Lactone modified mono- or dicarboxylic acid based adduct dispersant compositions

• US 5,032,320 A
• Filed: 02/28/1991
• Issued: 07/16/1991
• Est. Priority Date: 10/07/1986
• Status: Expired due to Fees

• Current Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Gutierrez, Antonio, Lundberg, Robert D.
• Primary Examiner(s): Medley, Margaret B.
• Application Number:
  US07/486,502
• Time in Patent Office: 138 Days
• Field of Search: 252/51.5 A, 252/56 S, 252/49.6, 44/66, 44/73, 260/404.5, 521/140, 525/186, 525/190, 560/1, 560/155, 560/185, 560/76, 564/134, 564/141, 549/263
• US Class Current: 508/198
• CPC Class Codes: C07D 263/14 with radicals substituted by oxygen atoms
• CPC Class Codes: C07D 315/00 Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
• CPC Class Codes: C08G 63/60 derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
• CPC Class Codes: C08G 63/91 Polymers modified by chemical after-treatment
• CPC Class Codes: C10L 1/221 compounds of uncertain formula; reaction products where mixtures of compounds are obtained
• CPC Class Codes: C10M 129/76 containing free hydroxy or carboxyl groups
• CPC Class Codes: C10M 129/95 Esters
• CPC Class Codes: C10M 133/16 Amides; Imides
• CPC Class Codes: C10M 133/48 the ring containing both nitrogen and oxygen
• CPC Class Codes: C10M 133/52 having a carbon chain of 30 or more atoms
• CPC Class Codes: C10M 159/12 Reaction products
• CPC Class Codes: C10M 2207/289 containing free hydroxy groups
• 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 2215/26 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 2227/09 Complexes with metals
• CPC Class Codes: C10N 2040/00 Specified use or application for which the lubricating composition is intended
• CPC Class Codes: C10N 2040/02 Bearings
• CPC Class Codes: C10N 2040/04 : Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
• CPC Class Codes: C10N 2040/042 : for automatic transmissions
• CPC Class Codes: C10N 2040/044 : for manual transmissions
• CPC Class Codes: C10N 2040/046 : for traction drives
• CPC Class Codes: C10N 2040/08 : Hydraulic fluids, e.g. brake-fluids
• CPC Class Codes: C10N 2040/20 : Metal working
• 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: C10N 2040/30 : Refrigerators lubricants or compressors lubricants
• CPC Class Codes: C10N 2040/32 : Wires, ropes or cables lubricants
• CPC Class Codes: C10N 2040/34 : Lubricating-sealants
• CPC Class Codes: C10N 2040/36 : Release agents or mold release agents
• CPC Class Codes: C10N 2040/38 : Conveyors or chain belts
• CPC Class Codes: C10N 2040/40 : Generators or electric motors in oil or gas winning field
• CPC Class Codes: C10N 2040/42 : Flashing oils or marking oils
• CPC Class Codes: C10N 2040/44 : Super vacuum or supercritical use
• CPC Class Codes: C10N 2040/50 : Medical uses
• CPC Class Codes: C10N 2070/02 : Concentrating of additives

Abstract

C₅ -C₉ lactone based adduct materials are made by reacting a C₅ -C₉ lactone with a polyol to form a lactone adduct intermediate, and thereafter reacting the intermediate with an aliphatic hydrocarbyl saturated or unsaturated, straight chain or branched chain monocarboxylic or dicarboxylic acylating agent having from about one to about 165 total carbon atoms in said straight or branched chain to insure that the resulting lactone adduct is hydrocarbon soluble. The resulting adduct material are useful per se, as oil soluble dispersant additives, and are useful in fuel and lubricating oil compositions including concentrates containing the additives.

Claims

1. A C₅ -C₉ lactone adduct material useful as a lubricating oil additive formed by reacting an aliphatic hydrocarbyl saturated or unsaturated, natural or synthetic, straight chain or branched chain monocarboxylic or dicarboxylic acylating agent having from about 12 to about 165 total carbon atoms with the reaction product of a C₅ -C₉ lactone with an aliphatic polyhydric alcohol containing up to about 100 carbon atoms and from about 2 to about 10 hydroxyl groups, said aliphatic acylating agent having at least about twelve carbon atoms in said straight or branched chain to produce lactone adduct material that is hydrocarbon soluble.

