Synthesis of Novel Aliphatic Poly(ester-carbonates) Containing Pendent Olefin and Epoxide Functional Groups

Abstract

The synthesis and polymerization of a novel cyclic carbonate monomer containing a pendent unsaturated ester group, 5-methyl-5-allyloxycarbonyl-1,3-dioxan-2-one (MAC) is reported. The random copolymerization of this cyclicmonomer with rac-lactide was performed using stannous ethoxide (Sn(OEt) 2 ) as the catalyst/initiator. Random copolymers containing various amounts of MAC and rac-LA were synthesized to introduce unsaturated groups pendent to the polymer backbone for possible crosslinking, epoxidation, or addition reactions. In addition, oligomeric macroinitiators of MAC were synthesized, and ring-opening polymerization of rac-LA yielded near monodisperse poly(rac-LA) with multiple double bonds pendent to one end of the polymer chain. Post-polymerization epoxidation reactions of the copolymers were performed with m-chloroperoxy benzoic acid to yield poly(ester-carbonates) with epoxide groups randomly along the backbone (random copolymer) or at one end of the polymer chain (from the MAC oligomeric macroinitiator). The epoxide groups provide a pathway for more organic transformations with alcohols, carboxylic acids, and amines.