Lubricant containing molybdenum compound and secondary diarylamine

• US 5,650,381 A
• Filed: 11/20/1995
• Issued: 07/22/1997
• Est. Priority Date: 11/20/1995
• Status: Expired

• Current Assignee: Afton Chemical Corporation
• Original Assignee: Ethyl Corporation (Newmarket Corporation)
• Inventors: Devlin, Mark Thomas, Gatto, Vincent James
• Primary Examiner(s): MEDLEY, MARGARET B
• Application Number:
  US08/559,879
• Time in Patent Office: 610 Days
• Field of Search: 252/35, 252/50, 508/364, 508/527
• US Class Current: 508/364
• CPC Class Codes: C10M 129/32 monocarboxylic
• CPC Class Codes: C10M 129/40 monocarboxylic
• CPC Class Codes: C10M 129/58 Naphthenic acids
• CPC Class Codes: C10M 133/12 having amino groups bound to a carbon atom of a six-membered aromatic ring
• CPC Class Codes: C10M 133/52 having a carbon chain of 30 or more atoms
• CPC Class Codes: C10M 137/10 Thio derivatives
• CPC Class Codes: C10M 139/06 having a metal-to-carbon bond metal complexes of unknown constitution C10M159/18
• CPC Class Codes: C10M 141/06 at least one of them being an organic nitrogen-containing compound
• CPC Class Codes: C10M 141/12 at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
• CPC Class Codes: C10M 143/04 containing propene
• CPC Class Codes: C10M 143/06 containing butene
• CPC Class Codes: C10M 143/12 containing conjugated diene
• CPC Class Codes: C10M 145/14 Acrylate; Methacrylate
• CPC Class Codes: C10M 145/16 polycarboxylic
• CPC Class Codes: C10M 159/18 Complexes with metals
• CPC Class Codes: C10M 159/20 Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
• CPC Class Codes: C10M 159/22 containing phenol radicals
• CPC Class Codes: C10M 159/24 containing sulfonic radicals
• CPC Class Codes: C10M 163/00 Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
• CPC Class Codes: C10M 167/00 Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
• CPC Class Codes: C10M 2205/00 : Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
• CPC Class Codes: C10M 2205/024 : Propene
• CPC Class Codes: C10M 2205/026 : Butene
• CPC Class Codes: C10M 2205/06 : containing conjugated dienes
• CPC Class Codes: C10M 2207/024 : having at least two phenol groups but no condensed ring
• CPC Class Codes: C10M 2207/026 : with tertiary alkyl groups
• CPC Class Codes: C10M 2207/028 : Overbased salts thereof
• CPC Class Codes: C10M 2207/09 : Metal enolates, i.e. keto-enol metal complexes
• CPC Class Codes: C10M 2207/121 : having hydrocarbon chains of seven or less carbon atoms
• CPC Class Codes: C10M 2207/122 : monocarboxylic
• CPC Class Codes: C10M 2207/125 : having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
• CPC Class Codes: C10M 2207/126 : monocarboxylic
• CPC Class Codes: C10M 2207/129 : having hydrocarbon chains of thirty or more carbon atoms
• CPC Class Codes: C10M 2207/14 : having carboxyl groups bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C10M 2207/142 : polycarboxylic
• CPC Class Codes: C10M 2207/16 : Naphthenic acids
• CPC Class Codes: C10M 2207/26 : Overbased carboxylic acid salts
• CPC Class Codes: C10M 2207/262 : derived from hydroxy substituted aromatic acids, e.g. salicylates
• CPC Class Codes: C10M 2207/289 : containing free hydroxy groups
• CPC Class Codes: C10M 2209/084 : Acrylate; Methacrylate
• CPC Class Codes: C10M 2209/086 : polycarboxylic, e.g. maleic acid
• CPC Class Codes: C10M 2215/04 : having amino groups bound to acyclic or cycloaliphatic carbon atoms
• CPC Class Codes: C10M 2215/06 : having amino groups bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C10M 2215/064 : Di- and triaryl amines
• CPC Class Codes: C10M 2215/065 : Phenyl-Naphthyl amines
• CPC Class Codes: C10M 2215/066 : Arylene diamines
• CPC Class Codes: C10M 2215/067 : Polyaryl amine alkanes
• CPC Class Codes: C10M 2215/068 : having amino groups bound to polycyclic aromatic ring systems, i.e. systems with three or more condensed rings
• CPC Class Codes: C10M 2215/22 : Heterocyclic nitrogen compounds
• CPC Class Codes: C10M 2215/221 : Six-membered rings containing nitrogen and carbon only
• CPC Class Codes: C10M 2215/225 : the rings containing both nitrogen and oxygen
• CPC Class Codes: C10M 2215/226 : Morpholines
• CPC Class Codes: C10M 2215/24 : having hydrocarbon substituents containing thirty or more carbon atoms , e.g. nitrogen derivatives of substituted succinic acid
• CPC Class Codes: C10M 2215/26 : Amines
• CPC Class Codes: C10M 2215/30 : Heterocyclic compounds
• CPC Class Codes: C10M 2217/046 : Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
• CPC Class Codes: C10M 2217/06 : Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
• CPC Class Codes: C10M 2219/022 : of hydrocarbons, e.g. olefines polyolefins C10M2221/041
• CPC Class Codes: C10M 2219/046 : Overbasedsulfonic acid salts
• CPC Class Codes: C10M 2219/066 : Thiocarbamic type compounds
• CPC Class Codes: C10M 2219/068 : Thiocarbamate metal salts
• CPC Class Codes: C10M 2219/082 : containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
• CPC Class Codes: C10M 2219/087 : containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
• CPC Class Codes: C10M 2219/088 : Neutral salts
• CPC Class Codes: C10M 2219/089 : Overbased salts
• CPC Class Codes: C10M 2219/108 : Phenothiazine
• CPC Class Codes: C10M 2223/045 : Metal containing thio derivatives
• CPC Class Codes: C10M 2223/065 : containing sulfur
• CPC Class Codes: C10M 2227/08 : having metal-to-carbon bonds metal complexes of unknown constitution C10M2227/09
• CPC Class Codes: C10M 2227/081 : with a metal carbon bond belonging to a ring, e.g. ferocene
• CPC Class Codes: C10M 2227/082 : Pb compounds
• CPC Class Codes: C10M 2227/083 : Sn compounds
• CPC Class Codes: C10M 2227/09 : Complexes with metals
• CPC Class Codes: C10N 2010/00 : Metal present as such or in compounds
• CPC Class Codes: C10N 2010/04 : Groups 2 or 12
• CPC Class Codes: C10N 2010/12 : Groups 6 or 16
• CPC Class Codes: C10N 2040/08 : Hydraulic fluids, e.g. brake-fluids
• CPC Class Codes: C10N 2040/25 : Internal-combustion engines
• CPC Class Codes: C10N 2040/251 : Alcohol fueled engines
• CPC Class Codes: C10N 2040/252 : Diesel engines
• CPC Class Codes: C10N 2040/253 : Small diesel engines
• CPC Class Codes: C10N 2040/255 : Gasoline engines
• CPC Class Codes: C10N 2040/28 : Rotary engines
• CPC Class Codes: C10N 2070/02 : Concentrating of additives

