Lubricating oil compositions and concentrates

• US 4,957,649 A
• Filed: 08/01/1988
• Issued: 09/18/1990
• Est. Priority Date: 08/01/1988
• Status: Expired due to Term

• Current Assignee: The Lubrizol Corporation (Berkshire Hathaway Incorporated)
• Original Assignee: The Lubrizol Corporation (Berkshire Hathaway Incorporated)
• Inventors: Chamberlin, William B. III, Ripple, David E.
• Primary Examiner(s): Howard, Jacqueline V.
• Application Number:
  US07/226,765
• Time in Patent Office: 778 Days
• Field of Search: 252/32.7 E, 252/51.5 A, 252/33.3, 252/39, 252/56 R
• US Class Current: 508/237
• CPC Class Codes: C10M 129/10 having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
• CPC Class Codes: C10M 129/40 monocarboxylic
• CPC Class Codes: C10M 129/42 polycarboxylic
• CPC Class Codes: C10M 129/76 containing free hydroxy or carboxyl groups
• CPC Class Codes: C10M 129/95 Esters
• CPC Class Codes: C10M 133/52 having a carbon chain of 30 or more atoms
• CPC Class Codes: C10M 133/56 Amides; Imides
• CPC Class Codes: C10M 135/10 Sulfonic acids or derivatives thereof
• CPC Class Codes: C10M 137/06 Metal salts
• CPC Class Codes: C10M 137/10 Thio derivatives
• CPC Class Codes: C10M 141/10 at least one of them being an organic phosphorus-containing compound
• 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 2205/06 containing conjugated dienes
• CPC Class Codes: C10M 2207/023 having hydroxy groups bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C10M 2207/026 with tertiary alkyl groups
• CPC Class Codes: C10M 2207/027 Neutral salts thereof
• CPC Class Codes: C10M 2207/028 Overbased salts thereof
• CPC Class Codes: C10M 2207/123 : polycarboxylic
• 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 2207/127 : polycarboxylic
• CPC Class Codes: C10M 2207/128 : containing hydroxy groups; Ethers thereof
• CPC Class Codes: C10M 2207/129 : having hydrocarbon chains of thirty or more carbon atoms
• CPC Class Codes: C10M 2207/144 : containing hydroxy groups
• CPC Class Codes: C10M 2207/146 : having carboxyl groups bound to carbon atoms of six-membeered aromatic rings having a hydrocarbon substituent of thirty or more carbon atoms
• CPC Class Codes: C10M 2207/16 : Naphthenic acids
• CPC Class Codes: C10M 2207/22 : Acids obtained from polymerised unsaturated 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 2207/287 : Partial esters
• CPC Class Codes: C10M 2207/288 : containing free carboxyl groups
• CPC Class Codes: C10M 2207/289 : containing free hydroxy groups
• 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 2209/109 : esterified
• 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 2215/22 : 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 2215/28 : 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 2219/044 : Sulfonic acids, Derivatives thereof, e.g. neutral salts
• CPC Class Codes: C10M 2219/046 : Overbasedsulfonic acid salts
• 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 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 2223/12 : obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
• CPC Class Codes: C10N 2010/00 : Metal present as such or in compounds
• CPC Class Codes: C10N 2010/02 : Groups 1 or 11
• CPC Class Codes: C10N 2010/04 : Groups 2 or 12
• CPC Class Codes: C10N 2010/06 : Groups 3 or 13
• CPC Class Codes: C10N 2010/08 : Groups 4 or 14
• CPC Class Codes: C10N 2010/10 : Groups 5 or 15
• CPC Class Codes: C10N 2010/12 : Groups 6 or 16
• CPC Class Codes: C10N 2010/14 : Group 7
• CPC Class Codes: C10N 2010/16 : Groups 8, 9, or 10

Abstract

Lubricating oil compositions for internal combustion engines are described with comprise (A) a major amount of oil of lubricating viscosity, and minor amounts of (B) at least one carboxylic derivative composition produced by reacting (B-1) at least one substituted succinic acylating agent with (B-2) at least one amine compound characterized by the present within its structure of at least one HN< group (C) at least one partial fatty acid ester of a polyhydric alcohol, and (D) at least one metal salt of a dihydrocarbyl dithiosphosphoric acid. The oil compositions also may contain (E) at least one carboxylic ester derivative composition, and/or (F) at least one neutral or basic alkaline earth metal salt of at least one acidic organic compound.

