 heteroatoms exemplified by pyridyl, furyl, thienyl, and imidazolyi.
21 In general, no more than about 2, preferably no more than 1, heteroatom 22 substituent will be present for every 10 carbon atoms in the hydrocarbyl 23 group. Typically, there will be no heteroatom substituents in the hydrocarbyl 24 group in which case the hydrocarbyl group is a hydrocarbon. Preferred is an alkyl group; more preferred, the hydrocarbyl group is tertiary butyl.

27 The organic polysulfides may be prepared as described in U.S. Patent 28 Nos. 6,489,721; 6,642,187; and 6,689,723, which are incorporated by 29 reference herein.

1 Non-Acidic Phosphorous Components 3 The lubricating oil composition of the present invention also employs a at least 4 two non-acidic phosphorous component. The at least two non-acidic phosphorus components, according to the present invention, are non-acidic 6 as defined herein and, more preferably, comprise two phosphorus 7 compounds, a trihydrocarbyl phosphite and a phosphoric acid derivative, i.e., 8 a dihyrocarbyl dithiophosphate.

Acidic phosphorus compounds as used herein mean compounds that contain 11 a hydrogen atom bonded directly to a phosphorus atom or a hydrogen atom 12 bonded to a hetero atom which is in turn bonded to a phosphorus atom.
13 Non-acidic phosphorus compounds as used herein means that the 14 trihydrocarbyl phosphite or the dithiophosphate derivative may contain an acid group, such as a carboxylic acid group, but do not contain a hydrogen atom 16 bonded directtyto a phosphorus atom or a hydrogen atom bonded to a hetero 17 atom which is in turn bonded to a phosphorus atom. Thus compounds having 18 -P-H, -P-O-H and -P-S-H would be considered to be acidic, whereas the 19 dithiophosphoric acid ester as described in U.S. Patent No. 5,922,657 would be considered non-acidic as used herein even though it has a carboxylic acid 21 functionality.

23 Acidic phosphoric acid compounds may be based on a phosphorus 24 compound as described in Salentine, U.S. Patent No. 4,575,431, the disclosure of which is incorporated by reference herein. Preferably, if an 26 amino phosphorus compound is employed, then the amino phosphorus 27 compound is an amine dithiophosphate (that is, an amine dithiophosphate 28 salt). Typical dithiophosphates useful in the lubricant of the present invention 29 are well known in the art. These dithiophosphates are those containing two hydrocarbyl groups and one hydrogen functionality, and are therefore acidic 31 and must be neutralized for use in the present composition. The hydrocarbyl 32 groups useful herein are preferably aliphatic alkyl groups of 3 to 8 carbon 33 atoms.

1 Representative dihydrocarbyt dithiophosphates include di-2-ethyl-l-hexyl 2 hydrogen dithiophosphate, diisoctyl hydrogen dithiophosphate, dipropyl 3 hydrogen dithiophosphate, and di-4-methyl-2-pentyl hydrogen 4 dithiophosphate.
6 Preferred dithiophosphates are dihexyl hydrogen dithiophosphate, dibutyl 7 hydrogen dithiophosphate, and di-n-hexyl hydrogen dithiophosphate.

9 For use in the present invention, acidic phosphates are completely neutralized by reaction with alkylamines, as disclosed in Salentine, U.S. Patent No. 4, 11 575,431. Neutralization must be at least least 80% complete. For best 12 results, neutralization should be in the range of 85% to 100%, wherein 100%
13 neutralization refers to the reaction of one alkylamine with each acid hydrogen 14 atom.
16 The amine moiety is typically derived from an alkylamine. The amine alkyl 17 group is from 10 to 30 carbon atoms, preferably 12 to 18 carbon atoms in 18 length. Typical amines include pentadecylamine, octadecylamine, cetylamine, 19 and the like. Most preferred is oleylamine. When using a mixture of dithiophosphates and sulfur-free phosphates, the mole ratio of the 21 dithiophosphates to the sulfur-free phosphates should be in the range of 22 70:30 to 30:70, preferably 55:45 to 45:55, and most preferably 1:1. The mole 23 ratio of the substituted dihydrogen phosphates to the disubstituted hydrogen 24 phosphates should be in the range 30:70 to 55:45, preferably 35:65 to 50:50, and most preferably 45:55.

