Cationic polymerization behavior of seven-membered cyclic sulfite

Authors

  • Natsuhiro Azuma,

    1. Research Laboratory of Resources Utilization, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226, Japan
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  • Fumio Sanda,

    1. Research Laboratory of Resources Utilization, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226, Japan
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  • Toshikazu Takata,

    1. Research Laboratory of Resources Utilization, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226, Japan
    Current affiliation:
    1. Department of Applied Chemistry, Faculty of Engineering, University of Osaka Prefecture, Gakuencho, Sakai, Osaka 593, Japan
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  • Takeshi Endo

    Corresponding author
    1. Research Laboratory of Resources Utilization, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226, Japan
    • Research Laboratory of Resources Utilization, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226, Japan
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Abstract

Cationic ring-opening polymerization behavior of a seven-membered cyclic sulfite (1) was examined. 1 was prepared by the reaction of 1,4-butanediol with SOCl2 in 58% yield. The cationic polymerization of 1 was carried out at 0, 25, 60, or 100°C with trifluoromethanesulfonic acid (TfOH), methyl trifluoromethanesulfonate (TfOMe), BF3 · OEt2, SnCl4, methyl p-toluenesulfonate (TsOMe), or MeI as an initiator in bulk under a nitrogen atmosphere to afford the polymer with M̄n 1000–10,400. The order of activities of the initiators for 1 was as follows, TfOH ≅ TfOMe > SnCl4 > BF3 · OEt2 > TsOMe ≅ MeI. The polymerization of 1 with TfOMe afforded a poly(sulfite) below 25°C, but afforded a polymer containing an ether unit at 60°C, which was formed by a desulfoxylation. The higher the activity of the initiator was, the more easily the desulfoxylation occurred. We expected volume expansion on polymerization because cyclic sulfites have large dipole moment values, but it turned out that 1 showed 4.34% shrinkage on polymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3673–3682, 1997

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