Title:
Compounds and Lubricating Compositions Containing the Compounds
Kind Code:
A1


Abstract:
An imidazoline compound comprising the reaction product of (i) a dicarbonyl, (ii) a primary amine moiety of a polyamine, and (iii) a hydrocarbyl carbonyl is disclosed. Lubricant and fuel additive compositions comprising the imidazoline compound are also disclosed.



Inventors:
Loper, John T. (Richmond, VA, US)
Application Number:
11/668291
Publication Date:
07/31/2008
Filing Date:
01/29/2007
Primary Class:
Other Classes:
44/330, 44/342, 508/283, 548/300.1
International Classes:
C10L1/22
View Patent Images:
Related US Applications:



Primary Examiner:
CAMPANELL, FRANCIS C
Attorney, Agent or Firm:
AFTON CHEMICAL CORPORATION (KNOXVILLE, TN, US)
Claims:
What is claimed is:

1. An imidazoline compound comprising the reaction product of (i) a dicarbonyl, (ii) a primary amine moiety of a polyamine, and (iii) a hydrocarbyl carbonyl.

2. The compound of claim 1, wherein the dicarbonyl is chosen from alpha-omega dicarboxylic acids, and esters thereof.

3. The compound of claim 1, wherein the dicarbonyl is a compound of Formula I: where n ranges from 0 to about 20; and R1, R2, R′ and R″ are independently chosen from a hydrogen atom and an alkyl group.

4. The compound of claim 3, wherein at least one of R′ and R″ is an alkyl group.

5. The compound of claim 3, where n is not 2 or 3.

6. The compound of claim 1, wherein the dicarbonyl is a dicarboxylic acid chosen from oxalic acid, malonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, hexadecanedioic acid and isophthalic acid, and esters of any of these dicarboxylic acids.

7. The compound of claim 1, wherein the dicarbonyl is dimethyl diethyl malonate.

8. The compound of claim 1, wherein the polyamine is a linear, branched or cyclic polyalkyleneamine having at least one primary amine moiety.

9. The compound of claim 1, wherein the polyamine is a compound of Formula II: wherein R6 is a hydrogen atom or a low molecular weight alkyl group having from about 1 to about 6 carbon atoms, q is an integer ranging from about 1 to about 3, and m is an integer ranging from about 2 to about 10.

10. The compound of claim 1, wherein the polyamine is selected from the group consisting of propylene diamine, butylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethyleneheptamine, dipropylene triamine and tripropylene tetramine.

11. The compound of claim 1, wherein the polyamine has at least three nitrogen atoms, and the compound is a reaction product of the hydrocarbyl carbonyl and a polyamine intermediate formed by reacting the dicarbonyl with the polyamine.

12. The compound of claim 11, wherein the polyamine intermediate is formed by reacting the dicarbonyl with two equivalents of the polyamine.

13. The compound of claim 11, wherein the polyamine intermediate comprises as least two unreacted primary amine moieties.

14. The compound of claim 11, wherein the polyamine intermediate comprises a compound chosen from, where n ranges from 0 to 20, m ranges from 2 to 10, x ranges from 1 to 11 and R′ and R″ are independently chosen from a hydrogen atom and an alkyl group.

15. The compound of claim 14, wherein the hydrocarbyl carbonyl is a compound of the following Formula IV: wherein R14 is a hydrocarbyl group.

16. The compound of claim 15, wherein R14 is a polyolefin radical having a number average molecular weight ranging from about 350 to about 10,000 daltons.

17. The compound of claim 15, wherein R14 is polyisobutene.

18. The compound of claim 11, wherein the hydrocarbyl carbonyl is chosen from hydrocarbyl substituted succinic anhydrides, hydrocarbyl substituted succinic acids, and esters of hydrocarbyl substituted succinic acids.

19. The compound of claim 1, wherein the hydrocarbyl carbonyl is a compound of the following Formula IV: wherein R14 is a hydrocarbyl group.

20. The compound of claim 19, wherein R14 is a polyolefin radical having a number average molecular weight ranging from about 350 to about 10,000 daltons.

21. The compound of claim 19, wherein R14 is polyisobutene.

22. The compound of claim 1, wherein the compound is a reaction product of the dicarbonyl and a mono-hydrocarbyl polyamine amine intermediate formed by reacting the hydrocarbyl carbonyl with the polyamine.

23. An imidazoline compound comprising the reaction product of a dicarbonyl and a mono-hydrocarbyl polyamine, wherein the mono-hydrocarbyl polyamine is formed by reaction of a hydrocarbyl carbonyl and a polyamine.

24. The compound of claim 23, wherein the dicarbonyl is a compound of Formula I: where n ranges from 0 to about 20, with the proviso that n is not 2 or 3; and R1, R2, R′ and R″ are independently chosen from a hydrogen atom and an alkyl group.

25. The compound of claim 24, wherein at least one of R′ and R″ is an alkyl group.

26. The compound of claim 23, wherein the dicarbonyl is a dicarboxylic acid chosen from oxalic acid, malonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, hexadecanedioic acid and isophthalic acid, and esters of any of these dicarboxylic acids.

27. The compound of claim 23, wherein the mono-hydrocarbyl polyamine is a compound of Formula V: where R14 is a hydrocarbyl group; R6 is a hydrogen atom or a low molecular weight alkyl group having from about 1 to about 6 carbon atoms; m is an integer ranging from about 2 to about 10; and q is an integer ranging from about 1 to 3.

28. The compound of claim 23, wherein the mono-hydrocarbyl polyamine is a fatty amine having at least one primary nitrogen atom.

29. The compound of claim 23, wherein the hydrocarbyl carbonyl is a compound of the following Formula IV: wherein R14 is a hydrocarbyl group.

30. The compound of claim 29, wherein R14 is a polyolefin radical having a number average molecular weight ranging from about 350 to about 10,000 daltons.

31. The compound of claim 23, wherein the hydrocarbyl carbonyl is chosen from dodecenylsuccinic anhydride, C16-18 alkenyl succinic anhydride, and polyisobutenyl succinic anhydride.

32. The compound of claim 23, wherein the polyamine is a linear, branched or cyclic polyalkyleneamine having at least one primary amine moiety.

