Lubricating oil compositions

• US 4,904,401 A
• Filed: 09/08/1988
• Issued: 02/27/1990
• Est. Priority Date: 06/13/1988
• Status: Expired due to Term

• Current Assignee: The Lubrizol Corporation (Berkshire Hathaway Incorporated)
• Original Assignee: The Lubrizol Corporation (Berkshire Hathaway Incorporated)
• Inventors: Schroeck, Calvin W., Ripple, David E.
• Primary Examiner(s): Howard, Jacqueline V.
• Application Number:
  US07/242,038
• Time in Patent Office: 537 Days
• Field of Search: 252/32.7 E, 252/33, 252/51.5 A
• US Class Current: 508/237
• CPC Class Codes: C10M 129/38 having 8 or more carbon atoms
• 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 135/02 Sulfurised compounds
• CPC Class Codes: C10M 135/10 Sulfonic acids or derivatives thereof
• CPC Class Codes: C10M 135/30 containing hydroxy groups; Derivatives thereof
• 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 2205/00 Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
• 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 2207/129 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 2207/18 Tall oil acids
• CPC Class Codes: C10M 2207/20 : Rosin 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 2207/28 : Esters epoxidised esters C10M2207/24
• CPC Class Codes: C10M 2207/283 : of polyhydroxy compounds
• 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 2209/104 : of alkylene oxides containing two carbon atoms only
• 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 2215/064 : Di- and triaryl amines
• 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 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 2219/044 : 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 2223/045 : Metal containing thio derivatives
• CPC Class Codes: C10M 2227/061 : Esters derived from boron
• CPC Class Codes: C10M 2229/02 : Unspecified siloxanes; Silicones
• CPC Class Codes: C10M 2229/05 : containing atoms other than silicon, hydrogen, oxygen or carbon
• 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
• CPC Class Codes: C10N 2040/25 : Internal-combustion engines
• CPC Class Codes: C10N 2040/251 : Alcohol fueled engines
• CPC Class Codes: C10N 2040/255 : Gasoline engines
• CPC Class Codes: C10N 2040/28 : Rotary engines
• CPC Class Codes: F02B 1/04 : with fuel-air mixture admission into cylinder
• CPC Class Codes: F02B 2075/125 : Direct injection in the combustion chamber for spark ignition engines, i.e. not in pre-combustion chamber
• CPC Class Codes: F02F 7/006 : Camshaft or pushrod housings

Abstract

A lubricating oil formulation is described which is useful in internal combustion engines. More particularly, lubricating oil compositions for internal combustion engines are described with comprise (A) a major amount of oil of lubricating viscosity, and at least 2.0% by weight 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 presence within its structure of at least one HN< group, and wherein said substituted succinic acylating agent consists of substituent groups and succinic groups wherein the substituent groups are derived from a polyalkylene, said polyalkene being characterized by 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, and (C) from about 0.05 to about 5% by weight of a mixture of metal salts of dihydrocarbyl phosphorodithioic acids wherein in at least one of the dihydrocarbyl phosphorodithioic acids, one of the hydrocarbyl groups (C-1) is an isopropyl or secondary butyl group, the other hydrocarbyl group (C-2) contains at least five carbon atoms, and at least about 20 mole percent of all of the hydrocarbyl groups present in (C) are isopropyl groups, secondary butyl groups or mixtures thereof, provided that at least about 25 mole percent of the hydrocarbyl groups in (C) are isopropyl groups, secondary butyl groups, or mixtures thereof when the lubrication oil compositions comprise less than about 2.5% by weight of (B). In one embodiment, the oil compositions contain at least about 0.05 weight percent of isopropyl groups, secondary butyl groups of mixtures thereof derived from the mixture of metal salts of phosphorodithioic acids (C). The oil compositions also may contain other desirable additives such as (D) at least one neutral or basic alkaline earth metal salt of at least one acidic organic compound and/or (E) at least one carboxylic ester derivative. In one embodiment, the oil compositions of the present invention contain the above additives and other additives described in the specification in amounts sufficient to enable the oil to meet all the performance requirements of the API Service Classification identified as "SG", and in another embodiment the oil compositions of the invention will contain the above additives and other additives described in the specification in amounts sufficient to enable the oils to satisfy the requirements of the API Service Classification identified as "CE".