Claims

1. A lubricating oil composition for internal combustion engines which comprises:

(A) a major amount of oil of lubricating viscosity, and minor amounts of

(B) at least one carboxylic derivative composition produced by reacting

(B-1) at least one substituted succinic acylating agent with

(B-2) from one equivalent up to two moles, per equivalent of acylating agent, of at least one amine compound characterized by the presence within its structure of at least one HN<

group wherein said substituted succinic acylating agents consist of substituent groups and succinic groups wherein the substituent groups are derived from polyalkene, said polyalkene being characterized by an Mn value of about 1300 to about 5000 and an Mw/Mn value of about 1.5 to about 4.5, said acylating agents being characterized by the presence within their structure of an average of at least 1.3 succinic groups for each equivalent weight of substituent groups,

(C) at least one partial fatty acid ester of a polyhydric alcohol, and

(D) at least one metal salt of a dihydrocarbyl dithiophosphoric acid wherein

(D-1) the dithiophosphoric acid is prepared by reacting phosphorus pentasulfide with an alcohol mixture comprising at least 10 mole percent of isopropyl alcohol, secondary butyl alcohol, or a mixture of isopropyl and secondary butyl alcohols, and at least one primary aliphatic alcohol containing from about 3 to about 13 carbon atoms, and

(D-2) the metal is a Group II metal, aluminum, tin, iron, cobalt, lead, molybdenum, manganese, nickel or copper.

2. The oil composition of claim 1 containing at least about 1% by weight of the carboxylic derivative composition (B).

3. The oil composition of claim 1 wherein the value of Mn in (B) is at least about 1500.

4. The oil composition of claim 1 wherein the value of Mw/Mn in (B) is at least about 2.0.

5. The oil composition of claim 1 wherein the substituent groups in (B) are derived from one or more polyalkenes selected from the group consisting of homopolymers and interpolymers of terminal olefins of from 2 to about 16 carbon atoms with the proviso that said interpolymers can optionally contain up to about 25% of polymer units derived from internal olefins of up to about 6 carbon atoms.

6. The oil composition of claim 1 wherein the substituent groups are derived from a member selected from the group consisting of polybutene, ethylene-propylene copolymer, polypropylene, and mixtures of two or more of any of these.

7. The oil composition of claim 1 wherein the amine (B-2) is an aliphatic, cycloaliphatic or aromatic polyamine.

8. The oil composition of claim 1 wherein the amine (B-2) is characterized by the general formula ##STR9## wherein n is from 1 to about 10;

each R³ is independently a hydrogen atom, a hydrocarbyl group or a hydroxy-substituted or an amino-substituted hydrocarbyl group having up to about 30 atoms, or two R³ groups on different nitrogen atoms can be joined together to form a U group, with the proviso that at least one R³ group is a hydrogen atom and U is an alkylene group of about 2 to about 10 carbon atoms.

9. The oil composition of claim 1 wherein the fatty acid ester in (C) contains from about 10 to about 22 carbon atoms.

10. The oil composition of claim 1 wherein the polyhydric alcohol of (C) is glycerol.

11. The oil composition of claim 1 wherein the primary aliphatic alcohol in (D-1) contains from about 6 to about 13 carbon atoms.

12. The oil composition of claim 1 wherein the metal of (D-2) is zinc, copper, or mixtures of zinc and copper.

13. The oil composition of claim 1 wherein the metal of (D-2) is zinc.

14. The oil composition of claim 1 wherein the alcohol mixture in (D-1) comprises at least 20 mole percent of isopropyl alcohol.

