Lactone modified, esterified dispersant additives useful in oleaginous compositions

• US 4,866,139 A
• Filed: 10/07/1986
• Issued: 09/12/1989
• 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): Smith, Edward J.
• Application Number:
  US06/916,114
• Time in Patent Office: 1,071 Days
• Field of Search: 525/331.7, 525/333.7, 548/237, 548/238, 549/267, 560/196, 560/198
• US Class Current: 525/333.7
• CPC Class Codes: C08G 63/00 Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule polyester-amides C08G69/44; polyester-imides C08G73/16
• CPC Class Codes: C10L 1/1817 Compounds of uncertain formula; reaction products where mixtures of compounds are obtained
• CPC Class Codes: C10L 1/221 compounds of uncertain formula; reaction products where mixtures of compounds are obtained
• CPC Class Codes: C10M 129/95 Esters
• CPC Class Codes: C10M 133/52 having a carbon chain of 30 or more atoms
• CPC Class Codes: C10M 145/22 Polyesters
• CPC Class Codes: C10M 159/12 Reaction products
• CPC Class Codes: C10M 2205/00 Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
• CPC Class Codes: C10M 2205/026 Butene
• CPC Class Codes: C10M 2205/06 containing conjugated dienes
• CPC Class Codes: C10M 2207/027 Neutral salts thereof
• CPC Class Codes: C10M 2207/028 Overbased salts thereof
• CPC Class Codes: C10M 2207/144 containing hydroxy groups
• CPC Class Codes: C10M 2207/146 having carboxyl groups bound to carbon atoms of six-membeered aromatic rings having a hydrocarbon substituent of thirty or more carbon atoms
• CPC Class Codes: C10M 2207/16 Naphthenic acids
• CPC Class Codes: C10M 2207/262 derived from hydroxy substituted aromatic acids, e.g. salicylates
• CPC Class Codes: C10M 2209/102 Polyesters
• CPC Class Codes: C10M 2215/04 having amino groups bound to acyclic or cycloaliphatic carbon atoms
• CPC Class Codes: C10M 2215/042 containing hydroxy groups; Alkoxylated derivatives thereof
• CPC Class Codes: C10M 2215/064 Di- and triaryl amines
• CPC Class Codes: C10M 2215/065 : Phenyl-Naphthyl amines
• CPC Class Codes: C10M 2215/086 : Imides
• CPC Class Codes: C10M 2215/22 : Heterocyclic nitrogen compounds
• CPC Class Codes: C10M 2215/221 : Six-membered rings containing nitrogen and carbon only
• CPC Class Codes: C10M 2215/225 : the rings containing both nitrogen and oxygen
• CPC Class Codes: C10M 2215/226 : Morpholines
• CPC Class Codes: C10M 2215/26 : Amines
• CPC Class Codes: C10M 2215/28 : Amides; Imides
• CPC Class Codes: C10M 2215/30 : Heterocyclic compounds
• CPC Class Codes: C10M 2217/046 : Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
• CPC Class Codes: C10M 2217/06 : Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
• CPC Class Codes: C10M 2219/044 : Sulfonic acids, Derivatives thereof, e.g. neutral salts
• CPC Class Codes: C10M 2219/046 : Overbasedsulfonic acid salts
• CPC Class Codes: C10M 2219/087 : containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
• CPC Class Codes: C10M 2219/088 : Neutral salts
• CPC Class Codes: C10M 2219/089 : Overbased salts
• CPC Class Codes: C10M 2223/04 : Phosphate esters
• CPC Class Codes: C10M 2223/042 : Metal salts thereof
• CPC Class Codes: C10M 2223/045 : Metal containing thio derivatives
• CPC Class Codes: C10M 2223/12 : obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
• CPC Class Codes: C10M 2225/04 : obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
• CPC Class Codes: C10M 2225/041 : Hydrocarbon polymers
• CPC Class Codes: C10M 2227/09 : Complexes with metals
• CPC Class Codes: C10M 2229/041 : containing aliphatic substituents
• CPC Class Codes: C10N 2010/04 : Groups 2 or 12
• CPC Class Codes: C10N 2010/14 : Group 7
• CPC Class Codes: C10N 2010/16 : Groups 8, 9, or 10
• CPC Class Codes: C10N 2070/02 : Concentrating of additives

