A Novel Synthesis of Poly(carbonate)s by the Polyaddition of Bis(epoxide)s with Diphenyl Carbonate

The synthesis of poly(carbonate)s with phenoxymethyl groups in their side chains by a polyaddition of bisphenol A diglycidyl ether ( 4a ) with diphenyl carbonate ( 2 ) using quaternary onium salts or crown ether complexes as catalysts is described. When the polyaddition was performed with the catalyst containing Cl - as a counteranion such as tetrabutylammonium chloride, tetrabutylphosphonium chloride, or 18-crown-6/KCl without solvent at 100 °C for 48 h, the corresponding poly(carbonate) with high molecular weight ( M n = 20 000−34 000) was successfully obtained. 1 H NMR and 13 C NMR spectra of the resulting polymer indicated that the reaction proceeded regioselectively at the epoxy groups of 4a to give the polycarbonate with pendant phenoxy groups. The polyaddition of various bis(epoxide)s with 2 also proceeded in bulk to provide the corresponding poly(carbonate)s with high molecular weight in good yield.