SYNTHESIS OF REACTIVE POLYESTERS BY A REGIOSELECTIVE ADDITION-REACTION OF DIEPOXIDES WITH DIACYL CHLORIDES AND THEIR CHEMICAL MODIFICATION

The polyaddition of diepoxides with diacyl chlorides using quaternary ammonium salts as a catalyst proceeded regioselectively under mild conditions to afford polyesters having pendant chloromethyl groups. Quaternary ammonium halides such as tetrabutylammonium chloride and bromide were very effective catalysts for the polyaddition, and polyesters with high molecular weight were obtained using these catalysts. The resulting polyesters exhibited excellent solubility characteristics to common organic solvents. The chemical modification of the pendant chloromethyl group by a substitution reaction with nucleophilic reagents, sodium dithiocarbamate (NaDC), sodium azide (NaN3), and potassium 3-phenyl-2,5-norbornadienecarboxylate (KNBD), was performed using a phase-transfer catalyst to give modified polyesters with high conversion.