Amidation of ester functionalized hydrocarbon polymers

• US 5,627,259 A
• Filed: 11/28/1995
• Issued: 05/06/1997
• Est. Priority Date: 06/17/1994
• Status: Expired due to Fees

• Current Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Zushma, Stephen, Gutierrez, Antonio, Gorda, Keith R., Dankworth, David C., Eckstrom, William B., Emert, Jacob I., Cusumano, Joseph V., Thaler, Warren A., Diana, William D.
• Primary Examiner(s): Seidleck, James J.
• Assistant Examiner(s): Hampton-Hightower, P.
• Application Number:
  US08/563,518
• Time in Patent Office: 525 Days
• Field of Search: 528/342, 528/345, 528/348, 526/272, 526/318.4, 526/318.6
• US Class Current: 528/342
• 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 255/10 on to butene polymers
• CPC Class Codes: C08F 8/32 by reaction with amines
• CPC Class Codes: C10L 1/2364 homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups C10L1/221 takes precedence
• CPC Class Codes: C10L 1/2366 homo- or copolymers derived from unsaturated compounds containing amine groups C10L1/221 takes precedence
• CPC Class Codes: C10L 1/238 obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds C10L1/221 takes precedence
• CPC Class Codes: C10L 1/2387 Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C) C10L1/221 takes precedence
• CPC Class Codes: C10L 10/00 Use of additives to fuels or fires for particular purposes additives for liquid carbonaceous fuels characterised by their chemical nature C10L1/10; using binders for briquetting solid fuels C10L5/10; using additives to improve the combustion of solid fuels C10L9/10
• CPC Class Codes: C10M 133/56 Amides; Imides
• 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 2217/046 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

Abstract

The present invention is directed to a process for preparing a polymeric amide which comprises the steps of:

(A) reacting a mixture of (i) functionalized hydrocarbon polymer containing ester functional groups comprising at least one member selected from the group consisting of substituted alkyl ester functional groups, the substituted alkyl moiety containing at least one electron withdrawing substituent group, and aryl ester functional groups, the hydrocarbon polymer having a number average molecular weight of at least about 500 prior to functionalization, and (ii) an amine having at least one reactive --NH₂ moiety, for a time and under conditions sufficient to form amide groups; and

(B) removing from the mixture during step (A) hydroxyl compound released from the ester functional groups in forming the amide groups.

The polymeric amides so produced are useful as fuel additives (e.g., detergents) and lubricating oil additives (e.g., dispersants).

Claims

1. A process for preparing a polymeric amide which comprises the steps of:

(A) reacting a mixture of (1) functionalized hydrocarbon polymer containing ester functional groups comprising at least one member selected from the group consisting of

(i) substituted alkyl ester functional groups of formula (I);

##STR6## wherein Ak is a substituted, linear or branched C₂ to C₁₀ alkyl group containing at least one electron withdrawing substituent group, and

(ii) aryl ester functional groups of formula (II);

##STR7## wherein Ar is an aryl group selected from an aromatic radical or a substituted aromatic radical,

wherein at least 50 mole % of the ester functional groups are neo ester functional groups, the hydrocarbon polymer having a number average molecular weight of at least about 500 prior to functionalization, and (2) an amine having at least one reactive --NH₂ moiety, for a time and under conditions sufficient to form amide groups; and

(B) removing from the mixture during step (A) hydroxy compound released from the ester functional groups in forming the amide groups, the released hydroxy compound having a pK_a of less than 12.

2. The process according to claim 1, wherein the amine comprises a heavy polyamine.

3. The process according to claim 1, wherein the amine comprises alkylene polyamine selected from the group consisting of ethylene polyamine, propylene polyamine and mixtures thereof.

4. The process according to claim 2, wherein the heavy polyamine comprises at least one heavy alkylene polyamine.

5. The process according to claim 4, wherein removing in step (B) comprises stripping the hydroxy compound from the mixture.

6. The process according to claim 5, wherein stripping comprises vacuum distillation.

7. The process according to claim 6, wherein the ester functional groups comprise an aryl ester functional group.

8. The process according to claim 7, wherein the aryl ester functional group comprises at least one member selected from the group consisting of phenyl ester and substituted phenyl esters.

9. The process according to claim 8, wherein the aryl ester functional group comprises at least one substituted phenyl ester selected from the group consisting of difluorophenyl esters, dichlorophenylesters, 4-methyldifluorophenyl esters, and 4-methyldichlorophenyl esters.

10. The process according to claim 9, wherein the substituted phenyl ester comprises 2,4-dichlorophenyl ester.

11. The process according to claim 6, wherein the ester functional groups comprise a substituted alkyl ester functional group.

12. The process according to claim 11, wherein the substituted alkyl ester functional group comprises a polyhaloalkyl ester functional group.

13. The process according to claim 12, wherein the polyhaloalkyl ester functional group comprises at least one member selected from the group consisting of polyfluoroalkyl ester functional groups.

14. The process according to claim 13, wherein the polyfluoroalkyl ester functional group comprises hexafluoroisopropyl ester functional group.

15. The process according to claim 2, wherein the hydrocarbon polymer prior to functionalization is selected from the group consisting of alpha-olefin homopolymers, alpha-olefin copolymers, ethylene-alpha-olefin copolymers, and mixtures thereof.

16. The process according to claim 15, wherein the hydrocarbon polymer comprises ethylene-alpha-olefin copolymer.

17. The process according to claim 16, wherein the ethylene-alpha-olefin polymer comprises ethylene-butene-1 copolymer.

18. The process according to claim 15, wherein the hydrocarbon polymer prior to functionalization is unsaturated, wherein at least about 30% of the polymer chains possess terminal ethenylidene unsaturation.

19. The process according to claim 1, wherein Ar is ##STR8## wherein X is an electron withdrawing group, each of which is the same or different;

T is a non-electron withdrawing group, each of which is the same or different; and

m and p are integers from 0 to 5.

20. The process according to claim 19, wherein X is halogen;

T is methyl or ethyl;

m is from 1 to 3; and

p is from 0 to 1.