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CA-3019184-C - POLYESTER DISPERSANTS, SYNTHESIS AND USE THEREOF

CA3019184CCA 3019184 CCA3019184 CCA 3019184CCA-3019184-C

Abstract

Disclosed is an oil soluble polyester composition, suitable for use as a dispersant in lubricating oils. The oil soluble polyester composition is prepared by reacting (a) a hydrocarbyl -substituted succinic acylating agent and (b) a di- hydroxyalkyl-substituted tertiary amine compound selected from a N,N'-di- hydroxyalkyl-substituted tertiary monoamine and a N,N'-di-hydroxyalkyl-substituted tertiary diamine.

Inventors

  • WILLIAM RAYMOND, JR. RUHE

Assignees

  • CHEVRON ORONITE COMPANY LLC

Dates

Publication Date
20260505
Application Date
20170711
Priority Date
20160714

Claims (7)

  1. WHAT IS CLAIMED IS: 1. An oil soluble polyester composition comprising a reaction product of: (a) a hydrocarbyl-substituted succinic acylating agent; and (b) a di-hydroxyalkyl-substituted tertiary amine compound selected from a N,N-di-hydroxyalkyl-substituted tertiary monoamine, a N,N’-di-hydroxyalkyl substituted tertiary diamine, and combinations thereof; and (c) poly(oxyalkyene) polyol having from 2 to 15 C2-4 alkylene oxide units per molecule.
  2. 2. The oil soluble polyester composition of claim 1, wherein the hydrocarbyl substituted succinic acylating agent comprises a polyisobutenyl succinic anhydride in which the polyisobutenyl group has a number average molecular weight (Mn) of from 500 to 5000.
  3. 3. The oil soluble polyester composition of claim 2, wherein the hydrocarbyl substituted succinic acylating agent further comprises a C12-20 hydrocarbyl substituted succinic acylating agent.
  4. 4. The oil soluble polyester composition of any one of claims 1 to 3, wherein the N,N-di-hydroxyalkyl-substituted tertiary monoamine has the following structure: (RO)xH R1 wherein: N (RO)yH (a) R1 is selected from C1-20 alkyl, C5-20 cycloalkyl, C6-20 aryl, 5- to 20-membered heteroaryl, and 5- to 20-membered heterocyclyl, and wherein the alkyl, cycloalkyl, aryl, heteroaryl, and heterocyclyl groups are substituted or unsubstituted; 33 (b) R in each of the x (RO) and the y (RO) groups is independently C2-4 alkylene; and (c) x and y are independently an integer of 1 to 5.
  5. 5. The composition of any one of claims 1 to 3, wherein the N,N-di-hydroxyalkyl substituted tertiary monoamine has the following structure: (RO)xH R2 wherein: N (RO)yH (a) R2 is hydrogen, C1-4 alkyl, —NH—(C6-10 aryl), —NH—(C7-16 aralkyl), —O— (C1-4 alkyl), —O—(C6-10 aryl), or —O—(C7-16 aralkyl) (b) R in each of the x (RO) and the y (RO) groups is independently C2-4 alkylene; and (c) x and y are independently an integer of 1 to 5.
  6. 6. The oil soluble polyester composition of claim 5, wherein the N,N-di hydroxyalkyl tertiary monoamine is selected from the group consisting of N,N-bis(2 hydroxyethyl)aniline, N,N-bis(2-hydroxypropyl)aniline, N,N-bis(2-hydroxyethyl)-N' phenyl-1,4-phenylenediamine, 4-phenoxy-N,N-bis(2-hydroxyethyl)aniline, and 4 benzyloxy-N,N-bis(2-hydroxypropyl)aniline, and combinations thereof.
  7. 7. The oil soluble polyester composition of claim 6, wherein the N,N-di hydroxyalkyl tertiary monoamine is N,N-bis(2-hydroxyethyl)aniline. 34 8. The oil soluble polyester composition of any one of claims 1 to 3, wherein the N,N-di-hydroxyalkyl-substituted tertiary monoamine has the following structure: Z N m n wherein: (RO)xH N (RO)yH (a) R in each of the x (RO) and the y (RO) groups is independently C2-4 alkylene; (b) x and y are independently an integer of 1 to 5; (c) Z is CH2, O, S, N—(C1-4 alkyl), or N—(C6-10 aryl); (d) m is an integer of 1 to 3; and (e) n is an integer of 1 to 6. 