27 The preferred non-acidic phosphoric acid derivative is a dithiophosphoric acid 28 ester as described in Camenzind, et al., U.S. Patent No. 5,992,657.
29 Preferably the dihydrocarbyl ester groups are alkyl as exemplified by Irgalube 353 from Ciba Specialty Chemicals.

32 The phosphorus component of the present invention also includes a 33 trihydrocarbyl phosphite, which is non-acidic. Trihydrocarbyl phosphites useful 1 in the present invention include (RO)3 P wherein R is a hydrocarbyl group of 2 about 4 to 24 carbon atoms, more preferably about 8 to 18 carbon atoms, and 3 most preferably about 10 to 14 carbon atoms. The hydrocarbyl may 4 be saturated or unsaturated. Preferably, the hydrocarbyl group is alkyl.
More preferably, the trialkyl phosphite contains at least 90 wt.% of the structure 6 (RO)3 P wherein R is as defined above. Representative trialkyl phosphites 7 include, but are not limited to, tributyl phosphite, trihexyl phosphite, trioctyl 8 phosphite, tridecyl phosphite, trilauryl phosphite and trioleyl phosphite. A
9 particularly preferred trialkyl phosphite is trilauryl phosphite, such as commercially available Duraphos TLP by Rhodia Incorporated Phosphorus 11 and Performance Derivatives or Doverphos 53 by Dover Chemical 12 Corporation. Such trialkyl phosphites may contain small amounts of dialkyl 13 phosphites as impurities, in some cases as much as 5 wt.%. Preferred are 14 mixtures of phosphites containing hydrocarbyl groups having about 10 to 20 carbon atoms. These mixtures are usually derived from animal or natural 16 vegetable sources. Representative hydrocarbyl mixtures are commonly 17 known as coco, tallow, tall oil, and soya.

19 Optionally, a dihydrocarbyl phosphite may be added to the present invention in addition to the trihydrocarbyl phosphite. Dihydrocarbyl phosphites useful in 21 the present invention include (RO)2POH where R is as described as above. A
22 particularly preferred dihydrocarbyl phosphite is dialkyl phosphite. More 23 preferred, dialkyl phosphite is dioleyl hydrogen phosphite, such as 24 commercially available Duraphos AP-240L by Rhodia Incorporated Phosphorus and Performance Derivatives. Such dialkyl phosphites may 26 contain small amounts of impurities, in some cases as much as 6 wt.%.
27 Preferred are mixtures of phosphites containing hydrocarbyl groups having 28 about 10 to 20 carbon atoms.

Polyalkylene Co-oligomer 32 Optionally, a polyalkylene co-oligomer may be employed in the present 33 invention. Preferred polyalkylene co-oligomers are co-oligomers of ethylene 1 and an olefin which have no polar groups. Particularly preferred 2 polyalkylenes are the Lucant series of synthetic oils which may be 3 purchased from Mitsui Chemicals (U.S.A.) Incorporated, New York, New York, 4 or the SpectraSyn Ultra series of synthetic oils which may be purchased from ExxonMobil Chemical Company. Typical oils in these series have 6 kinematic viscosities (ASTM D445, @ 100 C) of 10 to 2000 cSt. Preferred 7 oils are those having viscosities between 100 and 2000 cSt.

9 The Lubricating Oil Composition 11 The hydrated alkali metal borate, dihydrocarbyl polysulfide and non-acidic 12 phosphorus components are generally added to a base oil that is sufficient to 13 lubricate gears and other components which are present in automotive axles 14 and transmissions, and in stationary industrial gear drives. Typically, the lubricating oil composition of the present invention comprises a major amount 16 of oil of lubricating viscosity and a minor amount of the gear oil additive 17 package.

19 One embodiment of the present invention comprises the combination of: (1) sodium triborate; (2) tertiary butyl polysulfide; (3) trilauryl phosphite and (4) 21 dialkyl dithiophosphate ester in a major amount of oil of a lubricating viscosity.
22 Optionally a polyalkylene co-oligomer is added to the lubricating oil 23 composition.

