Lactone modified, esterfied or aminated additives useful in oleaginous compositions and compositions containing same

• US 4,866,141 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:
  US06/916,217
• Time in Patent Office: 1,071 Days
• Field of Search: 525/333.7, 548/237, 549/267, 560/196, 560/198, 564/159
• US Class Current: 525/333.7
• 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 63/912 derived from hydroxycarboxylic acids
• 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 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 2207/289 containing free hydroxy groups
• CPC Class Codes: C10M 2209/084 Acrylate; Methacrylate
• CPC Class Codes: C10M 2209/086 polycarboxylic, e.g. maleic acid
• 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 2010/12 : Groups 6 or 16
• CPC Class Codes: C10N 2070/02 : Concentrating of additives

Abstract

C₅ -C₉ lactone derived materials are made by simultaneously reacting (a) a C₅ -C₉ lactone with (b) a polyamine, a polyol or an amino alcohol and (c) a hydrocarbyl substituted C₄ -C₁₀ monounsaturated dicarboxylic acid producing material, e.g., a polyisobutenyl succinimide, which preferably was made by reacting a polymer of a C₂ to C₁₀ monoolefin, preferably polyisobutylene, having a molecular weight of about 300 to 10,000 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 molecule of said olefin polymer used in the reaction mixture. The resulting lactone derived materials, which may be post-treated, for example, with a boron compound, 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 derived material useful as an oil additive and formed by simultaneously reacting at a temperature of from about 100°

to about 220°

C. for a period of from about 1 to about 10 hours a hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material with a C₅ -C₉ lactone and a member selected from the group consisting of (a) a polyamine having from about 2 to 60 total carbon atoms and from about 2 to about 12 nitrogen atoms, (b) an aliphatic polyhydric alcohol containing up to about 100 carbon atoms and from about 2 to about 10 hydroxyl groups, (c) an amino alcohol containing up to about 50 total carbon atoms, from 1 to about 3 nitrogen atoms and from 1 to about 15 hydroxyl groups, or (d) mixtures thereof, 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 molar equivalents of dicarboxylic acid producing moieties per molar equivalent of said olefin polymer used in the reaction, said C₅ -C₉ lactone having undergone ring opening polymerization such that the degree of polymerization of said C₅ -C₉ lactone in the final C₅ -C₉ lactone derived material is from about 0.2 to about 100.

2. The C₅ -C₉ lactone derived material of claim 1, wherein said olefin polymer is polyisobutylene.

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

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

5. The C₅ -C₉ lactone derived material of claim 4, wherein there are about 1 to about 1.5 succinic anhydride units per polyisobutenyl moiety present in said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material and wherein the number average molecular weight of said polyisobutylene is from about 500 to about 3,000.

6. The C₅ -C₉ lactone derived material of claim 1, wherein said C₅ -C₉ lactone and said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material are reacted with a polyamine, and wherein said polyamine is an aliphatic saturated amine having the formula:

##STR8## wherein R and R'"'"' independently are selected from the group consisting of hydrogen, C₁ to C₂₅ straight or branched chain alkyl radicals, C₁ to C₁₂ alkoxy C₂ to C₆ alkylene radicals, and C₁ to C₁₂ alkylamino C₂ to C₆ alkylene radicals;

each s is the same or a different number of from 2 to 6, and t is a number of from 0 to 10, with the provision that when t=0, at least one of R or R'"'"' must be H such that there are at least two of either primary or secondary amino groups.

7. The C₅ -C₉ lactone derived material of claim 6, wherein said amine is selected from the group consisting of 1,2-diaminoethane;

1,3-diaminopropane;

1,4-diaminobutane;

1,6-diaminohexane;

diethylene triamine;

triethylene tetramine;

tetraethylene pentamine;

1,2-propylene diamine;

di-(1, 2-propylene)triamine;

di-(1,3-propylene) triamine;

N,N-dimethyl-1,3-diaminopropane;

N,N-di-(2-aminoethyl) ethylene diamine; and

N-dodecyl-1,3-propane diamine.

8. The C₅ -C₉ lactone derived material of claim 1, wherein said amine is selected from the group consisting alicyclic diamines, imidazolines, morpholines and N-aminoalkyl piperazines of the general formula:

##STR9## wherein G is independently selected from the group consisting of hydrogen and omega(nontertiary)-aminoalkylene radicals of from 1 to 3 carbon atoms, and p is a number of from 1 to 4.

