A novel group transfer polymerization of 1-trimethylsiloxy-benzocyclobutene via hetero Diels-Alder reaction

✍ Scribed by Keisuke Chino; Toshikazu Takata; Takeshi Endo

• Book ID: 102491855
• Publisher: John Wiley and Sons
• Year: 1996
• Tongue: English
• Weight: 245 KB
• Volume: 17
• Category: Article
• ISSN: 1022-1336
• DOI: 10.1002/marc.1996.030170302

✦ Synopsis

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.