The base oil employed may be any of a wide variety of oils of lubricating 26 viscosity. The base oil of lubricating viscosity used in such compositions may 27 be mineral oils or synthetic oils. A base oil having a viscosity of at least 28 2.5 cSt at 40 C and a pour point below 20 C, preferably at or below 0 C, is 29 desirable. The base oils may be derived from synthetic or natural sources.
Mineral oils for use as the base oil in this invention include, for example, 31 paraffinic, naphthenic and other oils that are ordinarily used in lubricating oil 32 compositions. Synthetic oils include, for example, both hydrocarbon synthetic 33 oils and synthetic esters and mixtures thereof having the desired viscosity.

1 Hydrocarbon synthetic oils may include, for example, oils prepared from the 2 polymerization of ethylene, polyalphaolefin or PAO oils, or oils (i.e., Fischer-3 Tropsch oils) prepared from hydrocarbon synthesis procedures using carbon 4 monoxide and hydrogen gases such as in a Fisher-Tropsch process.
Examples of Fischer-Tropsch oils used in the present invention include, but 6 are not limited to, those described in U.S. Patent Publication Nos.
7 US20060289337, US20060276355, US20040079078, and U.S. Patent Nos.
8 6080301, 6090989, 6165949, which are herein incorporated by reference.
9 Other Fischer-Tropsch oils that may be employed in the present process include those oils described in pending U.S. patent applications 11/613,883 11 and 11/400,570, which are herein incorporated by reference. Useful synthetic 12 hydrocarbon oils include liquid polymers of alpha olefins having the proper 13 viscosity. Especially useful are the hydrogenated liquid oligomers of C6 to 14 alpha olefins such as 1-decene trimer. Likewise, alkyl benzenes of proper viscosity, such as didodecyl benzene, can be used. Useful synthetic esters 16 include the esters of monocarboxylic acids and polycarboxylic acids, as well 17 as mono-hydroxy alkanols and polyols. Typical examples are didodecyl 18 adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, 19 dilaurylsebacate, and the like. Complex esters prepared from mixtures of mono and dicarboxylic acids and mono and dihydroxy alkanols can also be 21 used. Blends of mineral oils with synthetic oils are also useful.

23 Thus, the base oil can be a refined paraffin type base oil, a refined naphthenic 24 base oil, or a synthetic hydrocarbon or non-hydrocarbon oil of lubricating viscosity. The base oil can also be a mixture of mineral and synthetic oils.

1 Additionally, other additives well known in lubricating oil compositions may be 2 added to the additive composition of the present invention to complete a 3 finished oil.

The hydrated alkali-metal borate component will generally comprise 0.1 to 6 20.0 wt.% of the lubricant composition, preferably 0.5 to 15.0 wt.%, and more 7 preferably 1.0 to 9.0 wt.%. The dihydrocarbyl polysulfide component will 8 comprise 0.1 to 10.0 wt.% of the lubricant composition, preferably 0.2 to 4.0 9 wt.%, and more preferably 0.25 to 3.0 wt.%. The trihydrocarbyl phosphite component will comprise 0.01 to 15.0 wt.% of the Iubricant composition, 11 preferably 0.05 to 5.0 wt.%, and more preferably 0.20 to 1.5 wt.%. The 12 dihydrocarbyl dithiophosphate component will comprise 0.03 to 3.0 wt.% of 13 the lubricant composition, preferably 0.07 to 1.5 wt.%, and more preferably 14 0.15 to 0.9 wt.%. If a dihydrocarbyl phosphite is optionally added to the lubricating oil composition, it will generally comprise 0.01 to 10.0 wt% of the 16 lubricant composition, preferably 0.05 to 5.0 wt%, and more preferably 0.1 to 17 1.0 wt%.

19 Optionally, a polyalkylene co-oligomer may be employed in the lubricating oil composition. Preferably, the lubricating oil composition comprises from about 21 0.1 to 10 wt% of the polyalkene derivative. More preferred, the lubricating oil 22 composition comprises from about I to 7 wt% of the polyalkylene derivative.
23 Most preferred, the lubricating oil composition comprises from about 2 to 5 24 wt% of the polyalkylene derivative.
26 The lubricating composition described above can be made by addition of an 27 additive package to a lubricating base oil. Generally, the lubricating oil 28 composition will contain 1.0 to 50.0 wt.% of the additive package;
preferably, 29 the lubricating oil composition will contain 1 to 10.0 wt% of the additive package; and more preferably, the lubricating oil composition will contain 3.0 31 to 8.0 wt.% of the additive package.