15. The oil composition of claim 1 also containing

(E) at least one carboxylic ester derivative composition produced by reacting

(E-1) at least one substituted succinic acylating agent comprising substituent groups and succinic groups wherein the substituent groups have an Mn of at least about 700 with

(E-2) at least one alcohol of the general formula

16. The oil composition of claim 15 wherein the substituent groups in (E-1) are derived from a member selected from the group consisting of polybutene, ethylene-propylene copolymer, polypropylene, and mixtures of two or more of any of these.

17. The oil composition of claim 15 wherein the alcohol (E-2) is neopentyl glycol, ethylene glycol, glycerol, pentaerythritol, sorbitol, mono-alkyl or monoaryl ethers of a poly(oxyalkylene) glycol, or mixtures of any one of these.

18. The oil composition of claim 15 wherein the carboxylic ester derivative composition (E) prepared by reacting the acylating agent (E-1) with the alcohol (E-2) is further reacted with

(E-3) at least one amine containing at least one HN<

group.

19. The oil composition of claim 15 wherein the substituted succinic acylating agent (E-1) consists of substituent groups and succinic groups wherein the substituent groups are derived from a polyalkene, said polyalkene being characterized by an Mn value of about 1300 to about 5000 and an Mw/Mn value of from about 1.5 to about 4.5, said acylating agents being characterized by the presence within their structure of at least about 1.3 succinic groups for each equivalent weight of substituent group.

20. The oil composition of claim 19 wherein the carboxylic ester prepared by reacting the acylating agent with the alcohol is further reacted with (E-3) at least one amine containing at least one HN<

group.

21. The oil composition of claim 20 wherein the amine (E-3) is a polyamine.

22. The oil composition of claim 20 wherein the amine (E-3) is an alkylene polyamine.

23. The oil composition of claim 1 also containing

(F) at least one neutral or basic alkaline earth metal salt of at least one acidic organic compound.

24. The oil composition of claim 23 wherein the acidic organic compound in (F) is a sulfur acid, carboxylic acid, phosphorus acid, phenol, or mixtures thereof.

25. The oil composition of claim 23 wherein the acidic compound in (F) is at least one organic sulfonic acid.

26. The oil composition of claim 25 wherein the sulfonic acid is an alkylated benzene sulfonic acid.

27. A lubricating oil composition for internal combustion engines which comprises

(A) a major amount of oil of lubricating viscosity,

(B) from about 0.5% to about 10% by weight of at least one carboxylic derivative composition produced by reacting

(B-1) at least one substituted succinic acylating agent with from 1 equivalent up to about 2 moles, per equivalent of acylating agent, of

(B-2) at least one polyamine characterized by the presence within its structure of at least one HN<

group wherein said substituted succinic acylating agent consists of substituent groups and succinic groups wherein the substituent groups are derived from a polyalkene, said polyalkene being characterized by an Mn value of about 1300 to about 5000 and an Mw/Mn value of about 2 to about 4.5, said acylating agents being characterized by the presence within their structure of an average of at least 1.3 succinic groups for each equivalent weight of substituent groups,

(C) from about 0.01 to about 2% by weight of at least one partial fatty acid ester of a polyhydric alcohol,

(D) from about 0.05 to about 5% by weight of at least one metal salt of a dihydrocarbyl dithiophosphoric acid wherein

(D-1) the dithiophosphoric acid is prepared by reacting phosphorus pentasulfide with an alcohol mixture comprising at least 10 mole percent of isopropyl alcohol, secondary butyl alcohol or a mixture of isopropyl and secondary butyl alcohols, and at least one primary aliphatic alcohol containing from about 3 to about 13 carbon atoms, and

(D-2) the metal is a Group II metal, aluminum, tin, iron, cobalt, lead, molybdenum, manganese, nickel or copper,

(E) 0.1 to about 10% of at least one carboxylic ester derivative composition produced by reacting

