Reactivity of allyl pentosides in UV-initiated free radical copolymerization with acceptor monomers

There is an increasing demand for new routes yielding monomers derived from biomass feedstock. Owing to the large variety of synthetic polymerization methods and associated chain growth mechanisms, several approaches are currently addressed [2] Biosourced monomers for step-growth or for chain polymerization can be obtained by various chemical or biotechnological methods. In spite of the prime situation of free radical polymerization for synthetic polymers, the routes to unsaturated monomers with an original structure suitable for this specific type of chain polymerization are very few. Unsaturated acids and their derivatives can be obtained from sugar-derived building blocks and has also been reported to afford functional monomers for preparing soluble copolymers or polymeric materials of potential interest for analytic or biomedical applications [4]. We have evaluated an alternative route based on allyl functional glucides for free-radical copolymerization with monomers carrying electron-withdrawing groups, so as to favor donor-acceptor synergy for the cross-propagation mechanism [5]. Various allyloxy and vinyloxy compounds of increasing structural complexity were prepared and reacted for assessing the polymerizability of glucides bearing unsaturated functions with diethyl fumarate (DEF) and diethyl maleate (DEM). The unsaturated diesters can also be obtained from biosourced intermediates offering the possibility to modify favorably the content in renewable carbon within the final polymeric material.