On the synthesis and polymerization of t‐butyl‐p‐vinylperbenzoate and the grafting of its homo‐ and copolymers

The monomer initiator t‐butyl‐p‐vinylperbenzoate (TBVP) was synthesized and its homo‐ and copolymerization with styrene, methacrylonitrile, isoprene and phenylmethacrylate was investigated. TBVP is preponderantly incorporated in all four systems; values of Q = 2.27 and e = −0.13 characterize TBVP as a weak donor with a high monomer reactivity. Kinetic considerations show that all propagation steps in which TBVP takes part are faster or at least as fast as the self‐propagation steps of the comonomers used. Rate constants and activation energies of the thermal decomposition of poly(t‐butyl‐p‐vinylperbenzoate) and poly(t‐butyl‐p‐vinylperbenzoate‐co‐styrene) were determined. The polymer initiators were used for grafting experiments with styrene, acrylonitrile, and methyl methacrylate. The data evaluated for the grafting efficiency, the success of grafting, and the degree of grafting show that these polymers of p‐vinylperbenzoate are efficient initiators.