Lactone modified polymeric amines useful as oil soluble dispersant additives

• US 4,866,142 A
• Filed: 10/07/1986
• Issued: 09/12/1989
• Est. Priority Date: 10/07/1986
• Status: Expired due to Term

• 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:
  US06/916,303
• Time in Patent Office: 1,071 Days
• Field of Search: 525/331.7, 525/333.7, 525/334.1, 544/176, 544/386, 548/352, 564/152, 564/153, 564/201
• US Class Current: 525/333.7
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 2810/20 leading to a crosslinking, either explicitly or inherently
• CPC Class Codes: C08F 8/16 Lactonisation
• CPC Class Codes: C08G 63/08 Lactones or lactides
• CPC Class Codes: C10L 1/2383 Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C) C10L1/221 takes precedence
• CPC Class Codes: C10M 133/54 Amines
• CPC Class Codes: C10M 149/14 a condensation reaction being involved
• CPC Class Codes: C10M 159/18 Complexes with metals
• CPC Class Codes: C10M 2215/04 having amino groups bound to acyclic or cycloaliphatic carbon atoms
• CPC Class Codes: C10M 2215/26 Amines
• CPC Class Codes: C10M 2217/00 Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
• CPC Class Codes: C10M 2217/02 Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C10M 2217/04 Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C10M 2217/042 between the nitrogen-containing monomer and an aldehyde or ketone
• CPC Class Codes: C10M 2217/043 Mannich bases
• CPC Class Codes: C10M 2217/044 Polyamides
• CPC Class Codes: C10M 2217/045 Polyureas; Polyurethanes
• 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 2223/045 Metal containing thio derivatives
• CPC Class Codes: C10N 2010/04 : Groups 2 or 12
• CPC Class Codes: C10N 2040/00 : Specified use or application for which the lubricating composition is intended
• 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 2040/25 : Internal-combustion engines
• CPC Class Codes: C10N 2040/251 : Alcohol-fuelled engines
• CPC Class Codes: C10N 2040/252 : Diesel engines
• CPC Class Codes: C10N 2040/253 : Small diesel 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

Abstract

Hydroxyl terminated polymeric C₅ -C₉ lactone adducts are made by reacting a C₅ -C₉ lactone with the reaction product of a C₂ -C₁₀ olefin polymer or a halogenated derivative thereof having a number average molecular weight of 300 to about 10,000 with an amine containing from 2 to 60 total carbon atoms and from 1 to 12 nitrogen atoms. The resulting adducts are useful per se as oil soluble dispersant additives. They are also useful in fuel and lubricating oil compositions, as well as in concentrates and additive packages.

Claims

1. A hydroxyl terminated polymeric adduct of a C₅ -C₉ lactone and a polyalkylene amine material useful as an oil additive, said adduct being formed by reacting a C₅ -C₉ lactone with a polyalkylene amine at a temperature of from about 30 to about 200°

C. for a period sufficient to effect ring opening polymerization of said C₅ -C₉ lactone, said polyalkylene amine, in turn, being formed by reacting an olefin polymer material comprising a major molar amount of a C₂ -C₁₀ monoolefin and having a number average molecular weight of about 300 to about 10,000 or a halogenated derivative thereof with an amine compound that is reactive therewith to add amino groups onto said olefin polymer material, said amine compound being selected from the group consisting of amines of about 2 to about 60 total carbon atoms and about 1 to 12 nitrogen atoms in the amine molecule, and said adduct containing the unit ##STR6## where z is a number from 4 to 8 and m, which represents the degree of polymerization of said C₅ -C₉ lactone, has an average value of from about 0.2 to about 100.

2. The hydroxyl terminated polymeric adduct material according to claim 1, wherein said C₅ -C₉ lactone is E-caprolactone.

3. The hydroxyl terminated polymeric adduct material according to claim 2, wherein said olefin polymer is selected from polyisobutylene and halogenated polyisobutylene.

4. The hydroxyl terminated polymeric adduct material according to claim 3, wherein said amine compound is an aliphatic saturated amine having the formula:

##STR7## 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 aldylene 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, provided, however, that when t=0, at least one of R and R'"'"' must be hydrogen.

5. The hydroxyl terminated polymeric adduct material of claim 4, wherein said amine compound is selected from the group consisting of 1,2-diaminoethane;

1,3-diaminopropane;

1,4-diaminobutane;

1,6-diaminohexane;

diethylene amine;

triethylene tetramine;

tetraethylenepentamine;

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.

6. The hydroxyl terminated polymeric adduct material according to claim 3, wherein said amine compound is selected from the group consisting of alicylcic diamines, imidazolines, morpholines, and N-aminoalkyl piperazines of the general formula:

##STR8## wherein G is selected from the group consisting of hydrogen and omega-(nontertiary) aminoalkylene radicals of 1 to 3 carbon atoms, and p is a number from 1 to 4.