Abstract

There is disclosed a lubricating oil composition which contains from about 100 to 450 parts per million of molybdenum from a molybdenum compound which is substantially free of active sulfur and about 750 to 5,000 parts per million of a secondary diarylamine. This combination of ingredients provides improved oxidation control and friction modifier performance to the lubricating oil. The composition is particularly suited for use as a crankcase lubricant.

Claims

1. A lubricating composition comprising a major amount of lubricating oil, an oil soluble molybdenum compound providing about 100 to 450 parts per million of molybdenum, said molybdenum compound selected from the group consisting of a sulfur and phosphorus free organic amide molybdenum complex and a molybdenum carboxylate wherein the carboxylate anion has from about 4 to 30 carbon atoms and about 750 to 5,000 parts per million of an oil soluble secondary diarylamine.

2. The composition of claim 1 wherein the carboxylate is that of a monocarboxylic aliphatic acid having from about 4 to 18 carbon atoms or an alicyclic acid having from about 4 to 12 carbon atoms.

3. The composition of claim 1 wherein the diarylamine has from about 6 to 30 carbon atoms in each of the aryl groups.

4. The composition of claim 3 wherein at least one of the aryl groups is alkaryl having from 7 to 20 carbon atoms in the alkyl group.

5. The composition of claim 1 wherein the secondary diarylamine is of the formula:

##STR2## wherein R¹ and R² each independently represent an aryl group having from about 6 to 30 carbon atoms.

6. The composition of claim 1 wherein:

the molybdenum carboxylate is that of an aliphatic acid having from about 4 to 18 carbon atoms or an alicyclic acid having from 4 to 12 carbon atoms;

each of the aryl groups of the amine is a member selected from the group consisting of phenyl, naphthyl, alkphenyl wherein the alkyl portion has from about 4 to 18 carbon atoms and alknaphthyl wherein the alkyl portion has about 4 to 18 carbon atoms;

the quantity of molybdenum is from about 100 to 250 parts per million; and

the quantity of amine is from about 1,000 to 4,000 parts per million.

7. A method for improving the antioxidancy and friction properties of a lubricant which comprises including in the lubricant, a molybdenum compound which provides about 100 to 450 parts per million of molybdenum said molybdenum compound selected from the group consisting of a sulfur and phosphorus free organic amide molybdenum complex and a molybdenum carboxylate wherein the carboxylate anion has from about 4 to 30 carbon atoms and about 750 to 5,000 parts per million of an oil soluble secondary diarylamine.

