Kinetic Study on the Ring-Opening Polymerization of Tetrahydrofuran by Pyrosulfuryl Chloride Initiator

• Shiro Kobayashi

  Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University

• Takeo Saegusa

  Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University

• Yoshiaki Tanaka

  Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University

抄録

This paper deals with a kinetic study of the ring-opening polymerization of tetrahydrofuran (THF) initiated by pyrosulfuryl chloride (PSC). The kinetic analysis was based on the determination of the concentration of propagating species, [P*], by the phenoxyl end-capping method. The rate constants of the three elementary processes, propagation (kp), initiation (ki), and termination (kt), were determined. Activation parameters for the propagation were; ΔEp\eweq=12 kcal/mol, and Ap=7.6×106 l/mol·sec. From the kp values and the NMR study of the THF–PSC reaction, it is concluded that the propagation proceeds via the bis-oxonium species 5b. The ester type species 5a may be involved at a very early stage of polymerization. However, its contribution was quite small throughout the polymerization. The THF polymerization initiated by PSC was characterized by the fast initiation. The mechanism of termination was also examined. The THF polymerization by trifluoromethanesulfonic anhydride was also studied kinetically, which was characterized by a living propagation by bis-oxonium species.

収録刊行物

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 46 (10), 3220-3224, 1973-10-01

  Oxford University Press (OUP)

キーワード

• General Chemistry

詳細情報

• CRID: 1360283694076644608
• NII論文ID: 130001974542
• DOI: 10.1246/bcsj.46.3220
• ISSN: 13480634
• ISSN: 00092673
• Web Site: https://academic.oup.com/bcsj/article-pdf/46/10/3220/56085522/bcsj.46.3220.pdf
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