研究者情報 | 神奈川大学

キハラ　ノブヒロ Kihara Nobuhiro 木原　伸浩所属神奈川大学理学部理学科神奈川大学大学院理学研究科理学専攻（化学領域）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