Cationic ring-opening copolymerization of seven-membered cyclic sulfite and oxetane in one-shot feeding

Authors

  • Natsuhiro Azuma,

    1. Research Laboratory of Resources Utilization, Tokyo Institute of Technology, Nagatsuta-cho, Midori-ku, Yokohama 226, Japan
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  • Fumio Sanda,

    1. Research Laboratory of Resources Utilization, Tokyo Institute of Technology, Nagatsuta-cho, Midori-ku, Yokohama 226, Japan
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  • Toshikazu Takata,

    1. Research Laboratory of Resources Utilization, Tokyo Institute of Technology, Nagatsuta-cho, Midori-ku, Yokohama 226, Japan
    Current affiliation:
    1. Department of Applied Chemistry, Faculty of Engineering, University of Osaka Prefecture, Gakuen-cho, Sakai, Osaka 593, Japan
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  • Takeshi Endo

    Corresponding author
    1. Research Laboratory of Resources Utilization, Tokyo Institute of Technology, Nagatsuta-cho, Midori-ku, Yokohama 226, Japan
    • Research Laboratory of Resources Utilization, Tokyo Institute of Technology, Nagatsuta-cho, Midori-ku, Yokohama 226, Japan
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Abstract

Cationic copolymerization of seven-membered cyclic sulfite, 1,3,2-dioxathiepane-2-oxide (1) and oxetane (2) in one-shot feeding was carried out to obtain the corresponding copolymer. When a mixture of equimolar amount of 1 and 2 reacted at 0°C in the presence of methyl trifluoromethanesulfonate (T fOMe) as a cationic initiator, T fOMe and 2 were completely consumed without the consumption of 1. After rising the polymerization temperature up to 25°C, 1 started to be consumed to obtain the corresponding copolymer of 1 and 2. The obtained copolymer showed a unimodal GPC curve, and it afforded a polyether showing a unimodal GPC after alkaline hydrolysis. These results strongly suggested the occurrence of the block copolymerization in one-shot feeding. From the molecular orbital examination, the formation of block copolymerization in one-shot feeding was discussed to be caused by the much larger polymerizability of 2 than that of 1. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1007–1012, 1997

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