Radical Telomerization of Olefin with Isocyanide

Radical telomerization of olefin with isocyanide was studied. As the isocyanide telogen, t-butyl and benzyl isocyanides were employed. In the telomerizition of ethylene, isobutyl vinyl ether and ethyl trans-crotonate, telomers having degrees of polymerization below four as well as the isomerized product of cyanide were isolated by GLPC, and the structures of oligomers were shown to be expressed by the general formula, In the case of styrene, acrylonitrile, methacrylate, and 1,3-pentadiene, no low oligomer was isolated and polymers having the above general formula were produced. The chain transfer constant of t-butyl isocyanide in the thermal polymerization of styrene at 100°C was determined to be 0.33×10−2. The chain transfer reaction of isocyanide was schematized on the basis of the telomer structures and the radical-reaction behavior of isocyanide.