A Novel Synthesis of Reactive Polycarbonates with Pendant Chloromethyl Groups by the Polyaddition of Bis(epoxide)s with 2,2‘-Bis[(4-chloroformyl)oxyphenyl]propane

Abstract

The polyaddition of bisphenol A diglycidyl ether (4a) with 2,2'-bis[(4-chloroformyl)oxyphenyl]-propane (5) was examined using quaternary onium salts as catalysts. When the polyaddition was performed using catalysts containing Br - as a counteranion such as tetraphenylphosphonium bromide in chlorobenzene at 100 °C for 48 h, the corresponding poly(alkyl aryl carbonate) with high molecular weight (M n = 59 000) was obtained. It was found from the 1 H NMR and 13 C NMR spectra of the obtained polymer that the reaction proceeded regioselectively at the epoxy group of 4a to provide the polycarbonate with pendant chloromethyl groups. The polyaddition of various bis(epoxide)s with 5 also proceeded smoothly to give the corresponding poly(carbonate)s with high molecular weight in good yields. The chemical modification of the obtained poly(carbonate)s with pendant chloromethyl groups by the phase-transfer method was also investigated using nucleophiles such as potassium thiocyanate and potassium 3-phenyl-2,5-norbornadienecarboxylate.