1 Other Additives 3 A variety of other additives can be present in lubricating oils of the present 4 invention. These additives include antioxidants, viscosity index improvers, dispersants, rust inhibitors, foam inhibitors, corrosion inhibitors, other antiwear 6 agents, demulsifiers, friction modifiers, pour point depressants and a variety of 7 other well-known additives. Preferred dispersants include the well known 8 succinimide and ethoxylated alkylphenois and alcohols. Particularly preferred 9 additional additives are the oil-soluble succinimides, oil-soluble alkali or alkaline earth metal sulfonates, and dihydrocarbyl hydrogen phosphites.

12 The following additive components are examples of some of the components 13 that can be favorably employed in the present invention. These examples of 14 additives are provided to illustrate the present invention, but they are not intended to limit it:

16 1. Metal Detergents 17 Sulfurized or unsulfurized alkyl or alkenyl phenates, alkyl or alkenyl 18 aromatic sulfonates, borated sulfonates, sulfurized or unsulfurized 19 metal salts of multi-hydroxy alkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxy aromatic sulfonates, sulfurized or unsulfurized alkyl 21 or alkenyl naphthenates, metal salts of alkanoic acids, metal salts of an 22 alkyl or alkenyl multiacid, and chemical and physical mixtures thereof.

24 2. Anti-Oxidants Anti-oxidants reduce the tendency of mineral oils to deteriorate in 26 service which deterioration is evidenced by the products of oxidation 27 such as sludge and varnish-like deposits on the metal surfaces and by 28 an increase in viscosity. Examples of anti-oxidants useful in the 29 present invention include, but are not limited to, phenol type (phenolic) oxidation inhibitors, such as 4,4'-methylene-bis(2,6-di-tert-butylphenol), 31 4,4'-bis(2,6-di-tert-butylphenol), 4'-bis(2-methyl-6-tert-butylphenol), 32 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 1 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol), 2 4,4'-isopropylidene-bis(2,6-di-tert-butylphenol), 2,2'-methylene-bis(4-3 methyl-6-nonylphenol), 2,2'-isobutylidene-bis(4,6-dimethylphenol), 4 2,2'-5-methylene-bis(4-methyl-6-cyclohexylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butyl-6 phenol, 2,6-di-tert-l-dimethylamino-p-cresol, 2,6-di-tert-4-(N,N'-7 dimethylaminomethylphenol), 4,4'-thiobis(2-methyl-6-tert-butylphenol), 8 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3-methyl-4-hydroxy-5-tert-9 10-butylbenzyl)-sulfide, and bis(3,5-di-tert-butyl-4-hydroxybenzyl).
Diphenylamine-type oxidation inhibitors include, but are not limited to, 11 alkylated diphenylamine, phenyl-.alpha.-naphthylamine, and 12 alkylated-.alpha.-naphthylamine. Other types of oxidation inhibitors 13 include metal dithiocarbamate (e.g., zinc dithiocarbamate), and 14 1 5-methyl enebis(d i butyid ith ioca rba mate).
16 3. Anti-Wear Agents 17 As their name implies, these agents reduce wear of moving metallic 18 parts. Examples of such agents include, but are not limited to, 19 phosphates, carbamates, esters, and molybdenum complexes.
21 4. Rust Inhibitors (Anti-Rust Agents) 22 a) Nonionic polyoxyethylene surface active agents: polyoxyethylene 23 lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene 24 nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, 26 polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol 27 mono-oleate, and polyethylene glycol mono-oleate.
28 b) Other compounds: stearic acid and other fatty acids, dicarboxylic 29 acids, metal soaps, fatty acid amine salts, metal salts of heavy sulfonic acid, partial carboxylic acid ester of polyhydric alcohol, and 31 phosphoric ester.

1 5. Demulsifiers 2 Addition product of alkylphenol and ethylene oxide, polyoxyethylene 3 alkyl ether, and polyoxyethylene sorbitan ester.