33. The compound of claim 23, wherein the polyamine is a compound of Formula II: wherein R6 is a hydrogen atom or a low molecular weight alkyl group having from about 1 to about 6 carbon atoms, q is an integer ranging from about 1 to about 3, and m is an integer ranging from about 2 to about 10.

34. The compound of claim 23, wherein the polyamine is selected from the group consisting of propylene diamine, butylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethyleneheptamine, dipropylene triamine, and tripropylene tetramine.

35. A lubricating composition comprising: a base oil; and an imidazoline compound comprising the reaction product of (i) a dicarbonyl, (ii) a primary amine moiety of a polyamine, and (iii) a hydrocarbyl carbonyl.

36. The lubricating composition of claim 35, wherein the concentration of the imidazoline compound ranges from about 0.1% by weight to about 20% by weight relative to the total weight of the composition.

37. The lubricating composition of claim 35, wherein the dicarbonyl is a compound of Formula I: where n ranges from 0 to about 20; and R1, R2, R′ and R″ are independently chosen from a hydrogen atom and an alkyl group.

38. The lubricating composition of claim 37, wherein at least one of R′ and R″ is an alkyl group.

39. The lubricating composition of claim 37, wherein the polyamine is a compound of Formula II: wherein R6 is a hydrogen atom or a low molecular weight alkyl group having from about 1 to about 6 carbon atoms, q is an integer ranging from about 1 to about 3, and m is an integer ranging from about 2 to about 10.

40. The lubricating composition of claim 35, wherein the hydrocarbyl carbonyl is a compound of the following Formula IV: wherein R14 is a hydrocarbyl group.

41. The lubricating composition of claim 40, wherein R14 is polyisobutene.

42. A method of reducing deposits on a lubricated surface, the method comprising lubricating the surface with the lubricating composition of claim 35, wherein the imidazoline compound is present in an amount sufficient to reduce the amount of deposits on the lubricated surface, as compared to the amount of deposits on the surface subjected to the same operating conditions and lubricated with the same lubricant composition except that the composition is devoid of the imidazoline compound.

43. A method for improving the suspension of sludge comprising providing to a combustion system the lubricating composition of claim 35, wherein the imidazoline compound is present in an amount sufficient to maintain at least some sludge in suspension in the base oil for a period of time longer than if the base oil did not contain the imidazoline compound.

44. A lubricant additive package composition comprising: a diluent; and the imidazoline compound of claim 1.

45. The additive package of claim 44, wherein the concentration of imidazoline compound ranges from about 5 to about 75 weight percent relative to the total weight of the additive package composition.

46. The additive package of claim 44, further comprising one or more additional additives chosen from additional dispersants, detergents, anti-wear agents, supplemental antioxidants, viscosity index improvers, pour point depressants, corrosion inhibitors, rust inhibitors, foam inhibitors, and friction modifiers.

47. A fuel composition comprising: a base fuel; and an imidazoline compound comprising the reaction product of (i) a dicarbonyl, (ii) a primary amine moiety of a polyamine, and (iii) a hydrocarbyl carbonyl.

48. The fuel composition of claim 47, wherein the concentration of the imidazoline compound ranges from about 10 to about 10,000 parts per million.

49. The fuel composition of claim 47, wherein the dicarbonyl is a compound of Formula I: where n ranges from 0 to about 20; and R1, R2, R′ and R″ are independently chosen from a hydrogen atom and an alkyl group.

50. The fuel composition of claim 47, wherein the polyamine is a compound of Formula II: wherein R6 is a hydrogen atom or a low molecular weight alkyl group having from about 1 to about 6 carbon atoms, q is an integer ranging from about 1 to about 3, and m is an integer ranging from about 2 to about 10.

51. The fuel composition of claim 47, wherein the hydrocarbyl carbonyl is a compound of the following Formula IV: wherein R14 is a hydrocarbyl group.

52. The fuel composition of claim 51, wherein R14 is polyisobutene.

53. A method of reducing deposits in the fuel system of an internal combustion engine, the method comprising using as the fuel for the internal combustion engine the fuel composition of claim 47, wherein the imidazoline compound is present in the fuel in an amount sufficient to reduce the deposits in the fuel system, as compared to the amount of deposits in the fuel system operated in the same manner and using the same fuel composition except that the fuel composition is devoid of the imidazoline compound.

54. A method of dispersing soot, comprising providing to a combustion system the fuel composition of claim 47, wherein the imidazoline compound is present in an amount sufficient to maintain at least some soot in suspension in the base fuel for a period of time longer than if the base fuel did not contain the imidazoline compound.

55. A fuel additive package composition comprising: a diluent; and the imidazoline compound of claim 1.

56. The fuel additive package composition of claim 55, wherein the concentration of imidazoline compound ranges from about 5 weight percent to about 50 weight percent of the total fuel additive package composition.

57. A process for forming an imidazoline compound comprising reacting (i) a dicarbonyl, (ii) a primary amine moiety of a polyamine, and (iii) a hydrocarbyl carbonyl.

58. The process of claim 57, wherein the process comprises: (i) reacting the dicarbonyl with the polyamine under reaction conditions sufficient to form a polyamine imidazoline intermediate; and (ii) reacting the polyamine imidazoline intermediate with the hydrocarbyl carbonyl.

59. The process of claim 58, wherein the reaction conditions for forming the polyamine imidazoline intermediate include heating at reaction temperatures ranging from about 150° C. to about 250° C.

60. A process for forming an additive compound comprising reacting a dicarbonyl compound and a mono-hydrocarbyl polyamine.

61. The process of claim 60, wherein the dicarbonyl is a compound of Formula I: where n ranges from 0 to about 20; and R1, R2, R′ and R″ are independently chosen from a hydrogen atom and an alkyl group.

62. The process of claim 60, wherein the mono-hydrocarbyl polyamine is a fatty amine.

63. The process of claim 60, wherein the mono-hydrocarbyl polyamine is formed by reacting a hydrocarbyl carbonyl with a polyamine.

64. The process of claim 63, wherein the polyamine is a compound of Formula II: wherein R6 is a hydrogen atom or a low molecular weight alkyl group having from about 1 to about 6 carbon atoms, q is an integer ranging from about 1 to about 3, and m is an integer ranging from about 2 to about 10.

65. The process of claim 63, wherein the hydrocarbyl carbonyl is a compound of the following Formula IV: wherein R14 is a hydrocarbyl group.