8. The method of claim 7 wherein the amine is of the formula ##STR3## wherein each of R¹ and R² is alkphenyl having from about 4 to 18 carbon atoms in each alkyl group.

9. The method of claim 8 wherein the molybdenum carboxylate is prepared from an acid having from 4 to 18 carbon atoms and the quantity of molybdenum from the molybdenum carboxylate is from about 100 to 250 parts per million and the quantity of the amine is from about 1,200 to 3,000 parts per million.

10. The method of claim 9 wherein the acid is a monocarboxylic saturated fatty acid.

11. The method of claim 8 wherein the molybdenum carboxylate is molybdenum 2-ethylhexanoate.

12. The method of claim 7 wherein the molybdenum compound is a sulfur and posphorus free organic amide molybdenum complex.

13. A lubricating oil concentrate prepared by dissolving a total of from about 2.5 to 90 parts by weight of an oil soluble molybdenum compound selected from the group consisting of a sulfur and phosphorus free organic amide molybdenum complex and a molybdenum carboxylate derived from an organic carboxylic acid having about 4 to 30 carbon atoms and an oil soluble secondary diarylamine dissolved in 10 to 97.5 parts of a solvent wherein the weight ratio of molybdenum to amine is from about 0.02 to 0.6 parts of molybdenum for each part of amine.

14. The concentrate of claim 13 wherein the solvent is a mineral oil or synthetic oil and the ratio of molybdenum to amine is from about 0.04 to 0.4 parts of the molybdenum for each part of the amine, the molybdenum carboxylate is that of a monocarboxylic aliphatic acid having from about 4 to 18 carbon atoms or an alicyclic acid having from 4 to 12 carbon atoms, and at least one of the aryl groups of the amine is alkaryl having from 7 to 20 carbon atoms in the alkyl group.

15. The concentrate of claim 13 wherein one or more of the following additives are further present:

a dispersant;

a detergent; and

a zinc dihydrocarbyl dithiophosphate.

16. A lubricating oil composition prepared by mixing an oil soluble molybdenum compound selected from the group consisting of a sulfur and phosphorus free organic amide molybdenum complex and a molybdenum carboxylate derived from monocarboxylic acids selected from the group consisting of aliphatic acids having about 4 to 18 carbon atoms, alicyclic acids containing from 4 to 12 carbon atoms and aromatic acids containing from 7 to 14 carbon atoms and an oil soluble secondary diaryl amine in a lubricating oil wherein the concentration of the molybdenum in the oil is from about 100 to 450 parts per million and the concentration of the amine in the oil is from about 750 to 5,000 parts per million based on said composition.

17. The lubrication composition of claim 16 wherein:

A. the molybdenum compound is a molybdenum carboxylate of an aliphatic acid having from 4 to 18 carbon atoms and the concentration thereof is from about 100 to 250 parts per million of the composition; and

B. the diaryl amine is of the formula;

##STR4## wherein R¹ and R² each independently represent an aryl group having from about 6 to 30 carbon atoms and the concentration thereof is from about 1,000 to 4,000 parts per million of the composition.

18. The lubrication composition of claim 17 wherein the molybdenum carboxylate is that of a fatty acid having from about 4 to 18 carbon atoms and each of R¹ and R² of the amine is a member selected from the group consisting of phenyl, naphthyl, alkphenyl having from about 4 to 18 carbon atoms in the alkyl group and alknaphthyl having from about 4 to 18 carbon atoms in the alkyl group.

19. A method for improving the antioxidant and friction properties of a lubricant which comprises adding to the lubricant an oil soluble molybdenum carboxylate derived from an organic carboxylic acid having from about 4 to 30 carbon atoms and wherein said molybdenum carboxylate provides about 100 to 450 parts per million of molybdenum and about 750 to 5,000 parts per million of an oil soluble secondary diarylamine.

20. The method of claim 19 wherein the carboxylate is derived from a carboxylic acid selected from the group consisting of:

butyric acid;

valeric acid;

caproic acid heptanoic acid;

cyclohexanecarboxylic acid;

cyclodecanoic acid;

naphthenic acid;

phenyl acetic acid;

2-methylhexanoic acid;

2-ethylhexanoic acid;

suberic acid;

octanoic acid;

nonanoic acid;

decanoic acid;

undecanoic acid;

lauric acid, tridecanoic acid;

myristic acid;

pentadecanoic acid;

palmitic acid;

linolenic acid;

heptadecanoic acid;

stearic acid;

oleic acid;

nonadecanoic acid;

eicosanoic acid;

heneicosanoic acid;

docosanoic acid; and

erucic acid.

21. The method of claim 20 wherein:

the molybdenum carboxylate provides about 100 to 250 parts per million of molybdenum;

about 1,000 to 4,000 parts per million of the oil soluble secondary diarylamine are added to the lubricant and said amine is of the formula ##STR5## wherein each of R¹ and R² is alkphenyl having from about 4 to 18 carbon atoms in each alkyl group.