4 6. Extreme Pressure Anti-Wear Agents (EP/AW Agents) Zinc diaiky-l-dithiophosphate (primary alkyl, secondary alkyl, and aryl 6 type), diphenyl sulfide, methyl trich lorostea rate, chlorinated 7 naphthalene, fluoroalkylpolysiloxane, lead naphthenate, neutralized 8 phosphates, dithiophosphates, and sulfur-free phosphates.

7. Friction Modifiers 11 Fatty alcohol, fatty acid, amine, borated ester, other esters, 12 phosphates, phosphites and phosphonates.

14 8. Multifunctional Additives Sulfurized oxymolybdenum dithiocarbamate, sulfurized 16 oxymolybdenum organo phosphorodithioate, oxymolybdenum 17 monoglyceride, oxymolybdenum diethylate amide, amine-molybdenum 18 complex compound, and sulfur-containing molybdenum complex 19 compound.
21 9. Viscosity Index Improvers 22 Polymethacrylate type polymers, ethylene-propylene copolymers, 23 styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, 24 polyisobutylene, and dispersant type viscosity index improvers.
26 10. Pour Point Depressants 27 Polymethyl methacrylate.

29 11. Foam Inhibitors Alkyl methacrylate polymers and dimethyl silicone polymers.

1 12. Metal Deactivators 2 Disalicylidene propylenediamine, triazole derivatives, 3 mercaptobenzothiazoles, and mercaptobenzimidazoles.
4 13. Dispersants Alkenyl succinimides, alkenyl succinimides modified with other organic 6 compounds, alkenyl succinimides modified by post-treatment with 7 ethylene carbonate or boric acid, pentaerythritols, phenate-salicylates 8 and their post-treated analogs, alkali metal or mixed alkali metal, 9 alkaline earth metal borates, dispersions of hydrated alkali metal borates, dispersions of alkaline-earth metal borates, polyamide ashiess 11 dispersants and the like or mixtures of such dispersants.

3 The following Examples are illustrative of the present invention, but are not 4 intended to limit the invention in any way beyond what is contained in the claims which follow.

7 Automotive Gear Oil Examples 9 The additive concentrate package shown in Table 1 may be blended by any conventional method. An automotive gear lubricant of typical viscosity (8.0 -11 18.0 cSt @ 100 C) grade may be blended by any conventional method with at 12 least one base stock as shown in Table 2 to achieve the desired viscosity 13 range. Specific mixtures of polysulfides were chosen according to the present 14 invention to achieve desired ratios of di-, tri-, tetra- and higher polysulfides.
Using mixtures of commercially available polysulfides (such as TBPS 344, 16 TBPS 34, TBPS 454, and dialkyl disulfides available from ChevronPhittips 17 Chemical Company), the ratios of polysulfides (that is, the relative 18 concentrations) can be adjusted according to the present invention to achieve 19 optimum frictional performance while maintaining improved anti-wear performance.

Table 1- Typical Additive Packages com onents in weight %) Example I Example 2 Example 3 Example 4 Components Potassium triborate dispersion 55 62 56 40 Dialkyl polysulfides 5' 18 322 Dialkyl dithio hos hate 6.5 8 4 Trialkyl phosphite 13 15 5 Corrosion inhibitors 1.9 1.9 1.9 1.9 Succinate ester dispersant 8 8 9 8 Calcium sulfonate detergent 5 5 5 4 Foam Inhibitor 0.1 0.1 0.1 0.1 Diluent oil 5.5 5 5 5 Total weight % 100.00 100.00 ' The dialkylpolysulfide employed in Example 1 contained 7.3 wt% disulfide, 44.4 wt%
trisulfide, and 48.3 wt% tetrasulfide or higher.
2 The dialkylpolysulfide employed in Example 4 contained 2.8 wt% disulfide, 92.4 wt%
trisulfide and 4.8 wt% tetrasulfide or higher.