66. The process of claim 60, wherein the additive compound comprises a central polyamine chain of one or more polyamine groups linked together with one or more groups chosen from diamide groups, imidazoline-amide groups and bis imidazoline groups, and a hydrocarbyl carbonyl group being attached to at least one end of the polyamine chain.

Description:

DESCRIPTION OF THE DISCLOSURE

1. Field of the Disclosure

The present application is directed to compounds and methods for making the compounds, and more specifically, to compounds that can be employed in fuel and lubricant compositions.

2. Background of the Disclosure

Considerable effort has been expended to develop chemical products as dispersant additives for internal combustion engines. Oil-soluble dispersants for lubricating oil have been developed to control deposit and varnish formation, and to keep sludge and other solid matter, such as oxidized base oil, in suspension in the lubricating oil. Dispersants, when added to hydrocarbon fuels employed in the engines, effectively reduce deposit formation that ordinarily occurs in carburetor ports, throttle bodies, venturies, intake ports and intake valves. The reduction of these deposit levels has resulted in increased engine efficiency and a reduction in the level of hydrocarbon and carbon monoxide emissions.

Despite the advances in the use of dispersants as oil and fuel additives, there remains a need for continued improvements in the ability of dispersants to suspend sludge and/or disperse particulates. Thus, novel compounds exhibiting improved dispersant characteristics are desired.

SUMMARY OF THE DISCLOSURE

In accordance with the disclosure, one aspect of the present application is directed to an imidazoline compound comprising the reaction product of (i) a dicarbonyl, (ii) a primary amine moiety of a polyamine, and (iii) a hydrocarbyl carbonyl.

Another aspect of the present application is directed to an imidazoline compound comprising the reaction product of a dicarbonyl and a mono-hydrocarbyl polyamine, wherein the mono-hydrocarbyl polyamine is formed by reaction of a hydrocarbyl carbonyl and a polyamine.

Another aspect of the present application is directed to a lubricating composition comprising a base oil; and an imidazoline compound comprising the reaction product of (i) a dicarbonyl, (ii) a primary amine moiety of a polyamine, and (iii) a hydrocarbyl carbonyl.

Another aspect of the present application is directed to a method of reducing deposits on a lubricated surface, the method comprising lubricating the surface with a lubricating composition of the present application, wherein the imidazoline compound of the present application is present in the lubricating composition in an amount sufficient to reduce the amount of deposits on the lubricated surface, as compared to the amount of deposits on the surface subjected to the same operating conditions and lubricated with the same lubricant composition except that the composition is devoid of the imidazoline compound.

Another aspect of the present application is directed to a method for improving the suspension of sludge comprising providing to a combustion system the lubricating composition of the present application, wherein the imidazoline compounds are present in an amount sufficient to maintain at least some sludge in suspension in the base oil for a period of time longer than if the base oil did not contain the imidazoline compounds.

Another aspect of the present application is directed to a lubricant additive package composition comprising a diluent; and an imidazoline compound of the present application.

Another aspect of the present application is directed to a fuel composition comprising a base fuel; and an imidazoline compound comprising the reaction product of (i) a dicarbonyl, (ii) a primary amine moiety of a polyamine, and (iii) a hydrocarbyl carbonyl.

Another aspect of the present application is directed to a method of reducing deposits in the fuel system of an internal combustion engine, the method comprising using as the fuel for the internal combustion engine the fuel composition of the present application, wherein the imidazoline compound of the present application is present in the fuel in an amount sufficient to reduce the deposits in the fuel system, as compared to the amount of deposits in the fuel system operated in the same manner and using the same fuel composition except that the fuel composition is devoid of the imidazoline compound.

Another aspect of the present application is directed to a method of dispersing soot, comprising providing to a combustion system the fuel composition of the present application; wherein the imidazoline compound of the present application is present in an amount sufficient to maintain at least some soot in suspension in the base fuel for a period of time longer than if the base fuel did not contain the imidazoline compound.

Another aspect of the present application is directed to a fuel additive package composition comprising a diluent; and the imidazoline compound of the present application.

Another aspect of the present application is directed to a process for forming an imidazoline compound comprising reacting (i) a dicarbonyl, (ii) a primary amine moiety of a polyamine, and (iii) a hydrocarbyl carbonyl.

Still another aspect of the present application is directed to a process for forming an additive compound comprising reacting a dicarbonyl compound and a mono-hydrocarbyl polyamine.

Additional aspects and advantages of the disclosure will be set forth in part in the description which follows, and can be learned by practice of the disclosure. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure, as claimed.

DESCRIPTION OF THE EMBODIMENTS

One aspect of the present application is directed to the preparation of novel imidazoline compounds and their uses. The imidazoline compounds can comprise the reaction product of (i) a dicarbonyl, (ii) a primary amine moiety of a polyamine, and (iii) a hydrocarbyl carbonyl. The compounds of the present application are designed to have localized regions of polarity. These localized polar regions are envisioned to result in compounds which may have one or more advantages, such as, for example, an improved ability of the dispersant to suspend sludge and/or disperse soot through ionic and dipolar interactions; and/or an improved ability to remove injector and/or valve deposits in combustion engines.

In some aspects, the compounds of the present application are made by preparing a polyamine intermediate, which is reacted with a hydrocarbyl carbonyl. The intermediate can be prepared by reacting a dicarbonyl with a primary amine moiety of a polyamine. Other suitable methods for forming the compounds of the present application may be employed, as will be discussed in greater detail below.

Dicarbonyl Compounds

The dicarbonyl reactant compounds used in the present application can include any dicarbonyl compound suitable for forming the desired intermediate. Non-limiting examples of suitable diacarbonyl compounds include alpha-omega dicarboxylic acids, and esters thereof.

In one aspect, the dicarbonyl compound can be a compound of Formula I:

where n ranges from 0 to about 20, such as about 1 to about 16; and R1, R2, R′ and R″ are independently chosen from a hydrogen atom and an alkyl group. Suitable alkyl groups can include, for example, C1 to C10 linear or branched alkyl groups, such as methyl, ethyl and butyl.

In some aspects of the present application, it may be desirable that n is not chosen to be 2 or 3. This is because when n is 2 or 3, internal cyclization of the compound of Formula I can occur, which upon reaction with a polyamine can result in formation of a 5 or 6 atom imide ring structure, such as a succinimide. This can potentially hinder the desired reaction and preclude formation of an imidazoline. Thus, in such cases, the dicarbonyl compound is not succinic acid, glutaric acid or succinate or gluarate derivatives of Formula I.

