A novel insertion reaction of epoxy compounds into phenyl ester linkages in polymer chains

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AbstractThe insertion reaction of various epoxy compounds such as phenyl glycidyl ether (PGE), methyl glycidyl ether, butyl glycidyl ether (BGE), and styrene oxide into the phenyl ester linkage in the polymer chain was investigated using quaternary ammonium salts as catalysts in diglyme, anisole, sulfolane, o‐dichlorobenzene, or DMSO at 100–150°C. The reaction of PGE with poly[4‐(4‐nitrobenzoyloxy)styrene] (polymer 1a) proceeded almost quantitatively to give the corresponding polymer using tetrabutylammonium bromide (TBAB) as catalyst in diglyme at 100°C for 24 h. The reactions of BGE with poly(4‐nitrophenyl methacrylate), and copolyarylate derived from 2,2‐bis(4‐hydroxyphenyl)‐1,1,1,3,3,3‐hexafluoropropane and iso‐ and terephthaloyl chlorides also produced the corresponding polymers with 86 and 89 mol% new structural units, respectively, using TBAB in sulfolane at 150°C for 24 h. Furthermore, it was found that the degree of insertion of the epoxy compound into the ester linkage in the polymer chain was affected by the kind of epoxy compound, reaction solvent, catalyst concentration, substituent group on the phenyl ester, and structure of the polymer. Chiral polymers were also synthesized with high degrees of insertion by the reaction of chiral epoxides such as (R)‐1,2‐epoxyhexane, (R)‐1,2‐epoxyheptane, and (R)‐1,2‐epoxydecane with polymer 1a and poly(2,4‐dichlorophenyl methacrylate) using TBAB in diglyme at 120°C for 24 h.