초록

The present invention is directed to a method for preparation of polyolefins containing exo-olefin chain ends. The method involves quenching a cationic quasi-living polyolefin polymer system with one or more hindered secondary or tertiary amines.

대표청구항 ▼

What is claimed is: 1. A method for preparing a polyolefin containing one or more exo-olefinic end groups on the polymer chain from a monomer, comprising quenching a cationic quasi-living polyolefin polymer system with one or more hindered secondary or tertiary amines containing only carbon, hydrog

What is claimed is: 1. A method for preparing a polyolefin containing one or more exo-olefinic end groups on the polymer chain from a monomer, comprising quenching a cationic quasi-living polyolefin polymer system with one or more hindered secondary or tertiary amines containing only carbon, hydrogen, and nitrogen atoms, provided the hindered secondary or tertiary amines are not: (a) Triethylamine; (b) Tri-n-butylamine; (c) Trihexylamine; (d) Triisooctylamine; (e) 2-phenylpyridine; (f) 2,3-cyclododenopyridine; (g) Di-p-tolylamine; (h) Quinaldine; and (i) 1-pyrrolidino-1-cyclopentene wherein said quenching comprises addition of said one or more hindered secondary or tertiary amines containing only carbon, hydrogen, and nitrogen atoms to said cationic quasi-living polyolefin polymer system after high conversion of the monomer has occurred. 2. The method of claim 1, wherein the quenching of the cationic quasi-living polyolefin polymer system is at a temperature in the range of about-130�� C. to about 10�� C. 3. The method of claim 2, wherein the quenching is carried out at a temperature in the range of about-80�� C. to about 0�� C. 4. The method of claim 3, wherein the quenching is carried out at a temperature in the range of about-70�� C. to about-10�� C. 5. The method of claim 4, wherein the quenching is carried out at a temperature in the range of from about-60�� C. to about-20�� C. 6. The method of claim 1, wherein the polyolefin is prepared in situ. 7. The method of claim 1, wherein the polyolefin is polyisobutylene. 8. The method of claim 1, wherein the hindered secondary or tertiary amine has the general formula: wherein R1, R2 and R3 are independently hydrogen, alkyl containing one carbon atom to about 20 carbon atoms, cycloalkyl of about 3 to about 7 carbon atoms, aryl of about 6 to about 30 carbon atoms, alkaryl of about 7 to about 30 carbon atoms, or aralkyl of about 7 to about 30 carbon atoms; or at least one of R1 and R2, R2 and R3 and R3 and R1, taken in pairs, independently form a fused aliphatic ring of from about 4 carbon atoms to about 8 carbon atoms; providing that no more than one of R1, R2 and R3 is hydrogen, and provided that R1, R2, and R3 are not all linear alkyl of about 3 carbons or less. 9. The method of claim l, wherein the hindered amine is a tertiary amine of the general formula: wherein one of R1 and R5 is hydrogen and the other is a branched alkyl of about 3 to about 20 carbon atoms, aryl of about 10 to about 30 carbon atoms, or aralkyl of about 11 to about 30 carbon atoms; R2, R3 and R4 are independently hydrogen, alkyl of one carbon atom to about 20 carbon atoms, cycloalkyl of about 3 to about 7 carbon atoms, aryl of about 6 to about 30 carbon atoms, alkaryl of about 7 to about 30 carbon atoms, or aralkyl of about 7 to about 30 carbon atoms; or at least one of R1 and R2, and R3 and R4, and R4 and R5, taken in pairs, independently form a fused aromatic ring of from 5 carbon atoms to 7 carbon atoms or aliphatic ring of from about 4 carbon atoms to about 8 carbon atoms, provided that if R1 and R2 form a fused aliphatic or aromatic ring, then R5 is a branched alkyl of about 3 to about 20 carbon atoms, aryl of about 10 to about 30 carbon atoms, or aralkyl of about 11 to about 30 carbon atoms, and provided that if R4 and R5 form a fused aliphatic or aromatic ring, then R1 is a branched alkyl of about 3 to about 20 carbon atoms, aryl of about 10 to about 30 carbon atoms, or aralkyl of about 11 to about 30 carbon atoms. 10. The method of claim 9, wherein R1 is hydrogen and R5 is tert-butyl and R2, R3 and R4 are hydrogen. 