Direct synthesis of highly reactive polyisobutylenes via cationic polymerization of isobutylene co-initiated with TiCl sub(4) in nonpolar hydrocarbon media

Living cationic polymerization of isobutylene (IB) with 1-chlorine-2,4,4-trimethyl pentane (TMPCl)/TiCl sub(4)/isopropanol (iPrOH) or isoamylol (iAmOH) has been achieved in the presence of 2,6-di-tert-butylpyridine (DtBP) at -80 degree C. Polyisobutylenes with nearly theoretical M sub(n) based on TM...

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Bibliographic Details
Published in:Journal of applied polymer science 2015-08, Vol.132 (29), p.np-np
Main Authors: Yang, Xiao-jian, Guo, An-ru, Xu, Hui-chao, Wu, Yi-xian
Format: Article
Language:English
Subjects:
Cationic polymerization
Chains (polymeric)
Hydrocarbons
Manganese
Polarity
Polyisobutylenes
Synthesis
Terminals
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Summary:Living cationic polymerization of isobutylene (IB) with 1-chlorine-2,4,4-trimethyl pentane (TMPCl)/TiCl sub(4)/isopropanol (iPrOH) or isoamylol (iAmOH) has been achieved in the presence of 2,6-di-tert-butylpyridine (DtBP) at -80 degree C. Polyisobutylenes with nearly theoretical M sub(n) based on TMPCl molecules and more than 90% of tert-chlorine-end groups could be obtained at high [TMPCl]. The beta -proton elimination from --CH sub(3) in growing chain ends increased with increasing polymerization temperature and decreasing solvent polarity. A chain-transfer-dominated cationic polymerization process with H sub(2)O/TiCl sub(4)/iAmOH could be achieved in n-hexane at -30 degree C. The monomer conversion and content of exo-olefin end groups increased while molecular weight decreased with increasing [iAmOH]. To the best of our knowledge, this is the first example to achieve the direct synthesis of highly reactive polyisobutylene with low M sub(n) of 12001600, carrying more than 80% of exo-olefin terminals by a single-step process via cationic polymerization co-initiated by TiCl sub(4) in nonpolar hydrocarbon. copyright 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42232.
ISSN:0021-8995
1097-4628
DOI:10.1002/app.42232