(Meth)acrylate copolymers are one of the important polymers for industrial use. Copolymerization of (meth)acrylates and polymer reaction of (meth)acrylate homopolymers are used to obtain the copolymers. Each procedure has advantage and disadvantage. We paid attention the latter procedure because there is a possibility to obtain the copolymers having specific monomer composition, monomer sequence, and stereotacticity. But, transesterifications of ester group on poly(meth)acrylates side chain proceed under particular conditions generally. We have reported synthesis of aliphatic polycarbonate by irreversible polycondensation of diphenyl carbonate with diols catalyzed by dilithium tetra-tert-butylzincate (TBZL). The exchange reaction with phenol obtained as byproduct did not occur under these conditions because of low activity of phenol, while that with diols did. In this work, modifications of the polymer side chain by transesterification of ester group on poly[phenyl (meth)acrylate] [PPh(M)A] and alcohols using TBZL were developed. First, PPh(M)A having different MW and MWD was obtained by anionic polymerization using TBZL and by RAFT polymerization to use for the transesterification. The PPhMA was reacted with excess methanol in toluene or THF in the presence of catalytic amount of TBZL. PPhMA-MMA copolymer was obtained in this reaction conditions. MMA ratio was increased by extending the reaction time, and not affected by reaction solvent and MW of PPhMA. From these results, transesterifications of ester group on PPh(M)A side chain with alcohols other than methanol were also carried out. This reaction provides a process for the synthesis of specific (meth)acrylate copolymers.

Synthesis of (meth)acrylate copolymers from poly[phenyl (meth)acrylate] by transesterification using zinc art complex

2019 Spring National Meeting

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