Synthesis and controlled raddical copolymerisation of renewably-sourced carbonates

Non-phosgene derived carbonates are an extremely promising and attractive class of molecules that have found numerous applications. Especially in polymer chemistry, ROP or polyadditions of carbonate monomers are extremely effective for the synthesis of poly(carbonate)s or non-isocyanate poly(urethane)s. Yet these polymerisation pathways utilise the carbonate functionality for the synthesis of the copolymer backbone and thus exclude post-polymerisation modifications on the carbonate functionality. A strategy for retaining the carbonate is to attach a double bond to the carbonate and perform a radical polymerisation which results in copolymers containing pendant carbonates available for post-polymerisation functionalisation. However, few examples of this approach can be found in the literature, one of the reasons being that efficient and sustainable synthetic pathways for the combination of carbonates and double bonds are still rare. Additionally, such molecules often contain double bonds, which are extremely challenging to control by most CRP techniques. Herein we report on the one-pot synthesis of several allylic carbonate monomers from sustainable resources and, for the first time, report on the controlled radical polymerisation (CRP) of these novel allylic monomers with less activated monomers (LAMs), such as vinyl acetate.