9. The oil soluble polyester composition of claim 8, wherein the N,N-di hydroxyalkyl-substituted tertiary monoamine is selected from the group consisting of 2-pyrrolidino-N,N-bis(2-hydroxyethyl)ethylamine, 2-pyrrolidino-N,N-bis(2 hydroxypropyl)ethylamine, 2-piperidino-N,N-bis(2-hydroxyethyl)ethylamine, 2 piperidino-N,N-bis(2-hydroxypropyl)ethylamine, 3-piperidino-N,N-bis(2 hydroxyethyl)propylamine, 3-piperidino-N,N-bis(2-hydroxypropyl)propylamine, 2 morpholino-N,N-bis(2-hydroxyethyl)ethylamine, 2-morpholino-N,N-bis(2 hydroxypropyl)ethylamine, 3-morpholino-N,N-bis(2-hydroxyethyl)propylamine, and 3-morpholino-N,N-bis(2-hydroxypropyl)propylamine, and combinations thereof. 10. The oil soluble polyester composition of claim 9, wherein the N,N-di hydroxyalkyl-substituted tertiary monoamine is 3-morpholino-N,N-bis(2 hydroxyethyl)propylamine. 35 11. The oil soluble polyester composition of any one of claims 1 to 3, wherein the N,N-di-hydroxyalkyl-substituted tertiary monoamine has the following structure: (RO)xH N Ar_(OR)z wherein: (RO)yH (a) R in each of the x (RO), y (RO) and z (RO) groups is independently C2-4 alkylene; (b) x, y and z are independently an integer of 1 to 5; and (c) Ar is unsubstituted or substituted C6-20 aryl. 12. The oil soluble polyester composition of claim 11, wherein the N,N-di hydroxyalkyl-substituted tertiary monoamine has the following structure: O 13. O O HO N HO . The oil soluble polyester composition of any one of claims 1 to 3, wherein the N,N’-di-hydroxyalkyl-substituted tertiary diamine has the following structure: H(OR)x wherein: N N q 36 (RO)yH (a) R in each of the x (RO) and the y (RO) groups is independently C2-4 alkylene; and (b) 14. q is an integer of 1, 2, or 3. The oil soluble polyester composition of claim 13, wherein the N,N’-di hydroxyalkyl-substituted tertiary diamine is selected from the group consisting of N,N’-bis(2-hydroxyethyl)piperazine, N,N’-bis(2-hydroxypropyl)piperazine, N-(2 hydroxyethyl)-N’-(2-hydroxypropyl)piperazine, N-(2-hydroxyethyl)-N’-(2 hydroxybutyl)piperazine, N,N’-bis(2-hydroxyethyl)homopiperazine, N,N’-bis(2 hydroxypropyl)homopiperazine, and combinations thereof. 15. The oil soluble polyester composition of claim 14, wherein the N,N’-di hydroxyalkyl-substituted tertiary diamine is N,N’-bis(2-hydroxyethyl)piperazine. 16. The oil soluble polyester composition of any one of claims 4, 5, 8 11, and 13, wherein R in each of the x (RO) and the y (RO) groups is independently selected from ethylene and propylene. 17. The oil soluble polyester composition of any one of claims 4, 5, 8 11, and 13, wherein x is an integer of 1 and y is an integer of 1. 18. The oil soluble polyester composition of any one of claims 1 to 17, wherein the reaction product further comprises a poly(oxyalkyene) polyol having from 5 to 15 C2-4 alkylene oxide units per molecule. 19. The oil soluble polyester composition of any one of claims 1 to 18, wherein the reaction product further comprises an aliphatic dicarboxylic acid having 6 to 20 carbon atoms, an aromatic dicarboxylic acid having 8 to 20 carbon atoms, or a combination thereof. 37 20. A lubricating oil composition comprising (a) a major amount of an oil of lubricating viscosity and (b) from 0.05 to 15 wt. %, based on the total weight of the lubricating oil composition, of the oil soluble polyester composition of any one of claims 1 to 19. 21. The lubricating oil composition of claim 20, further comprising at least one additive selected from the group consisting of demulsifiers, detergents, dispersants, extreme pressure agents, foam inhibitors, friction modifiers, multifunctional additives, oxidation inhibitors, pour point depressants, rust inhibitors, and wear inhibitors. 22. A lubricating oil additive concentrate comprising from 80 to 20 wt. % of an organic liquid diluent and from 20 to 80 wt. % of the oil soluble polyester composition of any one of claims 1 to 19. 23. A method for controlling soot-induced viscosity increase experienced in diesel engine lubricating oils during use in diesel engines, the method comprising employing as the diesel engine lubricating oil the lubricating oil composition of claim 20. 