9. The C₅ -C₉ lactone derived material of claim 1, wherein said amine is a mixture of poly (ethyleneamines) averaging about 5 to about 7 nitrogen atoms per molecule.

10. The C₅ -C₉ lactone derived material of claim 1, wherein said amine is a polyoxyalkylene polyamine having the formula:

space="preserve" listing-type="equation">NH.sub.2 --alkylene--(O--alkylene).sub.m --NH.sub.2

wherein m has a value of about 3 to 70;

or

space="preserve" listing-type="equation">R--[alkylene--(O--alkylene).sub.n --NH.sub.2 ].sub.a

wherein n has a value of about 1 to 40 with the provision that the sum of all the n'"'"'s is from about 3 to about 70, R is a substituted saturated hydrocarbon radical of up to 10 carbon atoms, wherein the number of substituents on the R group is represented by the value of "a", which is a number from 3 to 6.

11. The C₅ -C₉ lactone derived material of claim 5, wherein said C₅ -C₉ lactone and said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material are reacted with a polyamine, and wherein said polyamine is an aliphatic saturated amine having the formula:

##STR10## wherein R and R'"'"' independently are selected from the group consisting of hydrogen, C₁ to C₂₅ straight or branched chain alkyl radicals, C₁ to C₁₂ alkoxy C₂ to C₆ alkylene radicals, and C₁ to C₁₂ alkylamino C₂ to C₆ alkylene radicals;

each s is the same or a different number of from 2 to 6; and

t is a number of from 0 to 10, with the provision that when t=0, at least one of R or R'"'"' must be H such that there are at least two of either primary or secondary amino groups.

12. The C₅ -C₉ lactone derived material of claim 11, wherein said amine is selected from the group consisting of 1,2-diaminoethane;

1,3-diaminopropane;

1,4-diaminobutane;

1,6-diaminohexane;

diethylene triamine;

triethylene tetramine;

tetraethylene pentamine;

1,2-propylene diamine;

di-(1,2-propylene)triamine;

di-(1,3-propylene) triamine;

N,N-dimethyl-1,3-diaminopropane;

N,N-di(2-aminoethyl) ethylene diamine; and

N-dodecyl-1,3-propane diamine.

13. The C₅ -C₉ lactone derived material of claim 5, wherein said amine is selected from the group consisting alicyclic diamines, imidazolines, morpholines, and N-aminoalkyl piperazines of the general formula:

##STR11## wherein G is independently selected from the group consisting of hydrogen and omega-(nontertiary)aminoalkylene radicals of from 1 to 3 carbon atoms, and p is a number of from 1 to 4.

14. The C₅ -C₉ lactone derived material of claim 5, wherein said amine is a mixture of poly (ethyleneamines) averaging about 5 to about 7 nitrogen atoms per molecule.

15. The C₅ -C₉ lactone derived material of claim 5, wherein said amine is a polyoxyalkylene polyamine having the formula:

space="preserve" listing-type="equation">NH.sub.2 --alkylene--(O--alkylene).sub.m --NH.sub.2

wherein m has a value of about 3 to 70;

or

space="preserve" listing-type="equation">R--[alkylene--(O--alkylene).sub.n --NH.sub.2 ].sub.a

wherein n has a value of about 1 to 40 with the provisions that the sum of all the n'"'"'s is from about to about 60, R is a substituted saturated hydrocarbon radical of up to 10 carbon atoms, wherein the number of substituents on the R group is represented by the value of "a", which is a number from 3 to 6.

16. The C₅ -C₉ lactone derived material of claim 1, wherein said C₅ -C₉ lactone and said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material are reacted with a polyhydric alcohol.

17. The C₅ -C₉ lactone derived material of claim 16, wherein said polyhydric alcohol is an aliphatic alcohol containing from 3 to 15 carbon atoms and at least three hydroxyl groups.

18. The C₅ -C₉ lactone derived material of claim 17, 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.

19. The C₅ -C₉ lactone derived material of claim 5, wherein said C₅ -C₉ lactone is reacted with a polyhydric alcohol.

20. The C₅ -C₉ lactone derived material of claim 19, wherein said polyhydric alcohol is an aliphatic alcohol containing from 3 to 15 carbon atoms and at least three hydroxyl groups.