Non-limiting examples of the dicarbonyl compound include dicarboxylic acids chosen from oxalic acid, malonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, hexadecanedioic acid and isophthalic acid, and esters of any of these dicarboxylic acids, such as, for example, methyl, ethyl and butyl esters. In one aspect of the present application, the dicarbonyl compound can be an alkylated diester. For example, R1 and R2 of Formula I can be methyl groups, R′ and R″ can be ethyl groups, and n can be 1; thereby forming the alkylated diester, dimethyl diethyl malonate.

Polyamine Compounds

In some aspects of the present application, the polyamine reactant used to form the polyamine intermediate of the present application can be a linear, branched or cyclic polyalkyleneamine having at least one primary amine moiety. In some aspects, the polyamine can have at least three nitrogen atoms.

For example, the polyamine can be a polyalkyleneamine of the following Formula II:

wherein R6 can be a hydrogen atom or a low molecular weight alkyl group having from about 1 to about 6 carbon atoms, q can be an integer ranging from about 1 to about 3 and m can be an integer ranging from about 2 to about 10, such as about 3 to about 8. Non-limiting examples of R6 alkyl groups include methyl, ethyl, propyl or butyl.

Non-limiting examples of suitable polyamines include propylene diamine, butylene diamine, diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA), hexaethyleneheptamine (HEHA), dipropylene triamine and tripropylene tetramine. The polyamines can include linear, branched or cyclic compounds, or mixtures thereof. In one aspect, the polyamine is a polyethyleneamine, such as DETA, TETA, TEPA, PEHA, and HEHA. In one aspect, the polyamine can be a copolymer of any one of the foregoing polyethyleneamines ranging in molecular weight from about 100 to about 600.

In some aspects, the polyamines can include mixtures of two or more polyamine compounds, such as mixtures of two or more compounds chosen from TEPA, PEHA, HEHA, and higher molecular weight polyethyleneamine products. In some aspects, the mixture can comprise heavy polyamines. A heavy polyamine is a mixture of polyalkyleneamines comprising small amounts of lower amine oligomers such as TEPA and PEHA, but primarily comprising oligomers with 7 or more nitrogen atoms, 2 or more primary amines per molecule, and more extensive branching than conventional amine mixtures.

The dicarbonyl and polyamine reactants can be combined at any suitable reaction conditions that result in the desired imidazoline intermediate compound. In one aspect, the dicarbonyl and polyamine can be combined and heated to a reaction temperature ranging from about 150° C. to about 250° C. under nitrogen, or another relatively inert atmosphere, such as under vacuum, until alcohol and/or water is removed and the imidazoline product is formed. This reaction time may be, for example, from about 2 hour to about 6 hours. At this point, the imidazoline product can be isolated to from a polyamine intermediate of the present application.

The reaction can be run neat or with solvents. Optionally, any water or solvent can be removed during or after the reaction to provide the desired polyamine intermediate.

In one aspect of the present application, the dicarbonyl to polyamine ratio can be any suitable ratio, such that there remain at least two unreacted primary amine moieties in the intermediate. For example, the molar ratio of dicarbonyl compounds to primary amine compounds can range from about 1:1.1 to about 1:2.

The resulting intermediate compound comprises one or more polyamine groups attached to one or more imidazoline-amide groups and/or one or more bis imidazoline groups. For example, the intermediate compound can be a polyamine imidazoline-amide compound of Formula IIIa, or a polyamine bis imidazoline of Formula IIIb, or mixtures thereof:

where x ranges from about 1 to about 11, and n, R′ and R″ are defined as above with regard to Formula I, and m is defined as above with regard to Formula II.

Hydrocarbyl Carbonyl Compound

The hydrocarbyl carbonyl reactant compound of the present application can be any suitable compound having a hydrocarbyl group and a carbonyl moiety, and that is capable of bonding with the polyamine intermediate compounds to form the compounds of the present application. Non-limiting examples of suitable hydrocarbyl carbonyl compounds include, but are not limited to, hydrocarbyl substituted succinic anhydrides, hydrocarbyl substituted succinic acids, and esters of hydrocarbyl substituted succinic acids. Specific examples include such compounds as dodecenylsuccinic anhydrides, C16-18 alkenyl succinic anhydride, and polyisobutenyl succinic anhydride (PIBSA). In some embodiments, the PIBSA may have a polyisobutylene portion with a molecular weight ranging from about 200 to about 6000 daltons and a vinylidene content ranging from about 4% to about 100%. In some embodiments, the ratio of the number of carbonyl groups to the number of hydrocarbyl moieties in the hydrocarbyl carbonyl compound can range from about 1:1 to about 6:1.

As used herein, the term “hydrocarbyl group” or “hydrocarbyl” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of a molecule and having a predominantly hydrocarbon character. Examples of hydrocarbyl groups include:

(1) hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form an alicyclic radical);

(2) substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of the description herein, do not alter the predominantly hydrocarbon substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);

(3) hetero-substituents, that is, substituents which, while having a predominantly hydrocarbon character, in the context of this description, contain other than carbon in a ring or chain otherwise composed of carbon atoms. Hetero-atoms include sulfur, oxygen, nitrogen, and encompass substituents such as pyridyl, furyl, thienyl, and imidazolyl. In general, no more than two, or as a further example, no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; in some embodiments, there will be no non-hydrocarbon substituent in the hydrocarbyl group.

In some aspects, the hydrocarbyl carbonyl compound can be a polyalkylene succinic anhydride reactant having the following Formula IV:

wherein R14 is a hydrocarbyl group, such as for example, a polyolefin radical having a number average molecular weight of from about 350 to about 10,000 daltons. For example, the number average molecular weight of R14 can range from about 1000 to about 5000 daltons as measured by GPC. Unless indicated otherwise, molecular weights in the present specification are number average molecular weights.

