LIVING CARBOCATIONIC POLYMERIZATION .30. ONE-POT SYNTHESIS OF ALLYL-TERMINATED LINEAR AND TRI-ARM STAR POLYISOBUTYLENES, AND EPOXY-TELECHELIC AND HYDROXY-TELECHELIC THEREFROM

Mono‐ and di‐ended linear and three‐arm star allyl‐telechelic polyisobutylenes, PIBA, APIBA and (where A = CH2CHCH2) 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 allphatic 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, unexpetedly, cationation to be rate determining. Quantitative derivatizations of the allyl termini have yielded mono‐, di‐, and tri‐epoxy‐ and ‐hydroxy‐telechelic PIBs. Strong rubbery networks have been made by curing the epoxy‐telechelic PIBs with triethylene tetramine and by reacting the hydroxy‐telechelic PIBs with MDI. Copyright © 1990 John Wiley & Sons, Inc.