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 polyaddition with polyamines to yield polymers such as non-isocyanate poly(urethane)s, have 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 reactive double bonds which are challenging to control by most radical polymerisation techniques. Herein we report on how cobalt-mediated radical polymerisation (CMRP) proves a powerful method for the (co)polymerisation of such monomers. Furthermore, the unique characteristics of the resulting (co)polymers and their value for applications in composites are highlighted.