(E-1) at least one substituted succinic acylating agent comprising substituent groups and succinic groups wherein the substituent groups are derived from a polyalkene, said polyalkene being characterized by an Mn value of about 1300 to about 5000 and an Mw/Mn value of from about 1.5 to about 4.5, said acylating agents being characterized by the presence within their structure of at least about 1.3 succinic groups for each equivalent weight of substituent group with

(E-2) at least one alcohol of the general formula

space="preserve" listing-type="equation">R.sup.3 (OH).sub.m (VIII)

wherein R³ is a monovalent or polyvalent organic group joined to the --OH groups through carbon bonds, and m is an integer of from 2 to about 10, and

(E-3) at least one polyamine compound containing at least one >

NH group, and

(F) from about 0.01 to about 5% by weight of at least one alkaline earth metal salt of an organic acid compound selected from the group consisting of sulfur acids, carboxylic acids, phosphorus acids, phenols, and mixtures of said acids.

28. The oil composition of claim 27 containing at least about 1.0% by weight of the carboxylic derivative composition (B).

29. The oil composition of claim 27 wherein the amines (B-2) and (E-3) are each independently polyamines characterized by the general formula ##STR10## wherein n is an integer from 1 to about 10, each R³ is independently a hydrogen atom, a hydrocarbyl group or a hydroxy-substituted or an amino-substituted hydrocarbyl group having up to about 30 atoms, or two R³ groups on different nitrogen atoms can be joined together to form a U group, with the proviso that at least one R³ group is a hydrogen atom and U is an alkylene group of about 2 to about 10 carbon atoms.

30. The oil composition of claim 27 wherein the primary aliphatic alcohol in (D-1) contains from about 6 to about 13 carbon atoms.

31. The oil composition of claim 27 wherein the metal of (D-2) is zinc, copper, or mixtures of zinc and copper.

32. The oil composition of claim 27 wherein the metal of (D-2) is zinc.

33. The oil composition of claim 27 wherein the alcohol mixture in (D-1) comprises at least 20 mole percent of isopropyl alcohol.

34. The oil composition of claim 27 wherein the alcohol (E-2) is neopentyl glycol, ethylene glycol, glycerol, pentaerythritol, sorbitol, mono-alkyl or monoaryl ethers of a poly(oxyalkylene) glycol, or mixtures of any two or more of these.

35. A lubricating oil composition for internal combustion engines which comprises

(A) a major amount of oil of lubricating viscosity,

(B) from about 1% to about 10% by weight of at least one carboxylic derivative composition produced by reacting

(B-1) at least one substituted succinic acylating agent with from 1.0 to about 1.5 equivalents, per equivalent of acylating agent, of

(B-2) at least one polyamine characterized by the presence within its structure of at least one HN<

group wherein said substituted succinic acylating agent consists of substituent groups and succinic groups wherein the substituent groups are derived from a polyalkene, said polyalkene being characterized by an Mn value of about 1300 to about 5000 and an Mw/Mn value of about 2 to about 4.5, said acylating agents being characterized by the presence within their structure of an average of at least 1.3 succinic groups for each equivalent weight of substituent groups,

(C) from about 0.05 to about 2% by weight of at least one partial fatty acid ester of glycerol,

(D) from about 0.05 to about 5% by weight of at least one metal salt of a dihydrocarbyl dithiophosphoric acid wherein

(D-1) the dithiophosphoric acid is prepared by reacting phosphorus pentasulfide with an alcohol mixture comprising at least about 20 mole percent of isopropyl alcohol and at least one primary aliphatic alcohol containing from about 6 to about 13 carbon atoms, and II metal,

(D-2) the metal is a Group II metal, aluminum, tin, iron, cobalt, lead, molybdenum, manganese, nickel or copper,

(E) 0.1 to about 10% of at least one carboxylic ester derivative composition produced by reacting

(E-1) at least one substituted succinic acylating agent comprising substituent groups and succinic groups wherein the substituent groups are derived from a polyalkene, said polyalkene being characterized by an Mn value of about 1300 to about 5000 and an Mw/Mn value of from about 1.5 to about 4.5, said acylating agents being characterized by the presence within their structure of at least about 1.3 succinic groups for each equivalent weight of substituent group with