21. The C₅ -C₉ lactone derived material 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 C₅ -C₉ lactone derived material of claim 1, wherein said C₅ -C₉ lactone and said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material reacted with an amino alcohol.

23. The C₅ -C₉ lactone derived material of claim 22, wherein said amino alcohol is a 2,2-disubstituted-2-amino-1-alkanol of the formula ##STR12## wherein X is 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.

24. The C₅ -C₉ lactone derived material of claim 23, wherein said amino alcohol tris (hydroxymethyl) amino methane.

25. The C₅ -C₉ lactone derived material of claim 5, wherein said C₅ -C₉ lactone is reacted with an amino alcohol.

26. The C₅ -C₉ lactone derived material of claim 25, wherein said amino alcohol is a 2,2-disubstituted-2-amino-1-alkanol of the formula:

##STR13## wherein X is 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.

27. The C₅ -C₉ lactone derived material of claim 26, wherein said amino alcohol tris (hydroxymethyl) amino methane.

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

(i) a hydrocarbyl substituted C₄ -C₁₀ monounsaturated dicarboxylic acid producing material formed by reacting olefin polymer of C₂ to C₁₀ monoolefin having a molecular weight of about 300 to 10,000 and a C₄ to 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;

(ii) a C₅ -C₉ lactone; and

(iii) at least one member selected from the group consisting of (a) a polyamine having from about 2 to 60 total carbon atoms and from about 2 to about 12 nitrogen atoms, (b) an aliphatic polyhydric alcohol containing up to about 100 total carbon atoms and from about 2 to about 10 hydroxyl groups, and (c) an amino alcohol containing up to about 50 total carbon atoms, from 1 to about 3 nitrogen atoms and from 1 to about 15 hydroxyl groups, wherein they are from 1 to about 5 molar equivalents of C₅ -C₉ lactone derived moieties per molar equivalent of the oil soluble dispersant reaction product, and wherein said reaction mixture has heated at a temperature of from about 100°

to about 220°

C. for a period of from about 1 to about 10.

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

30. An oil soluble dispersant according to claim 29, wherein said caprolactone and said hydrocarbyl substituted dicarboxylic acid producing material are reacted with a polyamine.

31. An oil soluble dispersant according to claim 30, wherein said polyamine is an aliphatic saturated amine having the general formula ##STR14## wherein R and R'"'"' independently are selected from the group consisting of hydrogen, C₁ to C₂₅ straight of branched chain alkyl radicals, C₁ to C₁₂ alkoxy C₂ to C₆ alkylene radicals, and C₁ to C₁₂ alkylamino C₂ to C₆ alkylene radicals:

each s is the same or a different number of from 2 to 6; and

t is a number of from 0 to 10, with the provision that when t=0, at least one of R or R'"'"' must be H such that there are at least two of either primary of secondary amino groups.

32. An oil soluble dispersant according to claim 31, wherein said polyamine is selected from the group consisting of 1,2-diaminoethane:

1,3-diaminopropane;

1,4-diaminobutane;

1,6-diaminohexane;

diethylene triamine;

triethylene tetramine;

tetraethylene pentamine;

1,2-propylene diamine;

di-(1,2-propylene)triamine;

di-(1,3-propylene) triamine;

N,N-dimethyl-1,3-diaminopropane;

N,N-di-(2-aminoethyl) ethylene diamine; and

N-dodecyl-1,3-propane diamine.

33. The oil soluble dispersant of claim 30, wherein said polyamine is selected from the group consisting alicyclic diamines, imidazoles, morpholines, and N-aminoalkyl piperazines of the general formula:

##STR15## wherein G is independently selected from the group consisting of hydrogen and omega-(nontertiary)-aminoalkylene radicals of from 1 to 3 carbon atoms, and p is a number of from 1 to 4.

34. The oil soluble dispersant of claim 30, wherein said polyamine is a mixture of poly(ethyleneamines) averaging about 5 to about 7 nitrogen atoms per molecule.

