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A novel group transfer polymerization of 1‐trimethylsiloxy‐benzocyclobutene via hetero Diels‐Alder reaction
Author(s) -
Chino Keisuke,
Takata Toshikazu,
Endo Takeshi
Publication year - 1996
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.1996.030170302
Subject(s) - polymer chemistry , polymerization , monomer , molar mass distribution , diels–alder reaction , chemistry , ethylene , polymer , catalysis , organic chemistry
Abstract A novel group transfer polymerization via hetero‐Diels‐Alder reaction is described. When 1‐trimethylsiloxybenzocyclobutene ( 1 ) was treated with a catalytic amount of p ‐anisaldehyde (4‐methoxybenzaldehyde) and TASF (tris(dimethylamino)sulfonium difluorotrimethylsilanide) at room temperature for 0.5 h, poly[1,2‐phenylene‐1‐(trimethylsiloxy)ethylene] was obtained quantitatively. The number‐average molecular weight of the polymer was M̄ n = 2000 and the molecular weight distribution was narrow (ratio of weight‐to number‐average molecular weights M̄ w /M̄ n = 1.18). Structural characteristics suggested a polymerization mechanism involving isomerization of 1 to o ‐quinodimethane and successive hetero‐Diels‐Alder reaction leading to poly[1,2‐phenylene‐1‐trimethylsiloxy ethylene]. The living‐like nature of the polymerization was supported by a monomer addition experiment in which the molecular weight increased according to the increase of the added monomer.