100.00 100.00 Table 2 - Typical Gear Lubricant Blend Component Weight %
Mineral or Synthetic Base Stocks 80 - 77 Viscosity index improver 9 Package in Table 1 6-9 Friction modifier 4 Pour Point Depressant I
Total weight % 100.00 Although frictional properties of the lubricating oil can be improved by the 6 addition of friction modifiers, the extent of the improvement is limited.
Addition 7 of too much friction modifier can lead to detrimental side effects such as loss 8 of oxidation stability. Table 3 shows the effect on oxidation performance of 9 adding too much friction modifier. Oxidation performance is measured by standard method CEC L-48-A-95 which measures the per cent increase in 11 viscosity after heating the lubricant for a specified length of time. Lower per 12 cent viscosity increase is better.
13 Table 3 Lube Oil using Example 1 No FM 0.5% FM
Limit Oxidation Test, CEC L-48-A-95 160 C / 192 hr 50%
% increase in viscosity @ 100 C max 45 95 17 Frictional performance is very important to gear shifting in both manual and 18 automatic transmissions. If the friction is too low, too much pressure must be 19 exerted on the friction plates to achieve synchronization of the gears prior to shifting. If the friction is too high, the friction plates do not release smoothly 21 after the shift is complete, leading to a jerky feel in the transmission.

1 Friction can be measured by measuring the amount of torque required to 2 cause the friction plates in a transmission to separate after the gear shift is 3 complete. Specifically, this type of torque is called the breakaway torque and 4 is measured in Newton meters of force.
6 Specifically, breakaway torque is measured by employing a gear cone that is 7 driven at a low rotating speed by an electric engine and gear reduction. A
8 pneumatic cylinder with controlled compressed air pushes the synchronizing 9 collar against the gear cone with a given axial force. Meanwhile the torque is measured. This method enables the determination of the static and dynamic 11 friction coefficients. After release of the applied force, the torque to release 12 the blocked synchronizing collar is determined, which is also known as the 13 breakaway torque.

With any new gear set, there is usually an initial break-in period of about 25 16 gear shifting cycles before smooth shifting occurs and an average break-away 17 torque can be measured. An ideal break-away torque after 25 cycles (new) is 18 below 10 Nm. In addition to the desired average break-away torque value 19 over 100 shifting cycles being close to 2.0 Nm, it is also important that the break-away torque remain relatively constant after the break-in period. This 21 can be evaluated by looking at the slope of the break-away torque curve over 22 time. It is desired that the curve be flat with a slope close to zero. If the slope 23 is negative, it will lead to lower and lower break-away torque. If the slope is 24 positive, it will lead to higher break-away torque. Neither situation is acceptable because of the changing feel of the automotive transmission to the 26 driver.

28 The examples of the present invention show how a lubricating oil composition 29 can be achieved, which meets the required frictional criteria mentioned above and produces optimum anti-wear performance, by appropriate balance of 31 components in the lubricating oil additive package. Table 4 shows the 32 average break-away torque after run-in for lubricating oils made as shown in 33 Table 2 using lubricating oil additive packages shown in Table 1.

3 Table 4 Target Oil1 Oil 2 Oil 3 Oil 4 Commercial Comp. Comp. Comp. Ex. Oil Ex. Ex.
Average Break- 2.0 2.070 1.445 0.712 2.496 1.354 Away Torque, Nm Slope of Curve flat flat negative flat negative negative Oil 1, prepared using the additive package of Example 1, contains an alkali 6 metal borate, a polysulfide with the specified ratio of tetra-, tri-, and di-sulfides, 7 a dialkyl dithiophosphate ester and a trialkyl phosphite. This particular 8 combination of components meets all frictional requirements and requires only 9 minimal amount of extra friction modifiers to achieve the final desired frictional properties. Oil 2, prepared using the additive package of Example 2, is a 11 similar blend but lacks trialkyl phosphite and dialkyl dithiophosphate ester 12 components. The resultant oil has an unacceptably low break-away torque.
13 Oil 3, prepared using the additive package of Example 3, lacks the 14 polysulfides which are an essential component of the present invention. Not only is the break-away torque extremely low, but the torque keeps changing 16 leading to a negative slope which is also unacceptable. Oil 4, prepared using 17 the additive package of Example 4, has all the basic components of Oil 1 18 except that the polysulfides in Oil 4 are not of the desired ratio of tetra-, tri-, 19 and di-sulfides as specified in the claims. This leads to an unacceptably high break-away torque.

