Synergistic antioxidant additive composition

• US 4,089,792 A
• Filed: 04/01/1976
• Issued: 05/16/1978
• Est. Priority Date: 04/01/1976
• Status: Expired due to Term

• Current Assignee: Chevron Research Company (Chevron Corp.)
• Original Assignee: Chevron Research Company (Chevron Corp.)
• Inventors: Lowe, Warren
• Primary Examiner(s): Gantz, Delbert E.
• Assistant Examiner(s): Vaughn, Irving
• Application Number:
  US05/672,804
• Time in Patent Office: 775 Days
• Field of Search: 252/32.7 E, 252/50, 252/47, 252/47.5, 252/402, 252/400 A
• US Class Current: 508/259
• CPC Class Codes: C10M 1/08 with additives
• CPC Class Codes: C10M 2201/083 nitrites
• CPC Class Codes: C10M 2203/02 Well-defined aliphatic compounds
• CPC Class Codes: C10M 2203/022 saturated
• CPC Class Codes: C10M 2203/024 unsaturated
• CPC Class Codes: C10M 2203/04 Well-defined cycloaliphatic compounds
• CPC Class Codes: C10M 2203/06 Well-defined aromatic compounds
• 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 2207/027 Neutral salts thereof
• CPC Class Codes: C10M 2207/04 Ethers; Acetals; Ortho-esters; Ortho-carbonates
• CPC Class Codes: C10M 2207/123 polycarboxylic
• 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 2207/22 Acids obtained from polymerised unsaturated acids
• CPC Class Codes: C10M 2207/282 of (cyclo)aliphatic oolycarboxylic acids
• CPC Class Codes: C10M 2207/34 Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
• CPC Class Codes: C10M 2209/103 Polyethers, i.e. containing di- or higher polyoxyalkylene groups
• CPC Class Codes: C10M 2209/104 : of alkylene oxides containing two carbon atoms only
• CPC Class Codes: C10M 2209/105 : of alkylene oxides containing three carbon atoms only
• CPC Class Codes: C10M 2215/02 : Amines, e.g. polyalkylene polyamines; Quaternary amines polyalkylene polyamines with eleven or more monomer units C10M2217/046
• CPC Class Codes: C10M 2215/04 : having amino groups bound to acyclic or cycloaliphatic carbon atoms
• CPC Class Codes: C10M 2215/042 : containing hydroxy groups; Alkoxylated derivatives thereof
• CPC Class Codes: C10M 2215/06 : having amino groups bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C10M 2215/062 : containing hydroxy groups bound to the aromatic ring
• CPC Class Codes: C10M 2215/064 : Di- and triaryl amines
• CPC Class Codes: C10M 2215/086 : Imides
• 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 2215/223 : Five-membered rings containing nitrogen and carbon only
• CPC Class Codes: C10M 2215/224 : Imidazoles
• CPC Class Codes: C10M 2215/225 : the rings containing both nitrogen and oxygen
• CPC Class Codes: C10M 2215/226 : Morpholines
• CPC Class Codes: C10M 2215/26 : Amines
• CPC Class Codes: C10M 2215/28 : Amides; Imides
• 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 2219/02 : Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
• CPC Class Codes: C10M 2219/022 : of hydrocarbons, e.g. olefines polyolefins C10M2221/041
• CPC Class Codes: C10M 2219/024 : of esters, e.g. fats
• CPC Class Codes: C10M 2219/044 : Sulfonic acids, Derivatives thereof, e.g. neutral salts
• CPC Class Codes: C10M 2219/06 : Thio-acids; Thiocyanates; Derivatives thereof
• CPC Class Codes: C10M 2219/082 : containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
• CPC Class Codes: C10M 2219/083 : Dibenzyl sulfide
• CPC Class Codes: C10M 2219/085 : containing carboxyl groups; Derivatives thereof
• CPC Class Codes: C10M 2221/04 : Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C10M 2221/041 : involving sulfurisation of macromolecular compounds, e.g. polyolefins
• CPC Class Codes: C10M 2223/04 : Phosphate esters
• CPC Class Codes: C10M 2223/041 : Triaryl phosphates
• CPC Class Codes: C10M 2223/042 : Metal salts thereof
• CPC Class Codes: C10M 2223/045 : Metal containing thio derivatives
• CPC Class Codes: C10M 2227/02 : Esters of silicic acids
• CPC Class Codes: C10M 2229/02 : Unspecified siloxanes; Silicones
• CPC Class Codes: C10M 2229/04 : Siloxanes with specific structure
• CPC Class Codes: C10M 2229/041 : containing aliphatic substituents
• CPC Class Codes: C10M 2229/042 : containing aromatic substituents
• CPC Class Codes: C10M 2229/043 : containing carbon-to-carbon double bonds
• CPC Class Codes: C10M 2229/044 : containing silicon-to-hydrogen bonds
• CPC Class Codes: C10M 2229/05 : containing atoms other than silicon, hydrogen, oxygen or carbon
• CPC Class Codes: C10N 2010/04 : Groups 2 or 12
• CPC Class Codes: C10N 2070/02 : Concentrating of additives

