Studies on Phosphorus-Containing Polymers. V. Ring-Opening Polymerization of Tetrahydrofuran Catalyzed by Linear Phosphonitrilic Chloride |
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| Authors: | Fumiaki Yamada Izumi Horii Toshihiko Yasui Isao Shinohara |
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| Institution: | 1. Department of Polymer , Chemistry Faculty of Science and Engineering Waseda University Nishiohkubo , Shinjuki-ku, Tokyo, 160, Japan;2. Department of Applied Chemistry , College of Technology and Engineering , Kogakuin University, Nishishinjuku, Shinjuku-ku, Tokyo, 160, Japan;3. Department of Polymer , Chemistry Faculty of Science and Engineering Waseda University Nishiohkubo , Shinjuki-ku, Tokyo, 160, Japan |
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| Abstract: | It was found that linear phosphonitrilic chloride could be used as a catalyst for ring-opening polymerization of tetrahydrofuran. Bulk polymerizations were carried out in a nitrogen atmosphere. After termination of polymerization, the reaction mixture was poured into water, thereby decomposing the catalyst. The product was dissolved in benzene and then subjected to lyophilization. The polymerization of tetrahydrofuran in the presence of linear phosphonitrilic chloride was found to be an equilibrium and a “living” polymerization. The polymerization product includes little phosphorus, and its infrared absorption spectrum agrees well with that of the polymer obtained with PF5 catalyst. The results of the polymerization using epichlorohydrin as a promoter show that the number of active sites in the molecule of linear phosphonitrilic chloride is considerably smaller. Consequently it is conceivable that the catalytic activity of the linear phosphonitrilic chloride is attributed to its terminal ～～P+Cl3PCl?6 structure. Furthermore we presume that the polymerization of tetra-hydrofuran in the presence of this catalyst proceeds through a cationic ring-opening mechanism. |
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