22 The effects described above can be seen more explicitly in Figures 1 - 5 23 which show the actual break-away torque measured at each cycle for Oils 1-24 5. The changes in break-away torque leading to an undesirable negative slope can be readily seen. Figure 1 is a graph depicting a flat slope and an 26 acceptable break-away torque. Figure 2 is a graph depicting a negative slope I with the breakaway torque gradually moving away from the acceptable range.
2 Figure 3 is a graph depicting a flat slope but a break-away torque which is too 3 low. Figure 4 is a graph depicting an undesirable negative slope in which the 4 breakaway torque never quite reaches the desired torque of 2.0 Nm. Figure 5 is a graph depicting a typical commercial oil which also has a negative slope.

7 While frictional performance is important for smooth shifting in a transmission, 8 a lubricating oil must also have acceptable anti-wear performance to protect 9 gears. The preferred lubricating oils described in the present invention also show improved anti-wear performance. This is shown in Table 5. Anti-wear 11 performance can be evaluated using the FZG narrow gear stage test 12 A10/16,6R/120 which measures changes in gear tooth appearance as greater 13 loads (stages) are placed on the gears. Thus a higher load stage result 14 reflects better performance. In Table 5, Oil 1 prepared from additive package 1 which uses trialkyl phosphite and polysulfides with an optimum ratio of tetra-16 , tri-, and disulfides shows improved anti-wear performance over the other oils 17 which lack the key components of the present invention.

19 Table 5 Oil 1 Oil 2 Oil 3 Oil 4 Commercial Oil FZG Pass Stage 10 9 9 8 9 21 Although used to prepare an automotive gear oil in the present example, the 22 additive concentrate described in Table 1 may also by used to prepare 23 industrial oils and greases as well.

Industrial Oil Example 27 Using the lubricating additive concentrates described in Examples 1- 4, Table 28 1, industrial gear oils may be blended as shown in Table 6 by any 29 conventional method to achieve any desired ISO viscosity range.

Table 6- Industrial Gear Lubricant Blend Component Weight %
Mineral or Synthetic Base Stocks 97 Packages in Table 1 2.75 Demulsifier 0.25 There are numerous variations on the present invention which are possible in 6 light of the teachings and supporting examples described herein. It is 7 therefore understood that within the scope of the following claims, the 8 invention may be practiced otherwise than as specifically described or 9 exemplified herein.

Claims

1. A lubricating oil composition comprising an oil of lubricating viscosity having dispersed therein a minor amount of a mixture of:

(a) at least one hydrated alkali metal borate component;

(b) at least one dihydrocarbyl polysulfide component comprising a mixture including less than about 64.5 wt.% dihydrocarbyl trisulfide, greater than about 5.5 wt.% dihydrocarbyl disulfide, and at least about 30.0 wt.% dihydrocarbyl tetrasulfide or higher polysulfides;

(c) at least one non-acidic phosphorus component comprising a trihydrocarbyl phosphite component, at least 90 wt.% of which has the formula (RO)3 P, wherein R is a hydrocarbyl group having 4 to 24 carbon atoms; and (d) at least one dihydrocarbyl dithiophosphate.

2. The composition of claim 1 wherein said lubricating oil composition also contains a minor amount of dihydrocarbyl hydrogen phosphite, at least 90 wt.% of which has the formula (RO)2 POH, wherein R is a hydrocarbyl group having 4 to 24 carbon atoms.

3. The composition of claim 1 wherein said lubricating oil composition comprises:

(a) 0.1 to 20.0 wt.% alkali metal borate;
(b) 0.1 to 10.0 wt.% the dihydrocarbyl polysulfide component;
(c) 0.01 to 15.0 wt.% of a non-acidic phosphorus component; and (d) 0.03 to 3.0 wt% of the dihydrocarbyl dithiophosphate.

