A NOVEL SYNTHESIS OF REACTIVE POLYMERS WITH PENDANT HALOMETHYL GROUPSBY THE POLYADDITION REACTION OF BIS(EPOXIDE)S WITH BIS(CHLOROACETOXY)ESTERS OR BIS(BROMOACETOXY) ESTERS

New reactive polymers with pendant halomethyl groups were successfully synthesized by polyaddition reactions of bis(epoxide)s with bis(chlor oacetoxy) ester such as 1,4-bis[(chloroacetoxy) methyl] benzene (BCAMB ) or 1,4-bis[(bromoacetoxy)-methyl]benzene (BBAMB) using quaternary on ium salts or crown ether complexes as catalysts, The polyaddition reac tion of diglycidyl ether of bisphenol A (DGEBA) with BCAMB proceeded v ery smoothly with high yields (83-96%) by the addition of quaternary o nium salts such as tetrabutylphosphonium bromide (TBPB) or crown ether complexes such as 18-crown-6/KBr as catalysts to produce high molecul ar weight polymers, although the reaction occurred without any catalys t to give low molecular weight polymer in low yield at 90 degrees C fo r 48 h. It was also found that the reaction proceeded smoothly in apro tic polar solvents such as N-methyl-2-pyrrolidone (NMP) and N,N-dimeth ylacetamide (DMAc) to produce high molecular weight polymers, Polyaddi tion reactions of DGEBA or digylcidyl ether of ethylene glycol (DGEEG) with BBAMB, other bis(chloroacetoxy) esters or bis(bromoacetoxy) este rs using TBPB in DMAc also proceeded smoothly to give the correspondin g polymers. The resulting poly(ether-ester)s contain reactive halometh yl groups as side chains, which were introduced during main chain form ation. (C) 1997 John Wiley & Sons, Inc.