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タイトル: 電子スピン共鳴法によるパナジウム錯体‐トリエチルアルミニウム系重合触媒に関する研究
その他のタイトル: Electron Spin Resonance Study on Polymerization Catalysts Derived from Vanadium Complex and Triethylaluminum
著者: 平木, 克磨 / 金子, 彰一 / 平井, 英史
著者(別表記) : Hiraki, Katsuma / Kaneko, Shoichi / Hirai, Hidefumi
発行日: 1973年12月
出版者: 長崎大学工学部 / Faculty of Engineering, Nagasaki University
引用: 長崎大学工学部研究報告, (4), pp.106-112; 1973
抄録: Homogeneous catalysts derived from tris(acetylacetonato)vanadium(III) and triethylaluminum polymerize butadiene to 1, 2-type polymer with fairly high yields at 15℃ and 40℃ at molar ratios of aluminum to vanadium (Al/V molar ratios) of 5-20. ESR spectra of these catalysts are investigated at several temperatures from -72℃ to 25℃ at Al/V molar ratios of 1-50. The catalyst at Al/V molar ratios less than 2 shows an ESR signal (V。 signal) with 8 components and with a coupling constant of 62 gauss at -72℃ to 25℃. This signal is assigned to ditoluenevanadium(O) complex. At Al/V molar ratios larger than 5, a new ESR signal (V2 signal) with 8 components and with a coupling constant of about 80 gauss is observed at -72℃. With increasing temperature, this signal decreases gradually, while the V。 signal grows overlapping with the former sigrial each other. The V2 signal is ascribed to an unstable vanadium(II) complex coordinated with triethylaluminum, At temperatures above -10℃, the V。 signal is predominant. In the polymerization system prepared in the presence of butadiene, another new signal (Vp signal) with 8 components and with a coupling constant of 77 gauss is found at whole temperatures from -72℃ to 25℃, but diminishes gradually with standing at 25℃ for 4-14 days. This signal is associated with a vanadium(II) complex, which is yielded with the reaction between butadiene and the unstable vanadium(II) complex corresponding to the V2 signal in the catalyst solution. The relationship between the Vp signal and the growing end of polybutadiene with this catalyst is discussed.
URI: http://hdl.handle.net/10069/23811
ISSN: 02860902
資料タイプ: Departmental Bulletin Paper
原稿種類: publisher

引用URI : http://hdl.handle.net/10069/23811



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