In some aspects, R14 can be a polyolefin radical comprising one or more polymer units chosen from linear or branched alkenyl units. In some aspects, the alkenyl units can have from about 2 to about 10 carbon atoms. For example, the polyolefin radical can comprise one or more linear or branched polymer units chosen from ethylene radicals, propylene radicals, butylene radicals, pentene radicals, hexene radicals, octene radicals and decene radicals. In some aspects, R14 can be a polyolefin radical in the form of, for example, a homopolymer, copolymer or terpolymer. For example, the polyolefin radical can be a copolymer of ethylene and propylene. In another example, the polyolefin radical is a homopolymer of polyisobutylene. The polyolefin compounds used to form the R14 polyolefin radicals can be formed by any suitable methods, such as by conventional catalytic oligomerization of alkenes.

In some aspects, high reactivity polyisobutenes having relatively high proportions of polymer molecules with a terminal vinylidene group can be used to form the hydrocarbyl substituent. In one example, at least 4% of the total terminal olefinic double bonds in such high reactivity polyisobutenes can be a methylvinylidene isomer. In other examples, 50% or more of the total terminal olefinic double bonds can be methylvinylidene isomers, such as at least 70%. Well known high reactivity polyisobutenes are disclosed, for example, in U.S. Pat. No. 4,152,499, the disclosure of which is herein incorporated by reference in its entirety.

The hydrocarbyl carbonyl compounds can be made using any suitable method. Methods for forming hydrocarbyl carbonyl compounds are well known in the art. One example of a known method for forming a hydrocarbyl carbonyl compound comprises blending a polyolefin and maleic anhydride. The polyolefin and maleic anhydride reactants are heated to temperatures of, for example, about 150° C. to about 250° C., optionally, with the use of a catalyst, such as chlorine or peroxide.

The hydrocarbyl carbonyl compound can be combined with the desired polyamine intermediate under any suitable reaction conditions that will result in the desired imidazoline compound of the present application. For example, a mixture of the hydrocarbyl carbonyl compound and polyamine intermediate can be heated to a temperature ranging from about 100° C. to about 200° C., such as about 140° C. to about 180° C., under nitrogen or another relatively inert atmosphere, such as vacuum. The reactant mixture can be heated at the reaction temperature until the desired succinimide product is formed, and optionally complete removal of water is achieved. Suitable reaction times can range, for example, from about 2 hours to about 4 hours. The reaction can be run neat or with solvents and/or diluents, such as process oil. After the reaction is completed the mixture can be filtered to afford the desired dispersant.

In an alternative embodiment, the reaction of the dicarbonyl, polyamine, and hydrocarbyl carbonyl compounds may be carried out in a different order than is described above. For example, instead of reacting a dicarbonyl compound and a polyamine compound to form the above described polyamine intermediate, the hydrocarbyl carbonyl compounds described above can be reacted with the polyamine compounds described above to form a mono-hydrocarbyl polyamine intermediate. The mono-hydrocarbyl polyamine intermediate can then be reacted with the dicarbonyl compounds described above to form the desired compounds of the present application.

In one aspect of the present application, the mono-hydrocarbyl amine compounds employed can have from about 3 to about 10 nitrogen atoms, and the amine portion can have at least one primary amine moiety. Examples of such mono-hydrocarbyl polyamine intermediate compounds can be of the following Formula V.

where R6, R14, q and m are as defined above with regard to Formulae II and IV. Non-limiting examples of such mono-hydrocarbyl polyamine compounds include polyamine succinimide compounds such as propylene diamine succinimide, butylene diamine succinimide, diethylene triamine (DETA) succinimide, triethylene tetramine (TETA) succinimide, tetraethylene pentamine (TEPA) succinimide, pentaethylene hexamine (PEHA) succinimide, hexaethyleneheptamine (HEHA) succinimide, dipropylene triamine succinimide and tripropylene tetramine succinimide, all of which are substituted with an R14 hydrocarbyl group.

The mono-hydrocarbyl amine compounds of the present application can be formed by reaction of the hydrocarbyl carbonyl and polyamine compounds under any conditions that will result in the desired mono-hydrocarbyl polyamine compounds. For example a 1:1 molar equivalent of a hydrocarbyl carbonyl compound and polyamine can be blended and heated to temperatures ranging from, for example, about 120° C. to about 250° C.

In yet another embodiment, the mono-hydrocarbyl polyamine compounds employed can be any suitable polyamines obtained from any suitable source. For example, fatty amine compounds, such as TETRAMEEN OV, available from Akzo Nobel, or ADOGEN 670 and ADOGEN 770 available from Degussa, can be employed as the mono-hydrocarbyl polyamine compounds of the present application. Other examples of fatty amine compounds include fatty acid amides, such as those of Formula:


R16C(O)—NH2(CH2)r—[NH(CH2)r]t—NH2

where R16 is a linear or branched, saturated or unsaturated C8 to C30 group, r=2 or 3 and t is 0 to 10. Such fatty acid amides can be formed by any suitable method known in the art, such as by the reaction of fatty acids with polyamine compounds.

The mono-hydrocarbyl polyamine compounds can be reacted with any of the dicarbonyl compounds described above, such as the dicarbonyl compounds of Formula I, to form the desired compounds of the present application. The reaction can be carried out by blending any suitable amounts of the mono-hydrocarbyl polyamine compounds and dicarbonyl compounds under suitable process conditions. For example, the molar ratio of dicarbonyl compounds to mono-hydrocarbyl polyamine compounds can range from about 1:2 to about 4:2, such as from 1:2 to about 3:4. The reaction can be performed neat or in a process oil at a temperature ranging from about 80° C. to about 200° C. The particular reaction temperature employed can effect the distribution of the reaction products. For example, diamides and linear amide arrays or polyamides can form at low temperatures ranging from about 80° C. to about 150° C., while cyclic products, such as imidazolines, can form by heating at higher temperatures, such as, for example from about 160° C. to about 200° C. Thus, to form the imidazolines compounds of the present application, the higher reaction temperatures can be employed. However, it may also be desirable to employ this method to form additive compounds at the lower temperatures, if compounds comprising the diamide groups are desired. Accordingly, the compounds formed by this method may comprise a central polyamine chain of one or more polyamine groups linked together with one or more groups chosen from diamide groups, imidazoline-amide groups and bis imidazoline groups, and a hydrocarbyl carbonyl group being attached to at least one end of the polyamine chain. The imidazolines are described in more detail below. The diamides can include compounds of the Formula X, as also shown below in the discussion of the product compounds, where Y is, for example XIa:

wherein R′, R″, and n are defined above with regard to Formula I.