7. The hydroxyl terminated polymeric adduct material according to claim 3, wherein said amine compound is a mixture of poly(ethyleneamines) averaging about 5 to 7 nitrogen atoms per molecule.

8. The hydroxyl terminated polymeric adduct material according to claim 3, wherein said amine compound is a polyoxyalkylene polyamine having the formulae:

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

where 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.

9. The hydroxyl terminated polymeric adduct material according to claim 2, wherein the average value of m is from about 1 to about 20.

10. The hydroxyl terminated polymeric adduct according to claim 3, wherein the average value of m is from about 1 to about 20.

11. The hydroxyl terminated polymeric adduct material according to claim 9, wherein said olefin polymer has a molecular weight in the range of about 700 to 5,000.

12. The hydroxyl terminated polymeric adduct material according to claim 10, wherein said olefin polymer has a number average molecular weight in the range of about 700 to 5,000.

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

(I) the reaction of (a) an olefin polymer of a C₂ to C₁₀ monoolefin having a number average molecular weight of about 300 to 10,000 or a halogenated derivative thereof and (b) an amine having from about 2 to about 60 total carbon atoms and about 1to 12 nitrogen atoms in the amine molecule; and

(II) a C₅ -C₉ lactone, wherein said C₅ -C₉ lactone has undergone ring opening polymerization and 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.

14. An oil soluble dispersant according to claim 13, wherein said C₅ -C₉ lactone is caprolactone and wherein said dispersant contains the unit ##STR9## wherein the average value of m is from 1 to about 20.

15. An oil soluble dispersant according to claim 13, wherein said amine is an aliphatic 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, provided, however, that when t=0, at least one of R and R'"'"' must be hydrogen.

16. An oil soluble dispersant according to claim 15, 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-propylenediamine;

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.

17. The oil soluble dispersant of claim 14, wherein said amine is selected from the group consisting of alicyclic diamines, imidazoles, morpholines, and N-aminoalkyl piperazines of the general formula:

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

18. An oil soluble dispersant according to claim 14, wherein said amine is a mixture of poly(ethyleneamines) averaging about 5 to about 7 nitrogen atoms per molecule.

19. A soluble dispersant according to claim 14, 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

where m has a value of about 3 to 70;

or

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

where 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.

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

(a) polymer or halogenated derivative thereof consisting essentially of C₂ to C₁₀ monoolefin, said polymer being of 300 to 10,000 number average molecular weight;

(b) amine containing 2 to 60 carbon atoms and 1 to 12 amino groups, and

(c) C₅ -C₉ lactone, wherein (a) is first reacted with (b) to add lactone-reactive amino groups to said polymer or halogenated derivative thereof, and then the resulting product is reacted with (c) at a temperature of from about 30°

to about 200°

C. for a period sufficient to effect ring opening polymerization of said C₅ -C₉ lactone, and wherein there are, on the average, from about 0.2 to about 100 molar proportions of (c) reacted per molar proportion of said oil soluble reaction product.

21. An oil soluble reaction product according to claim 20, wherein (b) is an aliphatic saturated amine having the general formula:

##STR12## 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 alklamino C₂ to C₆ alkylene radicals;

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

t is a number from 0 to 10, provided, however, that when t=0, at least one of R and R'"'"' is hydrogen.

22. An oil soluble reaction product according to claim 21, wherein (b) is a polyamine 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-propylenediamine;

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.

23. An oil soluble reaction product according to claim 20, wherein (b) is a mixture of poly(ethyleneamines) averaging about 5 to 7 nitrogen atoms per molecule.

24. An oil soluble reaction product according to claim 20, wherein (a) is polyisobutylene or a halogenated polyisobutylene of about 700 to 5,000 molecular weight.

25. An oil soluble reaction product according to claim 24, wherein (c) is E-caprolactone and wherein there/ are 1 to 20 molar proportions of (c) per molar proportion of said oil soluble reaction product.

26. An oil soluble reaction product according to claim 25, wherein (b) is an aliphatic saturated amine having the formula:

##STR13## 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 from 0 to 10, provided, however, that when t=0, at least one of R and R'"'"' is hydrogen.

27. An oil soluble reaction product according to claim 20, wherein (c) is E-caprolactone and wherein there are, on the average, about 1 to 20 molar proportions of (c) per molar proportion of said oil soluble reaction product.

28. An oil soluble reaction product according to claim 21, wherein (c) is E-caprolactone and wherein there are, on the average, about 1 to 20 molar proportions of (c) per molar proportion of sad oil soluble reaction product.

29. An oil soluble reaction product according to claim 27, wherein (b) is a polyamine 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-propylenediamine;

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.

30. An oil soluble reaction product according to claim 27, wherein (b) is a mixture of poly(ethyleneamines) averaging about 5 to 7 nitrogen atoms per molecule.