Living carbocationic polymerization. XXX. One-pot synthesis of allyl-terminated linear and tri-arm star polyisobutylenes, and epoxy- and hydroxy-telechelics therefrom

B. Iván, Joseph P. Kennedy

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169 Citations (Scopus)

Abstract

Mono- and di-ended linear and three-arm star allyl-telechelic polyisobutylenes, have been prepared by a rapid economical one-pot polymerization-functionalization process. The process involves the living polymerization of isobutylene (IB) by mono-, di-, or tri-functional initiating systems, specifically by aliphatic and aromatic tert-ester and -ether/TiCl4 combinations, followed by electrophilic functionalization of the living sites with allyl-trimethylsilane (ATMS). Structural characterization by 1H-NMR spectroscopy and end group titration with m-chloroperbenzoic acid (m-CPBA) indicate quantitative end allylation even with relatively slowly initiating systems like DiOAcTMH7/TiCl4. Detailed kinetic analysis of the latter system indicates, unexpectedly, cationation to be rate determining.

Original languageEnglish
Pages (from-to)89-104
Number of pages16
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume28
Issue number1
DOIs
Publication statusPublished - 1990

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Allylation
Living polymerization
Titration
Nuclear magnetic resonance spectroscopy
Stars
Ethers
Esters
Polymerization
Kinetics
Acids
Ether
titanium tetrachloride

ASJC Scopus subject areas

  • Polymers and Plastics
  • Materials Chemistry

Cite this

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abstract = "Mono- and di-ended linear and three-arm star allyl-telechelic polyisobutylenes, have been prepared by a rapid economical one-pot polymerization-functionalization process. The process involves the living polymerization of isobutylene (IB) by mono-, di-, or tri-functional initiating systems, specifically by aliphatic and aromatic tert-ester and -ether/TiCl4 combinations, followed by electrophilic functionalization of the living sites with allyl-trimethylsilane (ATMS). Structural characterization by 1H-NMR spectroscopy and end group titration with m-chloroperbenzoic acid (m-CPBA) indicate quantitative end allylation even with relatively slowly initiating systems like DiOAcTMH7/TiCl4. Detailed kinetic analysis of the latter system indicates, unexpectedly, cationation to be rate determining.",
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AB - Mono- and di-ended linear and three-arm star allyl-telechelic polyisobutylenes, have been prepared by a rapid economical one-pot polymerization-functionalization process. The process involves the living polymerization of isobutylene (IB) by mono-, di-, or tri-functional initiating systems, specifically by aliphatic and aromatic tert-ester and -ether/TiCl4 combinations, followed by electrophilic functionalization of the living sites with allyl-trimethylsilane (ATMS). Structural characterization by 1H-NMR spectroscopy and end group titration with m-chloroperbenzoic acid (m-CPBA) indicate quantitative end allylation even with relatively slowly initiating systems like DiOAcTMH7/TiCl4. Detailed kinetic analysis of the latter system indicates, unexpectedly, cationation to be rate determining.

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