In one exemplary aspect of the present application, a mono-hydrocarbyl polyamine compound can be heated to a temperature ranging from about 160° C. to about 250° C. under nitrogen, or another relatively inert atmosphere, such as vacuum. A dicarbonyl compound can then be added. The reactant mixture can be stirred and heated at the chosen reaction temperature until desired reaction product is formed, and optionally the water and/or alcohol is removed from the mixture. For example, suitable reaction times can range from about 1 hour to about 5 hours. The reaction can be run neat or with solvents and/or diluents, such as process oil. After the reaction is completed the mixture can be diluted with, for example, process oil and filtered to afford the desired dispersant.

Product Compounds

In some aspects, the compounds of the present application can comprise a central polyamine chain of one or more polyamine groups linked together with one or more diamide groups, imidazoline-amide groups and/or one or more bis imidazoline groups, and a hydrocarbyl carbonyl group being attached to one or both ends of the polyamine chain. In aspects of the present application, the reaction product compounds can have at least one titratable nitrogen. Non-limiting examples of the polyamine succinimide compounds include compounds of Formula X:

wherein z ranges from 0 to about 10, x ranges from about 1 to about 10, R14 is defined as above, with regard to Formula IV, and Y is chosen from one or more moieties of Formulae XIb and XIc:

where n, R′ and R″ are defined as set forth above, with regard to Formula I. The compounds of Formula X are exemplary only, and other compounds can be formed. For example, the ethylene amine units:

of Formulae X, XIa, XIb, and XIc could respectively be replaced with other amine units falling within the more general Formulae:

where q and R6 are defined as above, with regard to Formula II. In yet other embodiments, the imadazole compounds of the present application can also include other Y moieties in addition to the imidazole moieties of Formulae XIb and XIc, such as the diamide moieties of Formula XIa, described above.

As mentioned above, the compounds of the present application are designed to have localized regions of polarity. These localized polar regions are envisioned to result in compounds which may have one or more advantages, such as, for example, an improved ability of the dispersant to suspend sludge and/or disperse soot through ionic and dipolar interactions; and/or an improved ability to remove injector and/or valve deposits in combustion engines. In some aspects of the invention, it may be possible that the imidazoline-amide compounds present a unique hydrogen bonding network in a non-polar medium, as illustrated by Formula XII below, such as when the compounds are combined with a lubricant oil. The dotted lines in Formula XII represent potential hydrogen bonds.

wherein R14 is a hydrocarbyl group, such as for example, a polyolefin radical having a number average molecular weight of from about 350 to about 10,000 daltons.

When the compounds of this application are used as dispersants in lubricant compositions, they can be present in any suitable amount. In one example, the compounds can be present in an amount of from about 0.1 to about 20% by weight of the total composition, such as from about 0.5 to about 15% by weight, and in another example, from about 1 to about 7% by weight.

The lubricating compositions disclosed herein can comprise a base oil. Base oils suitable for use in formulating the disclosed compositions can be selected from, for example, synthetic or mineral oils, and mixtures thereof.

The base oil can be present in a major amount, wherein “major amount” is understood to mean greater than or equal to 50% by weight of the lubricant composition, such as from about 80% to about 98% by weight of the lubricant composition. The base oil typically has a viscosity of, for example, from about 2 to about 15 cSt and, as a further example, from about 2 to about 10 cSt at 100° C.

Non-limiting examples of mineral oils suitable as base oils include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as other mineral lubricating oils such as liquid petroleum oils and solvent treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils derived from coal or shale are also suitable. Further, oils derived from a gas-to-liquid process are also suitable.

Non-limiting examples of synthetic oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene isobutylene copolymers, etc.); polyalphaolefins such as poly(1-hexenes), poly-(1-octenes), poly(1-decenes), etc. and mixtures thereof; alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, di-nonylbenzenes, di-(2-ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls, terphenyl, alkylated polyphenyls, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof and the like.

Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic oils that can be used. Such oils are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of about 1000, diphenyl ether of polyethylene glycol having a molecular weight of about 500-1000, diethyl ether of polypropylene glycol having a molecular weight of about 1000-1500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-8 fatty acid esters, or the C13 Oxo acid diester of tetraethylene glycol.

Another class of synthetic oils that can be used includes the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.) Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid and the like.

Esters useful as synthetic oils also include those made from C5-12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.

Hence, the base oil used to make the compositions as described herein can be selected from any of the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. Such base oil groups are as follows:

Group I contain less than 90% saturates and/or greater than 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120; Group II contain greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120; Group III contain greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 120; Group IV are polyalphaolefins (PAO); and Group V include all other basestocks not included in Group I, II, III or IV.

The test methods used in defining the above groups are ASTM D2007 for saturates; ASTM D2270 for viscosity index; and one of ASTM D2622, 4294, 4927 and 3120 for sulfur.

Group IV basestocks, i.e. polyalphaolefins (PAO) include hydrogenated oligomers of an alpha-olefin, the most important methods of oligomerisation being free radical processes, Ziegler catalysis, and cationic, Friedel-Crafts catalysis.

The polyalphaolefins typically have viscosities in the range of 2 to 100 cSt at 100° C., for example 4 to 8 cSt at 100° C. They can, for example, be oligomers of branched or straight chain alpha-olefins having from about 2 to about 30 carbon atoms; non-limiting examples include polypropenes, polyisobutenes, poly-1-butenes, poly-1-hexenes, poly-1-octenes and poly-1-decene. Included are homopolymers, interpolymers and mixtures.

Regarding the balance of the basestock referred to above, a “Group I basestock” also includes a Group I basestock with which basestock(s) from one or more other groups can be admixed, provided that the resulting admixture has characteristics falling within those specified above for Group I basestocks.

Exemplary basestocks include Group I basestocks and mixtures of Group II basestocks with Group I basestock.

Basestocks suitable for use herein can be made using a variety of different processes including but not limited to distillation, solvent refining, hydrogen processing, oligomerisation, esterification, and re-refining.

