Controlled radical (co)polymerisation of allylic- and vinylic monomers originating from renewable resources

In light of recent efforts of applying principles of green and sustainable chemistry within macromolecular engineering, a large number of novel bio-sourced monomers are available. Especially cyclic carbonates (CCs), because of their effective ring-opening polymerisation to yield polymers such as non-isocyanate poly(urethane)s, has seen rapid progress during the past decade. Yet, very few examples exist of controlled radical polymerisations (CRP) of CCs bearing a double bond, part of the reason being that (i) up to now only some sustainable synthetic routes to such molecules are known and (ii) some interesting monomers contain an allylic-double bond that is challenging to control by most radical polymerization techniques. In this communication, we report on the synthesis of new bio-sourced polymers by the preparation of novel cyclic carbonate monomers from renewable resources followed by their controlled radical polymerization. Mainly bio-sourced allyl- or unconjugated vinyl-type cyclic carbonates are investigated. Cobalt-mediated radical polymerisation (CMRP) is used as a powerful CRP technique that is active for the polymerization of highly unreactive non-conjugated monomers under mild experimental conditions.