Claims

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

(A) a major amount of oil of lubrication viscosity

(B) at least about 2.5% by weight of at least one carboxylic derivative composition produced by reacting

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

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

group wherein said substituted succininc acrylating agents consist of substituent groups groups wherein the substituent groups are derived from polyalklene, said polyalkene being characterized characterized by an Mn value of 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, and

(C) from about 0.05 to about 5% by weight of a mixture of metal salts of dihydrocarbyl phosphorodithioic acids wherein in at least one of the dihydrocarbyl phosphorodithioic acids, one of the hydrocarbyl groups (C-1) is an isopropyl or secondary butyl group, the other hydrocarbyl group (C-2) contains at least five carbon atoms, and at least about 25 mole percent of all of the hydrocarbyl groups present in (C) are isopropyl groups, secondary butyl groups or mixtures thereof.

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

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

4. 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 6 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.

5. The oil composition of claim 1 wherein the substituent groups in (B) are derived from polybutene in which at least about 50% of the total units derived from butenes is derived from isobutene.

6. The oil composition of claim 1 wherein in (B), from about 0.5 equivalent up to about 2 moles of the amine (B-2) is reacted per equivalent of acylating agent (B-1).

7. The oil composition of claim 1 wherein in (B) from about 0.5 up to less than one equivalent of the amine (B-2) is reacted per equivalent of acylating agent (B-1).

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

9. The oil composition of claim 1 wherein the amine (B-2) is a hydroxy substituted monoamine, polyamine, or mixtures thereof.

10. The oil composition of claim 1 wherein the amine (B-2) is 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 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 Rhu 3 group is a hydrogen atom and U is an alkylene group of about 2 to about 10 carbon atoms.

11. The oil composition of claim 1 wherein the acylating agents are characterized by the presence within their structure of at least about 1.5 up to about 2.5 succinic groups for each equivalent weight of the substituent groups.

12. The oil composition of claim 1 wherein the other hydrocarbyl group (C-2) contains from about 6 to about 13 carbon atoms.

13. The oil composition of claim 1 wherein the other hydrocarbyl group (C-2) is a primary aliphatic group containing from about 6 to about 13 carbon atoms.

14. The oil composition of claim 1 wherein the metal of (C) is a Group II metal, aluminum, tin, iron, cobalt, lead, molybdenum, manganese, nickel or copper.

15. The oil composition of claim 1 wherein metal of (C) is zinc, copper, or mixture of zinc and copper.

16. The oil composition of claim 1 wherein the metal of (C) is zinc.

17. The oil composition of claim 1 wherein hydrocarbyl group (C-1) is an isopropyl group, and at least about 25 mole percent of all of the hydrocarbyl groups present in (C) are isopropyl groups.

18. The oil composition of claim 1 wherein at least one metal salt in (C) is derived from a dihydrocarbyl phosphorodithioic acid prepared by reacting phophorus pentasulfide with an alcohol mixture comprising at least 25 mole percent of isopropyl alcohol and at least one primary aliphatic alcohol containing from about 6 to about 13 carbon atoms.

19. The oil composition of claim 1 also containing

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

20. The oil composition of claim 19 wherein the acidic organic compound (D is a sulfur acid, carboxylic acid, phosphorus acid, phenol, or mixtures thereof.

21. The oil composition of claim 19 wherein the acidic compound in (D) is at least one organic sulfonic acid.

22. 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

23. The oil composition of claim 22 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.

24. The oil composition of claim 22 wherein the alcohol (E-2) is neopentyl glycol, ethylene glycol, glycerol, pentaerythritol, sorbitol, monoalkyl or monoaryl ethers of a poly(oxyalkylene) glycol, or mixtures of any of these.

25. The oil composition of claim 22 wherein the carboxylic ester derivative composition (E) prepared by reaction 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.

26. A lubrication oil composition for internal combustion engines which comprises:

(A) a major amount of oil of lubrication viscosity

(B) at least about 2.5% by by weight of 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 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 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 groups for each equivalent weight of substituent groups, and

(C) a mixture of metal salts of dihydrocarbyl phosphorodthoic acids wherein in at least one of the dihydrocarbyl phosphorodithioic acids, one of the hydrocarbyl groups (C-1) is an isopropyl or secondary butyl group and the other hydrocarbyl group (C-2) contains at least five carbon atoms, and the lubricating oil composition contains at least about 0.06 percent by weight of isopropyl groups, secondary butyl groups or mixtures thereof derived from (C).

