Investigation of the copolymerisation behaviour of bio-sourced vinylic and allylic cyclic carbonates

Cyclic carbonates belong to a versatile class of compounds, that are widely used for the synthesis of non-isocyanate polyurethanes and as precursors for chiral building blocks. Their incorporation as pendant groups in polymer chains is highly attractive for post-polymerisation functionalisation. The controlled radical polymerisation (CRP) of allylic or vinylic CCs is a route for the precision design of such type of polymers. Very few reports on the controlled copolymerisation of CCs are found in the literature 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 extremely challenging to control by most radical polymerisation techniques. Herein we report the synthesis of a new class of glycerol-based allylic cyclic carbonates and additionally report on the CRP of such and other CCs using cobalt-mediated radical polymerisation (CMRP).