Abstract

Poly(C₅ -C₉ lactone) adducts are made by reacting a C₅ -C₉ lactone with a post reacted hydrocarbyl substituted C₄ -C₁₀ monounsaturated dicarboxylic acid producing material, e.g., a polyisobutenyl succinic anhydride, which, in turn, preferably was made by reacting a polymer of a C₂ to C₁₀ monoolefin, preferably polyisobutylene, having a number average molecular weight of about 700 to 5,000, with a C₄ to C₁₀ monounsaturated acid, anhydride or ester, preferably maleic anhydride, such that there are 0.7 to 2.0 dicarboxylic acid producing moieties per molecular of said olefin polymer used in the reaction mixture, and then, post reacting the substituted acid, anhydride or ester with a polyol such as pentaerythritol or THAM. The resulting adducts are useful per se as oil soluble dispersant additives useful in fuel and lubricating compositions including concentrates containing the additives.

Claims

1. A poly (C₅ -C₉ lactone) adduct material useful as an oil additive and formed by reacting at a temperature of from about 50°

to about 200°

C. a C₅ -C₉ lactone (I) with the reaction product (II) of a hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material and a polyol selected from the group consisting of aliphatic polyhydric alcohols containing up to about 100 carbon atoms and about 2 to about 15 hydroxyl groups and 2,2-disubstituted-2-amino-1-alkanols having from two to three hydroxyl groups and containing a total of 4 to 8 carbons atoms, said reaction product (II) being prepared at a temperature of from about 100°

to about 250°

C. over a period of from about 1 to about 10 hours, said hydrocarbyl substituted acid producing material being formed by reacting an olefin polymer of a C₂ -C₁₀ monoolefin having a number average molecular weight of about 300 to about 10,000 and a C₄ -C₁₀ monounsaturated dicarboxylic acid material selected from the group consisting of acids, esters and anhydrides, wherein there are an average of from about 0.7 to about 2.0 moles of dicarboxylic acid producing material per mole of said olefin polymer used in the reaction, and said poly (C₅ -C₉ lactone) adduct containing the unit ##STR11## wherein m has an average value of from about 0.2 to about 100 and x is a whole number from 4 to 8.

2. The poly(C₅ -C₉ lactone) adduct of claim 1, wherein said polyol is an aliphatic polyhydric alcohol.

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

4. The poly(C₅ -C₉ lactone) adduct of claim 3, wherein said C₄ -C₁₀ monounsaturated dicarboxylic acid material is maleic anhydride.

5. The poly(C₅ -C₉ lactone) adduct of claim 4, wherein said olefin polymer is polyisobutylene.

6. The poly(C₅ -C₉ lactone) adduct material of claim 5, wherein said polyol is pentaerythritol.

7. The poly(C₅ -C₉ lactone) adduct of claim 6, wherein there are about 0.7 to 2.0 succinic anhydride units per polyisobutylene moiety present in said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material, and wherein the number average molecular weight of said polyisobutylene is from 300 to about 10,000.

8. The poly(C₅ -C₉ lactone) adduct of claim 6, wherein there are about 0.7 to 1.6 succinic anhydride units per polyisobutylene moiety present in said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material, and wherein the number average molecular weight of said polyisobutylene is from 300 to about 10,000.

9. The poly(C₅ -C₉ lactone) adduct of claim 8, wherein there are about 0.9 to 1.6 succinic anhydride units per polyisobutylene moiety present in said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material, and wherein the number average molecular weight of said polyisobutylene is from 300 to about 10,000.

10. The poly(C₅ -C₉ lactone) adduct of claim 9, wherein there are about 1.05 to 1.35 succinic anhydride units per polyisobutylene moiety present in said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material, and wherein the number average molecular weight of said polyisobutylene is from 300 to about 10,000.

11. The poly(C₅ -C₉ lactone) adduct of claim 6, wherein m has an average value of from about 0.5 to about 20.

12. The poly(C₅ -C₉ lactone) adduct of claim 1, wherein said polyol is a 2,2-disubstituted-2-amino-1-alkanol of the formula ##STR12## wherein X is an alkyl or hydroxyalkyl group with the alkyl groups having from 1 to 3 carbon atoms, wherein at least one of the X substituents is a hydroxyalkyl group of the formula (CH₂)_n OH, and wherein n is 1 to 3.