2. The C₅ -C₉ lactone adduct material of claim 1, wherein said acylating agent is a member selected from the group of long chain fatty acids or dimers thereof and hydrocarbyl substituted C₄ -C₁₀ monounsaturated dicarboxylic acid materials, wherein said hydrocarbyl group contains from about twelve to about eighteen carbon atoms.

3. The C₅ -C₉ lactone adduct material of claim 2, wherein said lactone is E-caprolactone.

4. The C₅ -C₉ lactone adduct material of claim 3, wherein said acylating agent is selected from the group consisting of isostearic acid, stearic acid, linoleic acid, oleic acid, dimers of said acids and octadecenyl succinic anhydride.

5. The C₅ -C₉ lactone adduct material of claim 1, wherein said polyhdric alcohol is an aliphatic alcohol containing from 3 to 15 carbon atoms and at least three hydroxyl groups.

6. The C₅ -C₉ lactone adduct material of claim 5, wherein said polyhydric alcohol is a member selected from the group consisting of glycerol, erythritol, pentaerythritol, mannitol, sorbitol, 1,2,4-hexanetriol and tetrahydroxy pentane.

7. The C₅ -C₉ lactone adduct material of claim 4, wherein said polyhydric alcohol is an aliphatic alcohol containing from 3 to 15 carbon atoms and at least three hydroxyl groups.

8. The C₅ -C₉ lactone adduct material of claim 7, wherein said polyhydric alcohol is a member selected from the group consisting of glycerol, erythritol, pentaerythritol, mannitol, sorbitol, 1,2,4-hexanetriol and tetrahydroxy pentane.

9. The C₅ -C₉ lactone adduct material of claim 1, which has been post-treated with a borating agent selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron esters and boron acids.

23. A lubricating oil composition comprising lubricating oil and about 0.01 to 15 wt. % of the C₅ -C₉ lactone adduct material of claim 3.

24. A lubricating oil comprising a major amount of lubricating oil and about 0.1 to 10 wt. % of the C₅ -C₉ lactone adduct material of claim 3.

25. A lubricating oil comprising a major amount of lubricating oil and about 0.01 to 15 wt. % of the C₅ -C₉ lactone adduct material of claim 4.

26. A lubricating oil comprising a major amount of lubricating oil about 0.1 to 10 wt. % of the C₅ -C₉ lactone adduct material of claim 5.

27. A lubricating oil comprising a major amount of lubricating oil about 0.1 to 10 wt. % of the C₅ -C₉ lactone adduct material of claim 9.

10. A process for preparing a C₅ -C₉ lactone adduct material useful as a lubricating oil additive, which comprises the steps of:

i) reacting a C₅ -C₉ lactone with an aliphatic polyhydric alcohol having up to 100 carbon atoms and from about 2 to about 10 hydroxyl groups to form a lactone adduct intermediate product; and

ii) reacting said intermediate product with an aliphatic hydrocarbyl saturated or unsaturated, natural or synthetic, straight chain or branched chain monocarboxylic or dicarboxylic acylating agent having from about twelve to about eighteen total carbon atoms and at least twelve carbon atoms in the hydrocarbyl group.

11. The process of claim 10, wherein said lactone is E-caprolactone.

12. The process of claim 11, wherein said acylating agent is selected from the group consisting of isostearic acid, stearic acid, linoleic acid, oleic acid, dimers of said acids and octadecenyl succinic anhydride.

13. The process of claim 10, wherein said polyhdric alcohol is an aliphatic alcohol containing from 3 to 15 carbon atoms and at least three hydroxyl groups.

14. The process of claim 13, wherein said polyhydric alcohol is a member selected from the group consisting of glycerol, erythritol, pentaerythritol, mannitol, sorbitol, 1,2,4-hexanetriol and tetrahydroxy pentane.