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

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

(B) at least 2.5% by weight of at least one carboxylic derivatives composition produced by reacting

(B-1) at least one substituted succinic acylating agent with from about 0.5 equivalent up to about two moles per equivalent of acylating agent of

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

group wherein said substituent 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 a 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, and

(C) from about 0.05 to about 5% by weight of a mixture of metal salts of dihydfocarbyl phosphorodithioic acids wherein in at least one of the dihydrocarbyl phosphorodithioic acids, one of the hydrocarbyl groups (C-1) is an isopropyl group, and the other hydrocarbyl group (C-2) contains at least five carbon atoms, and at least about 25 mole percent of all of the hydrocarbyl groups present in (C) are isopropyl groups.

28. The oil composition of claim 27 wherein at least 30 mole percent of all of the hydrocarbyl groups in (C) are isopropyl groups.

29. The oil composition of claim 27 wherein the value of Mn in (B) is at least about 1500.

30. The oil composition of claim 27 wherein the substituent groups in (B) are derived from polybutene in which at least about 50% of the total units derived from butenes is derived from isobutene.

31. The oil composition of claim 27 wherein the amine (B-2) is an aliphatic, cycloaliphatic or aromatic polyamine.

32. The oil composition of claim 27 wherein the am (B-2) is a hydroxy substituted monoamine, polyamine, or mixtures thereof.

33. The oil composition of claim 27 wherein the acylating agents are characterized by the presence within their structure of at least about 1.5 up to about 2.5 succinic groups for each equivalent weight of the substituent groups.

34. The oil composition of claim 27 wherein the other hydrocaryl group (C-2) is a primary aliphatic group containing from about 6 to about 13 carbon atoms

35. The oil composition of claim 27 wherein the metal in (C) is zinc, copper, or mixture of zinc and copper.

36. The oil composition of claim 27 wherein the metal in (C) is zinc.

37. The oil composition of claim 27 wherein at least one metal salt in (C) is derived from a dihydrocarbyl phosphorodithioic acid prepared by reaction phosphorus pentasulfide with an alcohol mixture comprising at least 30 mole percent of isopropyl alcohol and at least one primary aliphatic alcohol containing from about 6 to about 13 carbon atoms.

38. The oil composition of claim 27 also containing

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

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

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

(B) at least 2.5% by weight of at least one carboxylic derivative composition produced by reacting

(B-1) at least one substituted succinic acylating agent with from about 0.5 equivalent up to about two moles per equivalent of acylating agent of

(B-2) 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 a 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, and

(C) a mixture of metal salts of dihydrocarbyl phosphorodithioic acids wherein in at least one of the dihydrocarbyl phosphorodithioic acids, one of the hydrocarbyl groups (C-1) is an isopropyl group, and the other hydrocarbyl group (C-2) contains at least five carbon atoms, and the lubricating oil composition contains at least about 0.06 percent by weight of isopropyl groups derived from (C).

40. A lubrication oil composition for internal combustion engines which comprises:

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

(B) at least 2.5% by weight of at least one carboxylic derivative composition produced by reacting

(B-1) at least one substituted succinic acylating agent with from about 0.5 equivalent up to less than one equivalent per equivalent of acylating agent of

(B-2) 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 1300 to about 5000 and an Mw,/Mn value of about 2.0 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, and

(C) from about 0.05 to about 5% by weight of a mixture of metal salts of dihydrocarbyl phosphorodithioic acids wherein in at least one of the dihydrocarbyl phosphorodithioic acids, one of the hydrocarbyl groups (C-1) is an isopropyl group, and the other hydrocarbyl group (C-2) is a primary aliphatic group containing six to 13 carbon atoms, and at least about 30 mole percent of all of the hydrocarbyl groups present in (C) are isopropyl, groups.

41. The oil composition of claim 40 also containing (D) at least one neutral or basic alkaline earth metal salt of at least one organic sulfonic acid.

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

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

(B) at least 2.5% by weight of at least one carboxlic derivative composition produced by reacting

(B-1) at least one substituted succinic acylating agent with from about 0.5 equivalent up to less than one equivalent per equivalent of acylating agent of

(B-2) 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 1300 to about 5000 and an Mw/Mn value of about 2.0 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, and

(C) a mixture of metal salts of dihydrocarbyl phosphorodithioic acids wherein in at least one of the dihydrocarbyl phosphorodithioic aids, one of the hydrocarbyl groups (C-1) is an isopropyl group, and the other hydrocarbyl group (C-2) is a primary aliphatic group containing six to 13 carbon atoms, wherein the lubricating oil composition contains at least about 0.06 percent by weight of isopropyl groups derived from (C).

43. The oil composition of claim 42 containing at least about 0.08 percent by weight of isopropyl groups derived from (C).