Introduction of 2‐methoxycarbonylallyl end group by copolymerization of methyl α‐(phenoxymethyl)acrylate accompanying with addition‐fragmentation reaction

Copolymerizations of methyl α‐(phenoxymethyl)acrylate (MPMA) with methyl acrylate, methyl methacrylate, styrene, and methyl α‐ethylacrylate were carried out. Addition of a polymer radical to MPMA followed by the subsequent fragmentation of poly(MPMA) radical resulted in the 2‐methoxycarbonylallyl end group and phenoxy radical in the course of the copolymerization. The extent of the fragmentation determined by 1H‐NMR spectroscopy depends on reactivity of the MPMA radical toward the reference monomers. An increase in the addition rate of the MPMA radical to the reference monomer brought about suppression of the fragmentation. The addition of the MPMA radical to styrene seems to be sufficiently fast to prevent the fragmentation. Since the rate of the fragmentation relative to the propagation was considerably accelerated by raising the temperature to 110°C, MPMA can be used as a novel chain transfer agent to control molecular weight and end group at a temperature above 100°C.