(E-2) from about 0.1 to about 2 moles, per mole of acylating agent of at least one polyhydroxy compound selected from the group consisting of neopentyl glycol, ethylene glycol glycerol, pentaerythritol, sorbitol, mono-alkyl or mono-aryl ethers of a poly(oxyalkylene)glycol or mixtures of any two or more of these and

(E-3) at least one polyamine containing at least one >

NH group, and

(F) from about 0.01 to about 5% by weight of at least one alkaline earth metal salt of an organic acid compound selected from the group consisting of sulfonic acids, carboxylic acids, phenols, and mixtures of said acids.

36. The oil composition of claim 35 wherein the polyamines (B-2) and (E-3) are each independently polyamines characterized by the general formula ##STR11## wherein n is an integer from 1 to about 10, each R³ is independently a hydrogen atom, a hydrocarbyl group or a hydroxy-substituted or an amino-substituted hydrocarbyl group having up to about 30 atoms, or two R³ groups on different nitrogen atoms can be joined together to form a U group, with the proviso that at least one R³ group is a hydrogen atom and U is an alkylene group of about 2 to about 10 carbon atoms.

37. The oil composition of claim 35 wherein

(F) comprises a mixture of basic alkaline earth metal salts of organic sulfonic acids.

38. A concentrate for formulating lubricating oil compositions comprising from about 20 to about 90% by weight of a normally liquid, substantially inert organic diluent/solvent,

(B) from about 10 to about 50% by weight of at least one carboxylic derivative composition produced by reacting

(B-1) at least one substituted succinic acylating agent with at least one equivalent, per equivalent of acylating agent, of

(B-2) at least one amine characterized by the presence within its structure of at least one HN<

group wherein said substituted succinic acylating agent consists of substituent groups and succinic groups wherein the substituent groups are derived from a polyalkene, said polyalkene being characterized by an Mn value of about 1300 to about 5000 and an Mw/Mn value of about 1.5 to about 4.5, said acylating agents being characterized by the presence within their structure of an average of at least 1.3 succinic groups for each equivalent weight of substituent groups,

(C) from about 0.1 to about 15% by weight of at least one fatty acid ester of a polyhydric alcohol, and of

(D) from about 0.001 to about 15% by weight at least one metal salt of a dihydrocarbyl dithiophosphoric acid wherein

(D-1) the dithiophosphoric acid is prepared by reacting phosphorus pentasulfide with an alcohol mixture comprising at least 10 mole percent of isopropyl alcohol, secondary butyl alcohol or a mixture of isopropyl and secondary butyl alcohols, and at least one primary aliphatic alcohol containing from about 3 to about 13 carbon atoms, and

(D-2) the metal is a Group II metal, aluminum, tin, iron, cobalt, lead, molybdenum, manganese, nickel or copper.

39. The concentrate of claim 38 also containing from about 1% by weight to about 30% by weight of

(E) at least one carboxylic ester derivative composition produced by reacting

(E-1) at least one substituted succinic acylating agent comprising substituent groups and succinic groups wherein the substituent groups are derived from a polyalkene, said polyalkene being characterized by an Mn value of about 1300 to about 5000 and an Mw/Mn value of from about 1.5 to about 4.5, said acylating agents being characterized by the presence within their structure of at least about 1.3 succinic groups for each equivalent weight of substituent group with

(E-2) at least one alcohol of the general formula

40. The concentrate of claim 39 wherein the carboxylic ester (E) produced by reacting the acylating agent (E-1) with the alcohol (E-2) is further reacted with

(E-3) at least one polyamine containing at least one HN<

group.

41. The concentrate of claim 38 also containing from about 1% by weight to about 20% by weight of

(F) at least one neutral or basic alkaline earth metal salt of at least one acidic organic compound.

42. The concentrate of claim 39 also containing from about 1% by weight to about 20% by weight of

(F) at least one neutral or basic alkaline earth metal salt of at least one acidic organic compound.