11. The method of claim l, wherein the quasi-living polyolefin polymer is formed by contacting at least one cationically polymerizable monomer with an initiator, in the presence of a Lewis acid under reaction conditions suitable for quasi-living polymerization. 12. The method of claim 11, wherein the at least one cationically polymerizable monomer comprises at least one of isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, and beta-pinene. 13. The method of claim 12, wherein the at least one cationically polymerizable monomer is isobutylene. 14. The method of claim 13, wherein two or more different cationically polymerizable monomers are employed. 15. The method of claim 11, wherein the initiator is multi-functional. 16. The method of claim 15, wherein the initiator is di-functional. 17. The method of claim 16, wherein the di-functional initiator comprises at least one of 1,3-di(2-chloro-2-propyl)-5-tert-butylbenzene, 1,4-di(2-chloro-2-propyl)benzene and 1,4-di(2-acetoxy-2-propyl)benzene, 1,3-di(2-acetoxy-2-propyl)-5-tert-butylbenzene, 1,3-di(2-methoxy-2-propyl)-5-tert-butylbenzene and 1,4-di(2-methoxy-2-propyl)benzene. 18. The method of claim 11, wherein the initiator is mono-functional. 19. The method of claim 18, wherein the mono-functional initiator comprises at least one of 2-chloro-2-phenylpropane; 2-acetoxy-2-phenylpropane; 2-propionoxy-2-phenylpropane, 2-methoxy-2-phenylpropane, 2-ethoxy-2-phenylpropane, 2-chloro-2,4,4-trimethylpentane, 2-acetoxy-2,4,4-trimethylpentane, 2-propionoxy-2,4,4-trimethylpentane, 2-methoxy-2,4,4-trimethylpentane, and 2-ethoxy-2,4,4-trimethylpentane. 20. The method of claim 1, wherein the molecular weight distribution, Mw/Mn, of the polyolefin polymer is present in the range of about 1.01 to about 3.0. 21. The method of claim 20, wherein the molecular weight distribution, Mw/Mn, of the polyolefin polymer is present in the range of about 1.1 to about 2.0. 22. The method of claim 21, wherein the molecular weight distribution, Mw/Mn, of the polyolefin polymer is less than 1.5. 23. The method of claim 1, wherein the polyolefin has at least 20 percent exo-olefin end groups. 24. The method of claim 1, wherein the polyolefin has at least 50 percent exo-olefin end groups. 25. The method of claim 1, wherein the product has at least 70 percent exo-olefin end groups. 26. A method for preparing a polyolefin containing one or more exo-olefinic end groups on the polymer chain from a monomer, comprising quenching a cationic quasi-living polyolefin polymer system with one or more hindered secondary or tertiary amines containing only carbon, hydrogen, and nitrogen atoms, wherein the hindered secondary or tertiary amine compounds are pre-reacted with a Lewis acid, and provided the hindered secondary or tertiary amines are not: (a) Triethylamine; (b) Tri-n-butylamine; (c) Trihexylamine; (d) Triisooctylamine; (e) 2-phenylpyridine; (f) 2,3-cyclododenopyridine; (g) Di-p-tolylamine; (h) Quinaldine; and (i) 1-pyrrolidino-1-cyclopentene and wherein said quenching comprises addition of said one or more hindered secondary or tertiary amines containing only carbon, hydrogen, and nitrogen atoms to said cationic quasi-living polyolefin polymer system after high conversion of the monomer has occurred. 27. The above method of claim 26, wherein the Lewis acid is titanium tetrachloride. 28. A method for preparing a polyolefin containing one or more exo-olefinic end groups on the polymer chain, comprising guenching a cationic quasi-living polyolefin polymer system with one or more hindered secondary or tertiary amines containing only carbon, hydrogen, and nitrogen atoms, provided the hindered secondary or tertiary amines are not: (a) Triethylamine; (b) Tri-n-butylamine; (c) Trihexylamine; (d) Triisooctylamine; (e) 2-phenylpyridine; (f) 2,3-cyclododenopyridine; (g) Di-p-tolylamine; (h) Quinaldine; and (i) 1-pyrrolidino-1-cyclopentene, wherein the hindered amine is a nitrogen containing hereto-aromatic having the following formulas, (a), (b) or (c) or mixtures thereof wherein in formula (a) one of R1 and R4 is hydrogen and the other is alkyl of one carbon atom to about 20 carbon atoms, cycloalkyl of about 3 to about 8 carbon atoms, aryl of about 6 to about 