The base oil can be an oil derived from Fischer-Tropsch synthesized hydrocarbons. Fischer-Tropsch synthesized hydrocarbons can be made from synthesis gas containing H2 and CO using a Fischer-Tropsch catalyst. Such hydrocarbons typically require further processing in order to be useful as the base oil. For example, the hydrocarbons can be hydroisomerized using processes disclosed in U.S. Pat. No. 6,103,099 or 6,180,575; hydrocracked and hydroisomerized using processes disclosed in U.S. Pat. No. 4,943,672 or 6,096,940; dewaxed using processes disclosed in U.S. Pat. No. 5,882,505; or hydroisomerized and dewaxed using processes disclosed in U.S. Pat. Nos. 6,013,171; 6,080,301; or 6,165,949. The disclosures of each of these patents is incorporated herein by reference in its entirety as if fully set forth herein.

Unrefined, refined and rerefined oils, either mineral or synthetic (as well as mixtures of two or more of any of these) of the type disclosed hereinabove can be used in the base oils. Unrefined oils are those obtained directly from a mineral or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from primary distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques are known to those skilled in the art such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Rerefined oils are obtained by processes similar to those used to obtain refined oils, where the processes are applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives, contaminants, and oil breakdown products.

The lubricant compositions of the present application can be used in any engine or other combustion systems or mechanical devices that may benefit therefrom. For example, the lubricant compositions can be suitable for use in the crankcase of an internal combustion engine.

In some embodiments, the compounds of the present application can be added to the lubricant composition in the form of a lubricant additive package. Lubricant additive packages include concentrates dissolved in a diluent, such as mineral oil, synthetic hydrocarbon oils, and mixtures thereof. When blended with the base oil, these concentrate additive compositions can provide an effective concentration of the additives in the base oil. The amount of the compounds of the present application in the lubricant additive packages may vary from about 5 wt % to about 75 wt % of the concentrate additive composition, such as from about 5 wt % to about 50 wt %.

The lubricant additive package compositions and finished lubricants of the present application may contain other additional additives. Examples of such additional additives include additional dispersants other than the dispersants of the present application, detergents, anti-wear agents, supplemental antioxidants, viscosity index improvers, pour point depressants, corrosion inhibitors, rust inhibitors, foam inhibitors, and friction modifiers. Such additives are well known in the art, and choosing effective amounts of additional additives in lubricant compositions would be within the ordinary skill of the art. Non-limiting representative amounts of these additional additives are shown in range 1 and range 2 of Table 1, below:

Wt. %Wt. %
AdditiveRange 1Range 2
Antioxidant system0–50.01–3  
Metal Detergents0.1–15 0.2–8  
Corrosion Inhibitor0–50–2
Metal Dihydrocarby Dithiophosphate0.1–6  0.1–4  
Antifoaming Agent0–50.001–0.15 
Friction Modifier0–50–2
Supplemental Antiwear Agents  0–1.0  0–0.8
Pour Point Depressant0.01–5  0.01–1.5 
Viscosity Modifier0.01–10  0.25–7  
BasestockBalanceBalance

In one aspect, the present application is directed to a method of reducing deposits on a lubricated surface, wherein said method comprises using as the lubricating oil for said surface a lubricating oil containing the imidazoline compound of the present invention. The imidazoline compound can be present in an amount sufficient to reduce the amount of deposits on the surface, as compared to the amount of deposits that would be formed on the surface if it were subjected to the same operating conditions and using the same lubricating oil, except that the oil was devoid of the imidazoline compound. Representative examples of the deposits that may be reduced using the compositions of the present invention include piston deposits, ring land deposits, crown land deposits and top land deposits.

In another aspect, the present application is directed to a method for improving the suspension of sludge in a lubricating oil. The method comprises providing to a combustion system the lubricating oils of the present application, wherein the imidazoline compound is present in an amount sufficient to maintain at least some sludge in suspension in the oil for a period of time longer than if the oil did not contain the imidazoline compound.

The compounds of the present application are also useful as dispersants in fuels. Thus, another aspect of the present application is a fuel composition comprising a major amount of a fuel and a minor amount of compounds of the present application sufficient to provide a desired dispersancy. The term “minor amount” is understood to mean less than 50% by weight of the lubricant composition. The concentration of the additive in a fuel is dependent upon a variety of factors, including the type of fuel used, the presence of other dispersants or other additives, and the like. Non-limiting example concentrations can range from about 10 to about 10,000 parts per million, or from about 30 to about 5,000 parts per million.

The base fuels used in formulating the fuel compositions of the present invention include any base fuels suitable for use in the operation of spark-ignition or compression-ignition internal combustion engines such as diesel fuel, jet fuel, kerosene, leaded or unleaded motor and aviation gasolines, and so-called reformulated gasolines which can contain both hydrocarbons of the gasoline boiling range and fuel-soluble oxygenates, such as alcohols, ethers and other suitable oxygen-containing organic compounds. Examples of oxygenates suitable for use in the present application include methanol, ethanol, isopropanol, t-butanol, mixed C1 to C5 alcohols, methyl tertiary butyl ether, tertiary amyl methyl ether, ethyl tertiary butyl ether and mixed ethers. Oxygenates, when used, can be present in the base fuel in an amount below, for example, about 25% by volume. In some embodiments, the oxygenates can be present in an amount that provides an oxygen content in the overall fuel in the range of about 0.5 to about 5 percent by volume.

The base fuels used in formulating the fuel compositions of the present invention can include, for example, compression ignition fuels having a sulfur content of up to about 0.2% by weight, such as up to about 0.05% by weight, as determined by the test method specified in ASTM D 2622-98. In some embodiments, suitable compression-ignition fuels for use in the present invention are low sulfur content diesel fuels.

In yet another aspect of the present application, the compounds of the present application are useful as dispersants in fuel additive concentrates. The fuel concentrates can comprise an inert stable organic solvent for a diluent and from about 5 to 50 weight percent of a imidazoline compound of the present application. Non-limiting examples of suitable diluents include benzene, toluene, xylene or higher boiling aromatics.

In one aspect, the present application is directed to a method of reducing deposits in the fuel system of an internal combustion engine, the method comprising using as the fuel for the internal combustion engine the fuel compositions described above. The compounds of the present application can be present in the fuel in an amount sufficient to reduce the deposits in the fuel system. Deposits may be reduced as compared to the amount of deposits that would occur in the same fuel system operated in the same manner and using the same fuel composition, if the fuel composition were devoid of the imidazoline compound.