13. The poly(C₅ -C₉ lactone) adduct of claim 12, wherein said polyol is tris(hydroxymethyl) amino methane.

14. The poly(C₅ -C₉ lactone) adduct of claim 13, wherein said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material is first lactonized and then reacted with said tris(hydroxymethyl)amino methane to form a lactone-oxazoline intermediate, and wherein said intermediate is then reacted with said C₅ -C₉ lactone.

15. The poly(C₅ -C₉ lactone) adduct of claim 14, wherein said C₄ -C₁₀ monounsaturated dicarboxylic acid material is maleic anhydride, wherein said olefin polymer is polyisobutylene, and wherein said C₅ -C₉ lactone is E-caprolactone.

16. The poly(C₅ -C₉ lactone) adduct of claim 13, wherein said reaction product of said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material and said tris(hydroxymethyl)amino methane is a bis-oxazoline intermediate, and said bis-oxazoline intermediate being reacted with said C₅ -C₉ lactone.

17. The poly(C₅ -C₉ lactone) adduct of claim 16, wherein said C₄ -C₁₀ monounsaturated dicarboxylic acid material is maleic anhydride, wherein said olefin polymer is polyisobutylene, and wherein said C₅ -C₉ lactone is E-caprolactone.

18. The poly(C₅ -C₉ lactone) adduct of claim 13, wherein there are about 0.7 to 2.0 succinic anhydride units per polyisobutylene moiety present in said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material, and wherein the number average molecular weight of said polyisobutylene is from 300 to about 10,000.

19. The poly(C₅ -C₉ lactone) adduct of claim 13, wherein there are about 0.9 to 1.6 succinic anhydride units per polyisobutylene moiety present in said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material, and wherein the number average molecular weight of said polyisobutylene is from 300 to about 10,000.

20. The poly(C₅ -C₉ lactone) adduct of claim 13, wherein there are about 1.05 to 1.35 succinic anhydride units per polyisobutylene moiety present in said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material, and wherein the number average molecular weight of said polyisobutylene is from 300 to about 10,000.

21. The poly(C-C₉ lactone) adduct of claim 13, wherein there are about 1.05 to 1.35 succinic anhydride units per polyisobutylene moiety present in said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material, and wherein the number average molecular weight of said polyisobutylene is from 300 to about 10,000.

22. The poly(C₅ -C₉ lactone) adduct of claim 15, wherein m has an average value of from about 0.5 to about 20.

23. The poly(C₅ -C₉ lactone) adduct of claim 17, wherein m has an average value of from about 0.5 to about 20.

24. The poly(C₅ -C₉ lactone) adduct of claim 11, wherein the number average molecular weight of said polyisobutylene is from 700 to about 3000.

25. The poly(C₅ -C₉ lactone) adduct of claim 22, wherein the number average molecular weight of said polyisobutylene is from 700 to about 3000.

26. The poly(C₅ -C₉ lactone) adduct of claim 23, wherein the number average molecular weight of said polyisobutylene is from 700 to about 3000.

27. An oil soluble dispersant useful as an oil additive, comprising the product of a reaction mixture comprising as reactants:

(I) the reaction product of (a) a hydrocarbyl substituted C₄ -C₁₀ monounsaturated dicarboxylic acid producing material formed by reacting olefin polymer of C₂ -C₁₀ monoolefin having a number average molecular weight of about 300 to 10,000 and a C₄ -C₁₀ monounsaturated acid material selected from the group consisting of acids, esters and anhydrides, wherein there are from about 0.7 to about 2.0 molar equivalents of dicarboxylic acid producing moieties per molar equivalent of said olefin polymer in the reaction mixture, and (b) a polyol having up to about 100 carbon atoms and from about 2 to about 15 hydroxyl groups; and

(II) a C₅ -C₉ lactone, wherein there are, on the average, from about 0.2 to about 100 molar equivalents of C₅ -C₉ lactone derived moieties per molar equivalent of said reaction product (I) used in the reaction, said reaction product (I) having been prepared by heating together reactants (a) and (b) at a temperature of from about 100°

to about 250°

C. for a period of from about 1 to about 10 hours, and said dispersant having been prepared by heating together reactants (I) and (II) at a temperature of from about 50°

to about 200°

C. for a period of time sufficient to effect ring opening polymerization of said C₅ -C₉ lactone.

28. An oil soluble dispersant according to claim 27, wherein said C₅ -C₉ lactone is caprolactone and said dispersant contains the unit ##STR13## wherein m has an average value of from about 0.2 to about 50 and x is whole number of from 4 to 8.