24. A method of improving soot dispersancy in an internal combustion engine which comprises operating the engine with a lubricating oil composition comprising the oil soluble polyester composition of any one of claims 1 to 19 and a major amount of oil of lubricating viscosity. 25. A process for preparing an oil soluble polyester composition which comprises reacting a mixture comprising: (i) a hydrocarbyl-substituted succinic acylating agent; and 38 (ii) a di-hydroxyalkyl-substituted tertiary amine compound selected from a N,N-di-hydroxyalkyl-substituted tertiary monoamine, a N,N’-di-hydroxyalkyl substituted tertiary diamine, and combinations thereof; and (iii) poly(oxyalkyene) polyol having from 2 to 15 C2-4 alkylene oxide units per molecule, wherein a charge mole ratio of the di-hydroxalkyl-substituted tertiary amine compound to the hydrocarbyl succinic acylating agent in the mixture is maintained at 0.67 to 1.5:1. 26. The process of claim 25, wherein the mixture is maintained at a temperature of 150°C to 260°C. 27. The process of claim 25 or 26, wherein the hydrocarbyl-substituted succinic acylating agent comprises a polyisobutenyl succinic anhydride in which the polyisobutenyl group has a number average molecular weight (Mn) of from 500 to 5000. 28. A process for preparing an oil soluble polyester composition which comprises the steps of: (a) reacting a mixture comprising: (i) a first hydrocarbyl-substituted succinic acylating agent (HC-SAA1); and (ii) a di-hydroxyalkyl-substituted tertiary amine compound to form an intermediate material, wherein the di-hydroxyalkyl-substituted tertiary amine compound is selected from the group consisting of a N,N-di-hydroxyalkyl substituted tertiary monoamine, a N,N’-di-hydroxyalkyl-substituted tertiary diamine, and combinations thereof; and (iii) poly(oxyalkyene) polyol having from 2 to 15 C2-4 alkylene oxide units per molecule; and 39 (b) reacting the intermediate material of step (a) with a second hydrocarbyl substituted acylating agent (HC-SAA2); wherein a charge mole ratio of the di-hydroxalkyl-substituted tertiary amine compound to [(HC-SAA1)+(HC-SAA2)] is maintained at 0.67 to 1.5:1. 29. The process of claim 28, wherein steps (a) and (b) are maintained at a temperature of 150°C to 260°C. 30. The process of claim 28 or 29, wherein the first hydrocarbyl-substituted succinic acylating agent comprises a C12-20-hydrocarbyl-substituted acylating agent. 31. The process of claim 30, wherein the C12-20-hydrocarbyl-substituted acylating agent is selected from one or more of dodecenyl succinic anhydride, hexadecenyl succinic anhydride, and octadecenyl succinic anhydride. 32. The process of any one of claims 28 to 31, wherein the second hydrocarbyl substituted succinic acylating agent comprises a polyisobutenyl succinic anhydride in which the polyisobutenyl group has a number average molecular weight (Mn) of from 500 to 5000. 33. The process of any one of claims 25 to 32, wherein the N,N-di-hydroxyalkyl tertiary monoamine is selected from the group consisting of N,N-bis(2 hydroxyethyl)aniline, N,N-bis(2-hydroxypropyl)aniline, N,N-bis(2-hydroxyethyl)-N' phenyl-1,4-phenylenediamine, 4-phenoxy-N,N-bis(2-hydroxyethyl)aniline, and 4 benzyloxy-N,N-bis(2-hydroxypropyl)aniline, and combinations thereof. 34. The process of any one of claims 25 to 32, wherein the N,N-di-hydroxyalkyl substituted tertiary monoamine has the following structure: 40 HO O O O 35. N HO . The process of any one of claims 25 to 32, wherein the N,N’-di-hydroxyalkyl substituted tertiary diamine is selected from the group consisting of N,N’-bis(2 hydroxyethyl)piperazine, N,N’-bis(2-hydroxypropyl)piperazine, N-(2-hydroxyethyl) N’-(2-hydroxypropyl)piperazine, N-(2-hydroxyethyl)-N’-(2-hydroxybutyl)piperazine, N,N’-bis(2-hydroxyethyl)homopiperazine, N,N’-bis(2-hydroxypropyl)homopiperazine, and combinations thereof. 36. The process of any one of claims 25 to 32, wherein the poly(oxyalkylene)polyol is selected from one or more of polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, polypropylene glycol 400, and polypropylene glycol 725. 41

