Abstract

AbstractThe reactivity of trans‐1‐alkoxybutadienes in cationic homopolymerization and copolymerizations and structure of the polymers produced were investigated. 1‐Ethoxybutadiene is polymerized easily at −78°C by various acidic catalysis. The reactivity of 1‐ethoxybutadiene was similar to that of ethyl vinyl ether. The polymers produced possessed molecular weights of several thousands, and were composed of 70–95% 1,4 structure and 5–30% 3,4 structure. In the copolymerization of ethyl vinyl ether (M1) with 1‐ethoxybutadiene at −78°C in toluene by boron trifluoride diethyl etherate, r1 = 1.15, r2 = 2.62. From the Hammett plot of the relative reactivities of alkoxybutadienes (alkoxy: CH3O, C2H5O, i‐C3H7O), the reaction constant p* was determined to be −2.9. Results of the present study were compared with those of various butadiene derivatives.

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