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Synthesis of polymers containing pseudohalide groups by cationic polymerization—12. Polymerization of 2-methyl-propene initiated by the system DI(1-azido-1-methylethyl)-1,4-benzene/boron trichloride

✍ Scribed by Berhooz Rajabalitabar; Hung Anh Nguyen; Herve Cheradame

Publisher
Elsevier Science
Year
1995
Tongue
English
Weight
373 KB
Volume
31
Category
Article
ISSN
0014-3057

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✦ Synopsis

The polymerization of 2-methylpropene (MP) initiated by the system di(l-azido-l-methylethyl)-1,4-benzene (DAMEB)/boron trichloride in CH,CI, solution was carried out at different temperatures and with different ratios R = [BCl,]/[DAMEB]. At low temperature and for R higher than 2, the functionalities F,, and F, determined by FT i.r. and 'H NMR were higher than the theoretical values respectively of 2 and 1. Polymer analysis also indicates the presence of tert-butyl, tert-chlorine and terminal unsaturations. These results can be explained assuming that BCI,, a strong Lewis acid, can promote predominantly the dehydroazidation reaction of DAMEB giving rise to the formation in situ of a-methyl-styrene derivative, and the copolymerization of this latter with MP. HN, and/or H,O/BCl, combination can also initiate the MP polymerization leading to the formation of tert-butyl head-group. The presence of text-chlorine and azide end groups comes from the competition of two termination reactions: the recombination of the electrophilic-moiety with Cl and N; from the counterion.

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