New telechelic polymers and sequential copolymers by polyfunctional initiator-trans fer agents (inifers) - LV. Tert.-chlorine capped polyisobutylenes by aliphatic inifers

Soukhil Mah, Rudolf Faust, Miklos Zsuga, Joseph P. Kennedy

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8 Citations (Scopus)

Abstract

The unsaturated aliphatic dichlorides cis and trans Cl(CH3)2C-CH=CH-C(CH3)2Cl in conjunction with BCl3 have been found to be excellent binifers and yield tert.-Cl capped polyisobutylenes PIB in CH3Cl at -30°C. Intramolecul ar cyclization is absent and terminal chlorine functionality is Fn = 2.0±0.1. The normalized inifer constants have been determined: CI trans = 1.05, and CI cis = 3.8 and 1.05, respectively, for the first and second allylic chlorines in the cis isomer. The inequality of the chlorines have been analyzed. The cis and trans isomers have identical relative termination constants (kt/kp = 6×10-3). The structure of the PIBs obtained has been analyzed by a variety of techniques. Model experiments with isobutylene/Cl-(CH3)2C-CH=CH-C(CH3)2Cl = 2/1 in the presence of BCl3 gave the expected trans Cl(CH3)2CCH2-(CH3)2C-CH=CH-C(CH3)2-CH2C(CH3)2 -Cl. The end groups of polymers have been quantitated. The central position of the -CH=CH- residue in polymers has b een demonstrated by molecular weight determinations i.e., the Mn of PIB has decreased by a factor of two after oxidative cleavage. The uniform distribution of -CH=CH-group across all polymeric species has also been established.

Original languageEnglish
Pages (from-to)433-440
Number of pages8
JournalPolymer Bulletin
Volume18
Issue number5
DOIs
Publication statusPublished - Nov 1 1987

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ASJC Scopus subject areas

  • Chemistry(all)
  • Condensed Matter Physics
  • Polymers and Plastics
  • Materials Chemistry

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