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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 a nitrogen-containing five-membered aromatic ring having at least two hydrocarbyl substituent compounds

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 a nitrogen-containing five-membered aromatic ring having at least two hydrocarbyl substituent compounds attached to the ring.

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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 nitrogen-containing five-membered aromatic ring compounds selected f

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 nitrogen-containing five-membered aromatic ring compounds selected from pyrroles and imidazoles after high conversion of the monomer has occurred, wherein the pyrroles have the formula: wherein: (a) R1 and R2 form a fused aromatic ring of from 6 carbon atoms to 10 carbon atoms or an aliphatic ring of from 4 carbon atoms to about 8 carbon atoms, R4 is alkyl containing one carbon atom to about 20 carbon atoms, and R3 is hydrogen or 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 (b) R2 and R3 form a fused aromatic ring of from 6 carbon atoms to 10 carbon atoms or an aliphatic ring of from 4 carbon atoms to about 8 carbon atoms, and R1 and R4 are independently alkyl containing one carbon atom to about 20 carbon atoms; or (c) both R1 and R2, and R3 and R4, taken in pairs, independently form a fused aromatic ring of from 6 carbon atoms to 10 carbon atoms or an aliphatic ring of from 4 carbon atoms to about 8 carbon atoms; and the imidazoles have at least two hydrocarbyl substituents attached to the aromatic ring, provided the nitrogen containing five-membered aromatic ring is not: (a) 2-phenylindole; (b) 2-methylbenzimidazole; (c) 1,2-dimethylimidazole; (d) 2-phenylimidazole; and (e) 2,4,5-triphenylimidazole. 2. The method of claim 1, wherein the polyolefin is prepared in situ. 3. The method of claim 1, wherein the nitrogen-containing five-membered aromatic ring compound has the formula: wherein: (a) R1 and R2 form a fused aromatic ring of from 6 carbon atoms to 10 carbon atoms or an aliphatic ring of from 4 carbon atoms to about 8 carbon atoms, R4 is alkyl containing one carbon atom to about 20 carbon atoms, and R3 is hydrogen or 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 (b) R2 and R3 form a fused aromatic ring of from 6 carbon atoms to 10 carbon atoms or an aliphatic ring of from 4 carbon atoms to about 8 carbon atoms, and R1 and R4 are independently alkyl containing one carbon atom to about 20 carbon atoms; or (c) both R1 and R2, and R3 and R4, taken in pairs, independently form a fused aromatic ring of from 6 carbon atoms to 10 carbon atoms or an aliphatic ring of from 4 carbon atoms to about 8 carbon atoms. 4. The method of claim 3, wherein the pyrrole has the following formula: 5. The method of claim 1, wherein the polyolefin is polyisobutylene. 6. The method of claim 1, wherein the quenching is carried out at a temperature in the range of from about −130° C. to about 10° C. 7. The method of claim 6, wherein the quenching is carried out at a temperature in the range of from −80° C. to about 0° C. 8. The method of claim 7, wherein the quenching is carried out at a temperature in the range of from −70° C. to about −10° C. 9. The method of claim 8, wherein the quenching is carried out at a temperature in the range of from about −60° C. to about −20° C. 10. The method of claim 3, wherein each alkyl group on the pyrrole ring has from one carbon atom to about 12 carbon atoms. 11. The method of claim 10, wherein each alkyl group on the pyrrole ring has from one carbon atom to about 4 carbon atoms. 12. 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. 13. The method of claim 12, wherein the quasi-living polyolefin polymer product contains terminal tert-chloride chain ends. 14. The method of claim 12, wherein the Lewis acid is a titanium or boron halide. 15. The method of claim 14, wherein the Lewis acid is a titanium halide. 16. The method of claim 15, wherein the Lewis acid is titanium tetrachloride. 17. The method of claim 1, 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. 18. The method of claim 17, 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. 19. The method of claim 18, wherein the at least one cationically polymerizable monomer is isobutylene. 20. The method of claim 17, wherein two different cationically polymerizable monomers are employed. 21. The method of claim 17, wherein the initiator is multi-functional. 22. The method of claim 21, wherein the initiator is di-functional. 23. The method of claim 22, 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, 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. 24. The method of claim 17, wherein the initiator is mono-functional. 25. The method of claim 24, 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. 26. The method of claim 1, wherein the nitrogen-containing five-membered aromatic ring is an imidazole having at least two hydrocarbyl substituents attached to the aromatic ring. 27. The method of claim 26, wherein the imidazole having at least two hydrocarbyl substituents attached to the aromatic ring has the general formula: wherein R3 is branched alkyl containing from about 4 carbon atoms to about 20 carbon atoms, and wherein (a) R1 and R2 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, wherein at least one of R1 or R2 is not hydrogen; or (b) R1 and R2 form a fused aromatic ring of from 6 carbon atoms to 10 carbon atoms or an aliphatic ring of from 4 carbon atoms to 8 carbon atoms. 28. The method of claim 27, wherein R1 is methyl, R2 is hydrogen and R3 is tert-butyl. 29. 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. 30. The method of claim 29, wherein the molecular weight distribution, Mw/Mn, of the polyolefin polymer is present in the range of about 1.1 to about 2.0. 31. The method of claim 30, wherein the molecular weight distribution, Mw/Mn, of the polyolefin polymer is less than 1.5. 32. The method of claim 3, wherein the pyrrole is 2,3-dimethylindole. 33. The method of claim 1, wherein the polyolefin has at least 20 percent exo-olefin end groups. 34. The method of claim 1, wherein the polyolefin has at least 50 percent exo-olefin end groups. 35. The method of claim 1, wherein the polyolefin has at least 70 percent exo-olefin end groups. 36. 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 nitrogen-containing five-membered aromatic ring compounds selected from pyrroles and imidazoles after high conversion of the monomer has occurred, wherein the pyrroles have the formula: wherein: (a) R1 and R2 form a fused aromatic ring of from 6 carbon atoms to 10 carbon atoms or an aliphatic ring of from 4 carbon atoms to about 8 carbon atoms, R4 is alkyl containing one carbon atom to about 20 carbon atoms, and R3 is hydrogen or 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 (b) R2 and R3 form a fused aromatic ring of from 6 carbon atoms to 10 carbon atoms or an aliphatic ring of from 4 carbon atoms to about 8 carbon atoms, and R1 and R4 are independently alkyl containing one carbon atom to about 20 carbon atoms; or (c) both R1 and R2, and R3 and R4, taken in pairs, independently form a fused aromatic ring of from 6 carbon atoms to 10 carbon atoms or an aliphatic ring of from 4 carbon atoms to about 8 carbon atoms; and the imidazoles have at least two hydrocarbyl substituents attached to the aromatic ring, wherein the nitrogen containing five-membered aromatic ring compounds are pre-reacted with a Lewis acid, and provided the nitrogen containing five-membered aromatic ring is not: (a) 2-phenylindole; (b) 2-methylbenzimidazole; (c) 1,2-di-methylimidazole; (d) 2-phenylimidazole; and (e) 2,4,5-tri-phenylimidazole. 37. The method of claim 36 wherein the Lewis acid is TiCl4.