35. An oil soluble dispersant according to claim 30, wherein said polyamine is a polyoxyalkylene polyamine having the formula:

space="preserve" listing-type="equation">NH.sub.2 --alkylene--(--O--alkylene).sub.m --NH.sub.2

where m has a value of about 3 to 70;

or

space="preserve" listing-type="equation">R--[alkylene--(--O--alkylene).sub.n --NH.sub.2 ].sub.a

wherein n has a value of about 1 to 40 with the provision that the sum of all the n'"'"'s is from about 3 to about 70, R is a substituted saturated hydrocarbon radical of up to 10 carbon atoms, wherein the number of substituents on the R group is represented by the value of "a", which is a number from 3 to 6.

36. An oil soluble dispersant according to claim 29, wherein said caprolactone and said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material are reacted with a polyhydric alcohol.

37. An oil soluble dispersant according to claim 36, wherein said polyhydric alcohol is an aliphatic alcohol containing from 3 to 15 carbon atoms and at least three hydroxyl groups.

38. An oil soluble dispersant according to claim 37, 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.

39. An oil soluble dispersant according to claim 29, wherein said caprolactone and said hydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material are reacted with an amino alcohol.

40. An oil soluble dispersant according to claim 39, wherein said amino alcohol is a 2,2-disubstituted-2-amino-1-alkanol of the formula ##STR16## wherein X is a 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.

41. An oil soluble dispersant according to claim 40, wherein said amino alcohol is tris(hydroxymethyl)amino methane.

42. An oil soluble reaction product useful as an oil additive comprising:

(a) polymer consisting essentially of C₂ to C₁₀ monoolefin, said polymer being of 300 to 10,000 number average molecular weight and 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 succinic moieties per molar proportion of said polymer,

(b) amine containing 2 to 60 carbon atoms and 2 to 12 nitrogen groups, and,

(c) C₅ -C₉ lactone, wherein (a) (b) and (c) are reacted simultaneously at a temperature of from about 100°

to about 220°

C. for a period of from about 1 to about 10 hours, and wherein there are about 0.2 to 100 molar proportions of (c) per molar proportion of said oil soluble reaction product.

43. An oil soluble reaction product according to claim 42, wherein (a) is polyisobutylene of about 500 to 3,000 number average molecular weight substituted with succininc anhydride moieties, wherein (c) is E-caprolactone, and wherein there are about 0.5 to 20 molar proportions of (c) per molar proportion of said oil soluble reaction product.

44. An oil soluble reaction product useful as an oil additive having improved dispersancy and viscosity characteristics of:

(a) polymer consisting essentially of C₂ to C₁₀ monoolefin said polymer being of 300 to 10,000 number average molecular weight and 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 succinic moieties per molar proportion of said polymer,

(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 (a) (b) (c) are reacted simultaneously at a temperature of from about 100°

to about 220°

C. for a period of from about 1 to about 10 hours, and wherein there are about 0.2 to 100 molar proportions of (c) per molar proportion of said reaction product.

45. An oil soluble reaction product according to claim 44 wherein (a) is polyisobutylene of about 500 to 3,000 number average molecular weight substituted with succinic anhydride moieties, wherein (c) is E-caprolactone, and wherein there are about 0.5 to 20 molar proportions of (c) per molar proportion of said oil soluble reaction product.

46. An oil soluble reaction product useful as an oil additive which comprises:

(a) polymer consisting essentially of C₂ to C₁₀ monoolefin said polymer being of 300 to 10,000 number average molecular weight and 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 succinic moieties per molar proportion of said polymer,

(b) amino alcohol containing up to about 50 total carbon atoms, from 1 to about 3 nitrogen atoms and from 1 to about 15 hydroxyl groups, and

(c) C₅ -C₉ lactone, wherein (a) (b) and (c) are reacted simultaneously at a temperature of from about 100°

to about 220°

C. for a period of from about 1 to about 10 hours, and wherein there are about 0.2 to 100 molar proportions of (c) per molar proportion of said oil soluble reaction product.

47. An oil soluble reaction product according to claim 46 wherein (a) is polyisobutylene of about 500 to 3,000 molecular weight substituted with succinic anhydride moieties, wherein (c) is E-caprolactone, and wherein there are about 0.5 to 20 molar proporation of (c) per molar proportion of said oil soluble reaction product.