Abstract

A lubricating oil additive composition which imparts improved oxidaton properties to crankcase lubricants comprises an antioxidant selected from aromatic or alkyl sulfides and polysulfides, sulfurized olefins, sulfurized carboxylic acid esters and sulfurized ester-olefins, and a primary amine of the formula: ##STR1## wherein each A is independently hydrogen or alkyl, R is alkyl or alkenyl of at least 6 carbon atoms, R¹ is an alkyl group of at least 2 carbon atoms, x is an integer from 2 to 4, y is 1 to 4, and Het forms with the N atom, a 5- or 6-membered heterocyclic ring optionally containing an additional N or O hetero atom. Lubricating oil compositions containing this additive composition are also disclosed. Zn dithiophosphates may, also, be used in the additive composition.

Claims

1. An additive composition for use in crankcase lubricating oils comprising:

(1) an oil-soluble antioxidant selected from aromatic or alkyl sulfides and polysulfides, sulfurized olefins, sulfurized carboxylic acid esters, and sulfurized ester-olefins, and

(2) a primary amine of the formula;

##STR7## wherein each A is independently hydrogen or alkyl, R is alkyl or alkenyl of at least 6 carbon atoms, R¹ is an alkyl group of at least 2 carbon atoms, x is an integer from 2 to 4, y is 1 to 4, and Het forms with the N atom, a 5- or 6-membered heterocyclic ring optionally containing an additional N or O hetero atom and wherein the weight ratio of said anti-oxidant to said primary amine is 1;

0.001-21.

2. A lubricating oil composition comprising an oil of lubricating viscosity and an antioxidant amount of the composition of claim 1.

3. The composition of claim 1 comprising an oil of lubricating viscosity, from 0.25 to 10 weight percent of said antioxidant, and from 0.001 to 5 weight percent of said primary amine.

4. The composition of claim 3 which contains an antioxidant-antiwear amount of zinc dihydrocarbyldithiophosphate, and wherein said antioxidant is a wax sulfide or polysulfide.

5. The composition of claim 4 which contains from 2 to 40 mmoles of zinc per kilogram of composition, present as said oil-soluble zinc salt from 0.25 to 2 weight percent of a paraffin wax thiomer antioxidant and from 0.01 to 0.3 weight percent of said primary amine.

6. The composition of claim 3 wherein y is 1 to 4 and R is alkyl of 12 to 22 carbon atoms.

7. The composition of claim 5 wherein R is alkyl of 12 to 22 carbon atoms.

8. The composition of claim 7 wherein R is octadecyl.

9. The composition of claim 3 wherein y is 1 to 4, A is hydrogen and R is alkyl or alkenyl group of from 30 to 250 carbon atoms.

10. The composition of claim 5 wherein R is an alkyl or alkenyl group of from 30 to 250 carbon atoms, y is 1 to 4, A is hydrogen.

11. The composition of claim 10 wherein R is polyisobutenyl of from about 40 to about 120 carbon atoms and x is 2.

12. The composition of claim 8 wherein said zinc salt is a zinc dialkyldithiophosphate wherein each alkyl group contains from 4 to 8 carbon atoms.

13. The composition of claim 11 wherein said zinc salt is a zinc dialkyldithiophosphate wherein each alkyl group contains from 4 to 8 carbon atoms.

14. The composition of claim 4 wherein Het N-- is piperazinyl and R¹ is ethyl.

15. A lubricating oil additive concentrate which comprises from 90-10 percent weight of an oil of lubricating viscosity and from 10-90 percent weight of the composition of claim 1.

17. The composition of claim 8 wherein said zinc salt is a zinc diaryl dithiophosphate.

18. The composition of claim 11 where said zinc salt is a zinc diaryl dithiophosphate.

16. A method for inhibiting the oxidation of a lubricating oil which comprises adding to said lubricating oil from 0.25 to 10 percent weight of (1) an oil-soluble antioxidant selected from aromatic and alkyl sulfides and polysulfides, sulfurized olefins, sulfurized carboxylic acid esters and sulfurized ester-olefin, and of from 0.001 to 5 percent weight (2) a primary amine of the formula ##STR8## wherein each A is independently hydrogen or alkyl, R is alkyl or alkenyl of at least 6 carbon atoms, R'"'"' is an alkyl group of at least 2 carbon atoms, x is an integer from 2 to 4, y is 1 to 4, and Het forms with the N atom, a 5- or 6-membered heterocyclic ring optionally containing an additional N or O hetero atom.