Compared Reactivity of Allyl Ribosides in UV-Initiated Free Radical Copolymerization with Acceptor Monomers

The free radical copolymerization of allyl ribosides with diethyl fumarate and maleate was investigated for evaluating the potential of donor-acceptor type copolymerization applied to unsaturated monomers derived from renewable feedstock. The photochemically induced polymerization of model monomer blends was conducted in solution as well as in liquid films of bulk reactants. Infrared spectroscopy was used to monitor the consumption of the allylic donor monomer and of the butenedicarboxylate acceptor monomers. The method allowed examining the influence of the nature of the monomer pair and of their relative concentration on the kinetic profiles. Comparison with reference vinyl ether monomers confirmed the expected lower reactivity of the blends containing allylic derivatives. SEC and NMR analysis supported the occurrence of degradative chain transfer during the reactions involving allylic monomers. However, allyl derivatives of glycerol as well as O-allyl ribosides were shown to undergo polymerization with high conversion of both monomers when blended in appropriate molar ratios.