4. The composition of claim 1, wherein said alkali metal borate is a potassium or sodium triborate.

5. The composition of claim 1, wherein said trihydrocarbyl phosphite is a mixture of C10 to C20 trialkyl phosphites.

6. The composition of claim 1, wherein said dihydrocarbyl dithiophosphate is an amine dithiophosphate salt.

7. A gear oil additive package comprising a mixture of:
(a) a hydrated alkali metal borate component;

(b) a dihydrocarbyl polysulfide component comprising a mixture including less than about 64.5 wt.% dihydrocarbyl trisulfide, greater than about 5.5 wt.% dihydrocarbyl disulfide, and at least about 30.0 wt.% dihydrocarbyl tetrasulfide or higher polysulfides;

(c) a non-acidic phosphorus component comprising a trihydrocarbyl phosphite component, at least 90 wt.% of which has the formula (RO)3 P, where R is a hydrocarbyl of 4 to 24 carbon atoms; and (d) at least one dihydrocarbyl dithiophosphate.

8. A gear oil additive package comprising a mixture of:
(a) a hydrated alkali metal borate component;

(b) a dihydrocarbyl polysulfide component comprising a mixture including less than 70 wt.% dihydrocarbyl trisulfide, more than 5.5 wt.% dihydrocarbyl disulfide, and at least 30 wt.%
dihydrocarbyl tetrasulfide or higher polysulfides;

(c) a non-acidic phosphorus component comprising a trihydrocarbyl phosphite component, at least 90 wt.% of which has the formula (RO)3 P, where R is a hydrocarbyl group of 4 to 24 carbon atoms;
(d) at least one dihydrocarbyl dithiophosphate; and (e) a phosphorus component comprising a dihydrocarbyl phosphite component at least 90 wt.% of which has the formula (RO)2 POH, where R is alkyl of 4 to 24 carbon atoms.

9. A lubricating oil composition comprising a major amount of lubricating oil and a minor but effective amount of the gear oil additive package of claim 7 to improve the load carrying and frictional properties of the lubricating composition.

10. A lubricating oil composition comprising a major amount of lubricating oil and a minor but effective amount of the gear oil additive package of claim 8 to improve the load carrying and frictional properties of the lubricating composition

11. A lubricating oil composition wherein the composition contains a major amount of an oil of lubricating viscosity and from about 1.0 to about 10.0 wt.% of said gear oil additive package of claims 7 or 8

12. The gear oil additive package of claims 7 or 8, wherein said borate is a potassium or sodium triborate.

13. The gear oil additive package of claims 7 or 8, wherein said dihydrocarbyl dithiophosphate is an amine dithiophosphate salt.

14. The lubricating oil composition of Claim 1 wherein the major amount of an oil of lubricating viscosity is selected from the group comprising Group I, Group II, Group III, Group IV or Fischer-Tropsch base oils.

15. The lubricating oil composition of Claim 1 comprising a polyalkene co-oligomer.

16. The lubricating oil composition of Claim 15 comprising from about 1-20 wt% of the polyalkene co-oligomer.

17. A method of making a lubricating oil composition comprising mixing a major amount of an oil of lubricating viscosity with (a) at least one hydrated alkali metal borate component;

(b) at least one dihydrocarbyl polysulfide component comprising a mixture including less than about 64.5 wt.% dihydrocarbyl trisulfide, greater than about 5.5 wt.% dihydrocarbyl disulfide, and at least about 30.0 wt.% dihydrocarbyl tetrasulfide or higher polysulfides;

(c) at least one non-acidic phosphorus component comprising a trihydrocarbyl phosphite component, at least 90 wt.% of which has the formula (RO)3 P, wherein R is a hydrocarbyl group having 4 to 24 carbon atoms; and (d) at least one dihydrocarbyl dithiophosphate.

18. A method of making a gear additive package comprising mixing (a) at least one hydrated alkali metal borate component;

(b) at least one dihydrocarbyl polysulfide component comprising a mixture including less than about 64.5 wt.% dihydrocarbyl trisulfide, greater than about 5.5 wt.% dihydrocarbyl disulfide, and at least about 30.0 wt.% dihydrocarbyl tetrasulfide or higher polysulfides;

(c) at least one non-acidic phosphorus component comprising a trihydrocarbyl phosphite component, at least 90 wt.% of which has the formula (RO)3 P, wherein R is a hydrocarbyl group having 4 to 24 carbon atoms; and (d) at least one dihydrocarbyl dithiophosphate.