30 carbon atoms, alkaryl of about 7 to about 30 carbon atoms, or aralkyl of about 7 to about 30 carbon atoms, one of R2 and R3 is hydrogen and the other is alkyl of one carbon atom to about 20 carbon atoms, cycloalkyl of about 3 to about 8 carbon atoms, aryl of about 6 to about 30 carbon atoms, alkaryl of about 7 to about 30 carbon atoms, or aralkyl of about 7 to about 30 carbon atoms; or at least one of R1 and R2 and R3 and R4, taken in pairs, independently form a fused aromatic ring of from 5 carbon atoms to 7 carbon atoms or aliphatic ring of from about 4 carbon atoms to about 8 carbon atoms; wherein in formula (b) R1, R2 and R4 are independently hydrogen or alkyl of one carbon atom to about 20 carbon atoms, cycloalkyl of about 3 to about 8 carbon atoms, aryl of about 6 to about 30 carbon atoms, alkaryl of about 7 to about 30 carbon atoms, or aralkyl of about 7 to about 30 carbon atoms, R3 is hydrogen, alkyl of one carbon atom to about 20 carbon atoms, cycloalkyl of about 3 to about 8 carbon atoms, aryl of about 6 to about 30 carbon atoms, alkaryl of about 7 to about 30 carbon atoms, or aralkyl of about 7 to about 30 carbon atoms; or at least one of R2 and R3 or R3 and R4, taken in pairs, independently form a fused aromatic ring of from 5 carbon atoms to 7 carbon atoms or aliphatic ring of from about 4 carbon atoms to about 8 carbon atoms, provided that if R1 is hydrogen then R2 and R4 are independently alkyl of one carbon atom to about 20 carbon atoms, cycloalkyl of about 3 to about 8 carbon atoms, aryl of about 6 to about 30 carbon atoms, alkaryl of about 7 to about 30 carbon atoms, or aralkyl of about 7 to about 30 carbon atoms, and further provided that if R2 or R4 is hydrogen, then R1 is alkyl of one carbon atom to about 20 carbon atoms, cycloalkyl of about 3 to about 8 carbon atoms, aryl of about 6 to about 30 carbon atoms, alkaryl of about 7 to about 30 carbon atoms, or aralkyl of about 7 to about 30 carbon atoms; and wherein in formula (c) R1, R2 and R3 are independently hydrogen or alkyl of one carbon to about 20 carbon atoms, cycloalkyl of about 3 to about 8 carbon atoms, aryl of about 6 to about 30 carbon atoms, alkaryl of about 7 to about 30 carbon atoms, or aralkyl of about 7 to about 30 carbon atoms. 29. The method of claim 28, where the hindered amine has the formula: 30. The method of claim 28, where the hindered amine has the formula: 31. The method of claim 28, where the hindered amine has the formula: 32. The method of claim 1, wherein the polyolefin is prepared by quenching a quasi-living polyolefin polymer product containing terminal tert-chloride chain ends or a mixture of terminal tert-chloride chain ends and terminal olefinic chain ends in the presence of a Lewis acid. 33. The method of claim 32, wherein the quasi-living polyolefin polymer product contains terminal tert-chloride chain ends. 34. The method of claim 32, wherein the Lewis acid is a titanium or boron halide. 35. The method of claim 34, wherein the Lewis acid is titanium halide. 36. The method of claim 34, wherein the Lewis acid is titanium tetrachloride. 37. A method for preparing a polyolefin containing one or more exo-olefinic end groups on the polymer chain, comprising quenching a cationic quasi-living polyolefin polymer system with one or more hindered secondary or tertiary amines containing only carbon, hydrogen, and nitrogen atoms, provided the hindered secondary or tertiary amines are not: (a) Triethylamine; (b) Tri-n-butylamine; (c) Trihexylamine; (d) Triisooctylamine; (e) 2-phenylpyridine; (f) 2,3-cyclododenopyridine; (g) Di-p-tolylamine; (h) Quinaldine; and (i) 1-pyrrolidino-1-cyclopentene wherein said one or more hindered secondary or tertiary amines containing only carbon, hydrogen, and nitrogen atoms is selected from the group consisting of: wherein R6 is a divalent hydrocarbyl group of one carbon atom to about 4 carbon atoms, each of which may be substituted with an alkyl group having one carbon atom to about 6 carbon atoms, and R1, R2, R3, R4 and R5 are independently hydrogen, alkyl containing one carbon atom to about 20 carbon atoms, cycloalkyl of about 3 to about 8 carbon atoms, aryl of about 6 to about 30 carbon