キハラ ノブヒロ   Kihara Nobuhiro
  木原 伸浩
   所属   神奈川大学  理学部 化学科
   職種   教授
言語種別 英語
発行・発表の年月 1999/07
形態種別 学術雑誌
査読 査読あり
標題 Significance of Stoichiometric Imbalance in Step Polymerization via Reactive Intermediate
執筆形態 共著
掲載誌名 Macromolecules
巻・号・頁 32(15),pp.4776-4783
著者・共著者 Nobuhiro Kihara, Shin-ichi Komatsu, Toshikazu Takata, Takeshi Endo
概要 The polycondensations of 2,2-dichloro-1,3-benzodioxole (I) and bisphenol A were carried out in refluxing chlorobenzene to give polyorthocarbonate (II). The highest mol. wt. of II was obtained when ca. 0.7 equiv excess of I was used and was much higher than that calcd. according to the conventional step polymn. theory. In the model reaction of I and phenol at -40 °C, the rate of the first nucleophilic displacement reaction (k1') was 27 times lower than that of the second reaction (k2') of monochloride formed by the first condensation. Analyses of the kinetic equations of the polycondensation showed that Mn of the polymer is higher with more stoichiometric imbalance (S) for a shorter polymn. time. As time elapses, a greater Mn is obsd. for smaller S value. For step polymn. in which the first reaction gives rise to acceleration of rate of the second reaction, in general, stoichiometric imbalance practically enhances mol. wt. of the polymer.
DOI 10.1021/ma981835l
ISSN 0024-9297