Radical copolymerization of an electron‐accepting monomer, methyl cis‐β‐cyanoacrylate, with styrene or acrylonitrile

Abstract

AbstractThe electron‐accepting property and the radical copolymerizability of methyl cis‐β‐cyanoacrylate (MCA) were studied. The monomer was found to form a contact charge‐transfer complex with styrene (ST) in chloroform at 25°C and behaved as a weak electron acceptor. The copolymerization parameters were determined in dioxane at 50°C for systems involving ST or acrylonitrile (AN) as comonomer. The reactivity ratio of ST or AN was estimated by the Kelen–Tudös method considering both the penultimate unit effect and no homopropagation of MCA. The penultimate effect for the system ST–MCA was large compared with that for the system ST–dimethyl maleate (DMM), indicating that a polar effect is mainly responsible for the penultimate effect. The terpolymerization of ST, MCA, and maleic anhydride (MA) was also studied to compare the reactivity of MCA with that of MA.