Polymerization of 1,3‐dienes containing functional groups: 8. Free‐radical polymerization of 2‐triethoxysilyl‐ 1,3‐butadiene |
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Authors: | Katsuhiko Takenaka Satomi Kawamoto Masamitsu Miya Hiroki Takeshita Tomoo Shiomi |
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Affiliation: | Department of Materials Science and Technology, Nagaoka University of Technology, 1603‐1 Kamitomioka, Nagaoka, Niigata 940‐2188, Japan |
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Abstract: | The presence of a bulky substituent at the 2‐position of 1,3‐butadiene derivatives is known to affect the polymerization behavior and microstructure of the resulting polymers. Free‐radical polymerization of 2‐triethoxysilyl‐1,3‐butadiene ( 1 ) was carried out under various conditions, and its polymerization behavior was compared with that of 2‐triethoxymethyl‐ and other silyl‐substituted butadienes. A sticky polymer of high 1,4‐structure ( ) was obtained in moderate yield by 2,2′‐azobisisobutyronitrile (AIBN)‐initiated polymerization. A smaller amount of Diels–Alder dimer was formed compared with the case of other silyl‐substituted butadienes. The rate of polymerization (Rp) was found to be Rp = kAIBN]0.5 1 ]1.2, and the overall activation energy for polymerization was determined to be 117 kJ mol?1. The monomer reactivity ratios in copolymerization with styrene were r 1 = 2.65 and rst = 0.26. The glass transition temperature of the polymer of 1 was found to be ?78 °C. Free‐radical polymerization of 1 proceeded smoothly to give the corresponding 1,4‐polydiene. The 1,4‐E content of the polymer was less compared with that of poly(2‐triethoxymethyl‐1,3‐butadiene) and poly(2‐triisopropoxysilyl‐1,3‐butadiene) prepared under similar conditions. Copyright © 2010 Society of Chemical Industry |
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Keywords: | Diels– Alder dimerization microstructure radical polymerization 2‐triethoxysilyl‐1 3‐butadiene |
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