15. The process of claim 10, further comprising the step of post-treating the C₅ -C₉ lactone adduct material with a borating agent selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron esters and boron acids.

16. An oleaginous composition comprising (I) an oleaginous material selected from the group consisting of lubricating oils and (II) a C₅ -C₉ lactone adduct material, said adduct material being prepared by reacting (i) a C₅ -C₉ lactone with (ii) an aliphatic polyhydric alcohol containing up to about 100 total carbon atoms and from about 2 to about 100 total carbon toms and from about 2 to about 10 hydroxyl groups to form an intermediate lactone adduct, and then reacting said intermediate lactone adduct with (iii) an aliphatic hydrocarbyl saturated or unsaturated, natural or synthetic, straight chain or branched chain monocarboxylic or dicarboxylic acylating agent having from about 12 to 165 total carbon atoms and at least about twelve carbon atoms in said straight or branched chain to insure that the resulting lactone adduct material is hydrocarbon soluble.

17. The oleaginous composition of claim 16, wherein said acylating agent is a member selected from the group of long chain fatty acids or dimers thereof and hydrocarbyl substituted C₄ -C₁₀ monounsaturated dicarboxylic acid materials, wherein said hydrocarbyl group contains from about twelve to about eighteen carbon atoms.

18. The oleaginous composition of claim 17, wherein said lactone is E-caprolactone.

19. The oleaginous composition of claim 18, wherein said acylating agent is selected from the group consisting of isostearic acid, stearic acid, linoleic acid, oleic acid, dimers of said acids and octadecenyl succinic anhydride.

20. The oleaginous composition of claim 16, wherein said polyhdric alcohol is an aliphatic alcohol containing from 3 to 15 carbon atoms and at least three hydroxyl groups.

21. The oleaginous composition of claim 20, wherein said polyhydric alcohol is a member selected from the group consisting of glycerol, erythritol, pentaerythritol, mannitol, sorbitol, 1,2,4-hexanetriol and tetrahydroxy pentane.

22. The oleaginous composition of claim 16, wherein said C₅ -C₉ lactone adduct material has been post-treated with a borating agent slected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron esters and boron acids.

28. A lubricating oil soluble dispersant useful as an oil additive, comprising the product of a reaction mixture comprising:

(i) an aliphatic hydrocarbyl saturated or unsaturated natural or synthetic, straight chain or branched chain monocarboxylic or dicarboxylic acylating agent having from about 12 to about 165 total carbon atoms; and

(ii) a C₅ -C₉ lactone adduct formed by reacting (a) a C₅ -C₉ lactone with (b) an aliphatic polyhydric alcohol containing up to about 100 total carbon atoms and from about 2 to about 10 hydroxyl groups,

wherein there are from 1 to about 10 C₅ -C₉ lactone derived moieties per unit of said adduct (II) used in the reaction.

29. An oil soluble dispersant according to claim 28, wherein said C₅ -C₉ lactone is caprolactone.

30. An oil soluble dispersant according to claim 28, wherein said polyhydric alcohol is an aliphatic alcohol containing from 3 to 15 carbon atoms and at least three hydroxyl groups.

31. An oil soluble dispersant according to claim 30, wherein said polyhydric alcohol is a member selected from the group consisting of glycerol, erythritol, pentaerythritol, mannitol, sorbitol, 1,2,4-hexanetriol and tetrahydroxy pentane.

32. An oil soluble dispersant according to claim 29, which has been post-treated with a borating agent selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron esters and boron acids.

33. A lubricating oil soluble reaction product useful as an oil additive of:

(a) an aliphatic hydrocarbyl saturated or unsaturated, natural or synthetic, straight chain or branched chain monocarboxylic or dicarboxylic acylating agent having from about 12 to about 18 total carbon atoms

(b) aliphatic polyhydric alcohol containing up to about 100 total carbon atoms and from 2 to about 10 hydroxyl groups, and

(c) C₅ -C₉ lactone,

wherein (b) is first reacted with (c) and the resulting product is then reacted with (a), and wherein there are about 0.5 to 20 molar proportions of (c) per molar proportion of said reaction product.