Description

POLYESTER DISPERSANTS. SYNTHESIS AND USE THEREOF TECHNICAL FIELD [001] This disclosure relates to a novel polyester dispersant additive with soot handling attributes, its synthesis, and its use in lubricants, particularly for reducing soot-induced viscosity increase in heavy duty diesel engine lubricants. BACKGROUND [002] Internal combustion engines function by the combustion of fuels which in turn generate the power needed to propel vehicles. In the case of a diesel engine, the fuel is a diesel fuel and the combustion thereof generally results in emissions from the exhausts of such vehicles which comprise three main components: soot and particulate matter, carbon monoxide and nitrogen oxides (NOx). To alleviate environmental concerns, research is ongoing to reduce the levels of these emissions. NOx emissions can be reduced by lowering the temperature at which the fuel is combusted in the engine. Typically this is achieved by retarding the combustion, i.e., by injecting the fuel shortly after the peak temperature is reached in the cylinder. However, this retarded combustion has the disadvantage that it causes more soot to accumulate in the engine lubricant partly due to incomplete combustion of the fuel because of the lower combustion temperature, and partly due to increased soot deposition on the cylinder wall which is drawn down into the lubricant with the downward stroke of the piston. The presence of soot in the lubricant has the adverse effect of causing viscosity increase and accelerated wear. It is important that soot induced viscosity increase be controlled such that the lubricant stays within viscosity grade in order to maintain its expected performance and to enable quick and clean drainage of the engine during servicing. [003] Lubricating oil compositions comprise a major amount of base oil and additives that improve the performance and increase the useful life of the lubricant. Nitrogen-containing dispersants are commonly used lubricant additives. The function of a dispersant is to maintain in suspension within the oil, insoluble materials formed 1 WO 2018/013527 PCT/0S2017/041477 by oxidation and other mechanisms during use of the oil, to prevent sludge flocculation and precipitation of the insoluble materials. Another function of the dispersant is to reduce the agglomeration of soot particles, thus reducing increases in the viscosity of the lubricating oil upon use. In the severe environment of diesel engines, it has been found that soot induced viscosity increase cannot be controlled by conventional dispersants, even when the amounts of such conventional dispersants are increased. Therefore, compounds providing potent soot dispersing properties and crankcase lubricants providing improved soot dispersing performance are continuously demanded. [004] The present disclosure provides a dispersant having improved performance in engine tests, providing a good viscosity index and good soot dispersion and toleration properties, particularly in diesel engines, and especially in heavy duty diesel engines employing exhaust gas recirculation. SUMMARY [005] The present disclosure is directed in part to an oil soluble polyester composition which may be added to lubricating oils and contributes to improvements in the viscosity characteristics, the dispersancy and amelioration of soot thickening, and to improving wear characteristics when employed in lubricating oil formulations for mechanical equipment. [006] In one aspect, there is provided an oil soluble polyester composition which is a reaction product of (a) a hydrocarbyl-substituted succinic acylating agent; and (b) a di-hydroxyalkyl-substituted tertiary amine compound selected from a N,Ndi- hydroxyalkyl-substituted tertiary monoamine, a N,N'-di-hydroxyalkyl-substituted tertiary diamine, and combinations thereof. [007] In another aspect, there is provided a lubricating oil composition comprising a major amount of an oil of lubricating viscosity and a minor amount of any one of the embodiments described herein for the oil soluble polyester composition. 2 [008] In a further aspect, there is provided an additive concentrate comprising from 80 to 20 wt.% of an organic liquid diluent and from 20 to 80 wt. % of any one of the embodiments described herein for the oil soluble polyester composition. [009] In yet a further aspect, there is provided a method of improving soot dispersancy in an internal combustion engine which comprises operating the engine with a lubricating oil composition comprising a major amount of oil of lubricating viscosity and an effective amount of any one of the embodiments described herein for the oil soluble polyester composition. [01 0] In still yet a further aspect, there is provided a process for preparing an oil soluble polyester composition which comprises reacting a mixture comprising: (i) a hydrocarbyl-substituted succinic acylating agent; and (ii) a di-hydroxyalkylsubstituted tertiary amine compound selected from a N,N-di-hydro