徳島大学 教育・研究者情報データベース(EDB)

1. 徳島大学.大学院ソシオテクノサイエンス研究部.ライフシステム部門.物質変換化学(2006年4月1日〜2016年3月31日)

1. 佐藤 恒之

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2. (英) Hasegawa Makoto

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3. 妹尾 真紀子

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4. 平野 朋広([徳島大学.大学院社会産業理工学研究部.理工学域.応用化学系.物質合成化学分野]/[徳島大学.理工学部.理工学科.応用化学システムコース.物質合成化学講座])

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(英) Radical polymerization behavior of diemthyl vinylphosphonate: homopolymerization and copolymerization with trimethoxyvinylsilane

(英) Dialkyl vinylphosphonates such as dimethyl vinylphosphonate (DMVP) and diethyl vinylphosphonate were quantitatively polymerized with dicumyl peroxide (DCPO) at 130°C in bulk. The polymerization of DMVP with DCPO was kinetically studied in bulk by fourier transform near-infrared spectroscopy (FTNIR) and electron spin resonance (ESR) spectroscopy. The initial polymerization rate (Rp) was given by Rp = k[DCPO]0.5[DMVP]1.0 at 110°C, being the same as that of the conventional radical polymerization involving bimolecular termination. The overall activation energy of the polymerization was estimated to be 26.2 kcal/mol. The polymerization system involved ESR-observable propagating polymer radicals under the practical polymerization conditions. ESR-determined rate constants of propagation (kp) and termination (kt) were kp = 19 L/mol s and kt = 5.8 × 103 L/mol s at 110°C, respectively. The molecular weight of the resultant poly(DMVP)s was low (Mn = 3.4 - 3.5 × 103), because of the high chain transfer constant (Cm = 3.9 × 10-2 at 110°C) to the monomer. DMVP (M1) showed a considerably high reactivity in the radical copolymerization with trimethoxyvinylsilane (TMVS) (M2) at 110°C in bulk, giving an inorganic component-containing functional copolymer with potential flame-retardant properties; r1 = 1.6 and r2 = 0.

(日) リン原子にビニル基が結合したモノマーのラジカル重合を行い，重合速度が通常の二分子停止を含む速度式で表わせることやモノマーへの連鎖移動反応が起こりやすいことなどを見出した．