34. An oil soluble reaction product according to claim 33 wherein wherein (c) is E-caprolactone, and wherein there are about 1 to 5 molar proportions of (c) per molar proportion of said reaction product.

35. A lubricating oil composition comprising lubricating oil and an oil soluble reaction product useful as an oil additive, said reaction product being the product of reaction of the intermediate product formed by reacting (a) a C₅ -C₉ lactone with an aliphatic polyhydric alcohol containing up to about 100 total carbon atoms and from about 2 to about 10 hydroxyl groups, wherein there are 0.2 to 100 molar proportions of (b) in said intermediate product, further reacted with (c) an aliphatic hydrocarbyl saturated or unsaturated, natural or synthetic, straight chain or branched chain monocarboxylic or dicarboxylic acylating agent having from about 12 to about 18 total carbon atoms.

36. A lubricating oil composition according to claim 35, wherein (a) is caprolactone, and wherein there are from about one to about five molar proportions of caprolactone per molar proportion of product obtained by the reaction of (a) with (b).

37. A lubricating crankcase motor oil composition for automotive vehicles and trucks comprising a major amount of lubricating oil;

from about 0.01 to 15 wt. % of a dispersant formed by reacting an aliphatic hydrocarbyl saturated or unsaturated, natural or synthetic, straight chain or branched chain monocarboxylic or dicarboxylic acylating agent having from about 12 to about 18 total carbon atoms with the reaction product of a C₅ -C₉ lactone and an aliphatic polyhydric alcohol containing up to about 100 total carbon atoms and from about 2 to about 10 hydroxyl groups, wherein said dispersant has about one to five molar proportion of acylating agent moieties; and

about 3 to 25 wt. % of a metal containing detergent additive.

38. A composition according to claim 37, wherein said C₅ -C₉ lactone is caprolactone.

39. A composition according to claim 38, wherein said composition also contains an effective amount of a zinc dihydrocarbyl dithiophosphate.

40. A composition according to claim 39 wherein said dispersant has been post-treated with a borating agent slected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron esters and boron acids.

41. An additive concentrate comprising about 20 to 80 wt. % lubricating oil and 20 to 80 wt. % of a dispersant which is a C₅ -C₉ lactone adduct material formed by first reacting about 0.2 to 100 molar proportions of a C₅ -C₉ lactone per molar proportion of an aliphatic polyhydric alcohol containing up to about 100 total carbon atoms and from about 2 to about 10 hydroxyl groups to form a lactone adduct intermediate, and then reacting said intermediate with an aliphatic hydrocarbyl saturated or unsaturated, natural or synthetic, straight chain or branched chain monocarboxylic or dicarboxylic acylating agent having from about 12 to about 18 total carbon atoms.

42. A concentrate according to claim 41, wherein said C₅ -C₉ lactone is caprolactone and which also contains an effective amount of a viscosity modifier.

43. A concentrate according to claim 42, which also contains an effective amount of a zinc dihydrocarbyl dithiophosphate.

44. A concentrate according to claim 41, wherein said C₅ -C₉ lactone adduct material has been post-treated with a borating agent selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron esters and boron acids.

45. An additive concentrate comprising about 20 to 80 wt. % lubricating oil and about 20 to 80 wt. % of an oil soluble reaction product of a caprolactone adduct and an acylating agent selected from the group consisting of long chain fatty acids, long chain fatty acid dimers and hydrocarbyl substituted C₄ to C₁₀ monounsaturated dicarboxylic acid producing material having from about twelve to about 18 carbon atoms in said hydrocarbyl substituent, said caprolactone adduct being prepared by reacting caprolactone with an aliphatic polyhydric alcohol containing up to about 100 total carbon atoms and from about 2 to about 10 hydroxyl groups.

46. An additive concentrate according to claim 45, wherein said hydrocarbyl substituted C₄ to C₁₀ acid producing material is octadecenyl succinic anhydride.

47. An additive concentrate according to claim 45, wherein said long chain fatty acids and said long chain fatty acid dimers are selected from the group consisting of isostearic acid, stearic acid, linoleic acid, oleic acid and dimers thereof.