29. An oil soluble dispersant according to claim 28, wherein said polyol is selected from the group consisting of aliphatic polyhydric alcohols having from about 2 to about 20 total carbon atoms and from 2 to about 15 hydroxyl groups and 2,2-disubstituted-2-amino-1-alkanols.

30. An oil soluble dispersant according to claim 29, wherein m has an average value of from about 0.5 to 20, and said polyol is pentaerythritol.

31. An oil soluble dispersant according to claim 29, wherein m has an average value of from about 0.5 to 20, and said polyol is tris(hydroxymethyl) amino methane.

32. An oil soluble dispersant according to claim 31, wherein said reaction product (I) is a bis-oxazoline.

33. An oil soluble dispersant according to claim 31, wherein said reaction product (I) is a lactone-oxazoline.

34. An oil soluble dispersant according to claim 29, wherein said C₄ to C₁₀ monounsaturated dicarboxylic acid material is maleic anhydride and said olefin polymer is polyisobutylene.

35. An oil soluble dispersant according to claim 34, wherein m has an average value of from about 0.5 to 20, and said polyol is pentaerythritol.

36. An oil soluble dispersant according to claim 34, wherein m has an average value of from about 0.5 to 20, and said polyol is tris(hydroxymethyl) amino methane.

37. An oil soluble reaction product useful as an oil additive, comprising.

(a) a polymer consisting essentially of C₂ to C₁₀ monoolefin, said polymer being of 300 to 10,000 number average molecular weight and being substituted with succinic moieties selected from the group consisting of acid, anhydride and ester groups, wherein there are from about 0.7 to about 2.0 molar proportions of said succinic moieties per molar proportion of said polymer,

(b) a polyol selected from the group consisting of aliphatic polyhydric alcohols containing from about 2 to about 20 carbon atoms and from 2 to about 15 hydroxyl groups and 2,2-disubstituted-2-amino-1-alkanol of the formula ##STR14## wherein X is an alkyl or hydroxyalkyl group with the alkyl groups having from 1 to 3 carbon atoms, wherein at least one of the X substituents is a hydroxyalkyl group of the formula--(CH₂)_n OH, and wherein n is 1 to 3 and containing 2 to 60 carbon atoms and 2 to 12 nitrogen groups, and

(c) a C₅ -C₉ lactone, wherein (a) is first reacted with (b) at a temperature of from about 100°

to about 250°

C. for a period of from about 1 to about 10 hours to form an intermediate reaction product which is then reacted with (c) at a temperature of from about 50°

to about 200°

C. for a period sufficient to effect ring opening polymerization of (c), and wherein there are an average of from about 0.2 to about 100 molar proportions of (c) per molar proportion of said oil soluble reaction product.

38. An oil soluble reaction product according to claim 37, wherein (b) is selected from pentaerythritol and tris(hydroxymethyl) amino methane.

39. An oil soluble reaction product according to claim 38, wherein said C₅ -C₉ lactone is caprolactone.

40. An oil soluble reaction product according to claim 38, wherein (a) is polyisobutylene of about 700 to 3,000 number average molecular weight substituted with succinic anhydride moieties.

41. An oil soluble reaction product according to claim 40, wherein (c) is E-caprolactone and wherein there are an average of from 0.5 to 20 molar proportions of (c) per molar proportion of said reaction product.

42. An oil soluble reaction product according to claim 41, wherein (b) is pentaerythritol.

43. An oil soluble reaction product according to claim 41, wherein (b) is tris(hydroxymethyl) amino methane, and wherein (a) and (b) are reacted to form a bis-oxazoline intermediate which is then reacted with (c).

44. An oil soluble reaction product according to claim 41, wherein (b) is tris(hydroxymethyl) amino methane, and wherein (a) and (b) are reacted to form a lactone-oxazoline intermediate which is then reacted with (c).