In one aspect, the present application is directed to a method of cleaning intake valve deposits in an engine. The method comprises providing to a combustion system the fuel compositions of the present application, wherein the imidazoline compound is present in the fuel in an amount sufficient to maintain cleaner intake valve deposits for a period of time longer than if the fuel did not contain the imidazoline compound.

The following Examples are offered to specifically illustrate this invention. These Examples and illustrations are not to be construed in any way as limiting the scope of this invention.

EXAMPLES

Example 1

To a 3 L resin kettle equipped with an overhead stirrer was charged 1087 g of alkyleneyl succinic anhydride (acid number=0.552). The PIBSA was heated to 180° C. and stirred under nitrogen atmosphere. 113.4 g of TEPA was added via an addition funnel. The reaction mixture was heated at 180° C. under reduced pressure for 3 hours 777.1 g of process oil was added. The reaction mixture was then heated to 180° C. followed by addition of 48.1 g of Diethyl malonate. The reaction mixture was heated at 180° C. under reduced pressure for 3 hours. The reaction mixture was then filtered affording 1863 g of desired reaction product.

Example 2

To a 3 L resin kettle equipped with an overhead stirrer was charged 1087 g of alkyleneyl succinic anhydride (acid number=0.552). The PIBSA was heated to 180° C. and stirred under nitrogen atmosphere. 113.4 g of TEPA was added via an addition funnel. The reaction mixture was heated at 180° C. under reduced pressure for 3 hours 781.6 g of process oil was added. The reaction mixture was then heated to 180° C. followed by addition of 52.3 g of dimethyl adipate. The reaction mixture was heated at 180° C. under reduced pressure for 3 hours. The reaction mixture was then filtered affording 1853 g of desired reaction product.

Example 3

To a 3 L resin kettle equipped with an overhead stirrer was charged 1087 g of alkyleneyl succinic anhydride (acid number=0.552). The PIBSA was heated to 180° C. and stirred under nitrogen atmosphere. 113.4 g of TEPA was added via an addition funnel. The reaction mixture was heated at 180° C. under reduced pressure for 3 hours 807.7 g of process oil was added. The reaction mixture was then heated to 180° C. followed by addition of 78.4 g of dimethyl adipate. The reaction mixture was heated at 180° C. under reduced pressure for 3 hours. The reaction mixture was then filtered affording 1748 g of desired reaction product.

Example 4

To a 3 L resin kettle equipped with an overhead stirrer was charged 1087 g of alkyleneyl succinic anhydride (acid number=0.552). The PIBSA was heated to 180° C. and stirred under nitrogen atmosphere. 113.4 g of TEPA was added via an addition funnel. The reaction mixture was heated at 180° C. under reduced pressure for 3 hours 801.4 of process oil was added. The reaction mixture was then heated to 180° C. followed by addition of 72.1 g of diethyl malonate. The reaction mixture was heated at 180° C. under reduced pressure for 3 hours. The reaction mixture was then filtered affording 1027 g of desired reaction product.

Example 5

To a 3 L resin kettle equipped with an overhead stirrer was charged 1087 g of alkyleneyl succinic anhydride (acid number=0.552). The PIBSA was heated to 180° C. and stirred under nitrogen atmosphere. 113.4 g of TEPA was added via an addition funnel. The reaction mixture was heated at 180° C. under reduced pressure for 3 hours 787.6 of process oil was added. The reaction mixture was then heated to 180° C. followed by addition of 58.3 g of dimethyl isophthalate. The reaction mixture was heated at 180° C. under reduced pressure for 3 hours. The reaction mixture was then filtered affording 1840 g of desired reaction product.

The dispersant additives of Examples 1 through 3 were each blended into a passenger car motor oil formulation utilizing other components, including metal-containing sulfonates, zinc dithiophosphate wear inhibitors, sulfur-containing antioxidants, diaryl amine and phenolic antioxidants, oleate and molybdenum friction modifiers, a pour point depressant, a viscosity index improver (HiTEC®5751) and a lubricating base oil. These other components were in concentrations typically found in fully formulated multi-grade passenger car motor oils.

The kinematic viscosity at 100° C. (KV100) (mm2/s) and cold cranking simulator viscosity at 30° C. (CCS-30) (centipoise) were determined and the results are shown in Table 2 below.

TABLE 2
5W 30 Blend Study Results
DispersantPIB MnSolidsKV100CCS-30
Example 121002.510.626010
Example 221002.511.286005
Example 321002.512.075990

In Table 3 below, the sludge containing properties of lubricants containing the dispersants of examples 1, 2, 3, and 5, as described above, and a comparative lubricant containing a commercially available dispersant were compared using the Sequence VG engine test (an industry dispersant sludge test) to determine average engine sludge (“AES”). The lubricants used were fully formulated lubricants. In each sample, the ingredients of the lubricant were exactly the same except for the dispersant.

The Sequence VG engine sludge and varnish deposit test is a fired engine-dynamometer test that evaluates the ability of a lubricant to minimize the formation of sludge and varnish deposits. The test method was a cyclic test, with a total running duration of 216 hours, consisting of 54 cycles of 4 hours each. The test engine was a Ford 4.6 L, spark ignition, four stroke, eight cylinder “V” configuration engine. Features of this engine included dual overhead camshafts, a cross-flow fast burn cylinder head design, two valves per cylinder, and electronic port fuel injection. A 90-minute break-in schedule was conducted prior to each test, because a new engine build is used for each test. Upon test completion, the engine was disassembled and rated for sludge. Average engine sludge was calculated for each sample.

The results of this testing are shown in Table 3. The pass limits for each performance measure are also indicated in the table.

TABLE 3
Sequence VG engine test data
Dispersant CodeAES
Example 19.24
Example 28.90
Example 39.53
Example 59.48
Comparative7.91
Pass limits7.80

As shown from Table 3 above, the lubricant containing the dispersants of Examples 1, 2, 3 and 5 not only passed each performance measure, but resulted in higher AES test scores than the Comparative Example A. The results of this test indicate improved performance of the dispersant of the present application.

The disclosures of each patent or publication cited in the foregoing disclosure are incorporated herein by reference as if fully set forth herein.

For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

It is noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the,” include plural referents unless expressly and unequivocally limited to one referent. Thus, for example, reference to “an acid” includes two or more different acids. As used herein, the term “include” and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items.

While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or can be presently unforeseen can arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they can be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.