atoms, alkaryl of about 7 to about 30 carbon atoms, or aralkyl of about 7 to about 30 carbons; provided if R1, R2, R3, and R4 are hydrogen, then R5 is a branched alkyl having from about 4 to about 20 carbon atoms, aryl of about 6 to about 30 carbon atoms, or aralkyl of about 7 to about 30 carbon atoms, and provided if R5 is hydrogen, then R1, R2, R3, and R4, cannot be hydrogen unless either R1 or R2 and either R3 or R4 is a branched alkyl from about 4 to about 20 carbon atoms; and wherein R1 is a divalent hydrocarbyl group of one carbon atom to about 4 carbons and R2, R3, R4, R7, R8, and R9 are independently hydrogen, alkyl containing one carbon atom to about 20 carbon atoms, cycloalkyl of about 3 to about 8 carbon atoms, aryl of about 6 to about 30 carbon atoms, alkaryl of about 7 to about 30 carbon atoms, or aralkyl of about 7 to about 30 carbons, and one of R5 and R6 is hydrogen and the other is linear alkyl from one carbon atom to about 20 carbon atoms. 38. The method of claim 37, wherein the hindered amine is a tertiary amine of the formula: 39. The method of claim 37, wherein the hindered amine is a secondary amine of the formula: 40. The method of claim 37, wherein the hindered amine is a tertiary amine of the formula: 41. The method of claim 37 wherein the hindered amine is a tertiary amine of the formula: 42. The method of claim 37, wherein the hindered amine is a tertiary or secondary amine having the general formula: wherein R6 is a divalent hydrocarbyl group of one carbon atom to about 4 carbon atoms, each of which may be substituted with an alkyl group having one carbon atom to about 6 carbon atoms, and R1, R2, R3, R4 and R5 are independently hydrogen, alkyl containing one carbon atom to about 20 carbon atoms, cycloalkyl of about 3 to about 8 carbon atoms, aryl of about 6 to about 30 carbon atoms, alkaryl of about 7 to about 30 carbon atoms, or aralkyl of about 7 to about 30 carbons; provided if R1, R2, R3, and R4 are hydrogen, then R5 is a branched alkyl having from about 4 to about 20 carbon atoms, aryl of about 6 to about 30 carbon atoms, or aralkyl of about 7 to about 30 carbon atoms, and provided if R5 is hydrogen, then R1, R2, R3, and R4, cannot be hydrogen unless either R1 or R2 and either R3 or R4 is a branched alkyl from about 4 to about 20 carbon atoms. 43. The method of claim 42, wherein the hindered amine is a secondary or tertiary amine of the formula: wherein R5 is hydrogen or methyl. 44. The method of claim 37, wherein the hindered secondary or tertiary amine has the general formula: wherein R1 is a divalent hydrocarbyl group of one carbon atom to about 4 carbons and R2, R3, R4, R7, R8, and R9 are independently hydrogen, alkyl containing one carbon atom to about 20 carbon atoms, cycloalkyl of about 3 to about 8 carbon atoms, aryl of about 6 to about 30 carbon atoms, alkaryl of about 7 to about 30 carbon atoms, or aralkyl of about 7 to about 30 carbons, and one of R5 and R6 is hydrogen and the other is linear alkyl from one carbon atom to about 20 carbon atoms. 45. The method of claim 44, wherein one of R5 an R6 is hydrogen. 46. The method of claim 44, wherein the amine has the formula: 47. A method for preparing a polyolefin containing one or more exo-otefinic end groups on the polymer chain, comprising quenching a cationic quasi-living polyolefin polymer system with one or more hindered secondary or tertiary amines containing only carbon, hydrogen, and nitrogen atoms, wherein the hindered secondary or tertiary amine compounds are pre-reacted with a Lewis acid, and provided the hindered secondary or tertiary amines are not: (a) Triethylamine; (b) Tri-n-butylamine; (c) Trihexylamine; (d) Triisooctylamine; (e) 2-phenylpyridine; (f) 2,3-cyclododenopyridine; (g) Di-p-tolylamine; (h) Quinaldine; and (i) 1-pyrrolidino-1-cyclopentene, wherein the hindered amine is selected from the group consisting of 1 ,2,2,6,6-pentamethylpiperidine and 2,2,6,6-tetramethylpiperidine. 48. The method of claim 47, wherein the hindered amine is 1,2,2,6,6-pentamethylpiperidine. 49. The method of claim 47, wherein the Lewis acid is titanium tetrachloride and the hindered secondary or tertiary amine is 2,2,6,6-tetramethylpiperidine.