The unexpected behaviour of epoxidised macromonomers derived from catalytic chain transfer during ring opening copolymerisation

In our attempts to combine catalytic chain transfer polymerisation (CCTP) with ring-opening polymerisation (ROP), we investigated the homopolymerisation and copolymerisation behaviour of epoxidised CCTP-derived (macro)monomers. Attempts at polymerisation and copolymerisation proved futile. However, some interesting end-functionalised polymers were generated during the attempted copolymerisation reactions. The cationic ROP of epoxidised CCTP-derived (macro)monomers was unsuccessful due to the formation of stable 5-membered rings, incapable of propagation. In a copolymerisation of these epoxides with tetrahydrofuran (THF), however, we observed that the epoxides did not act as a comonomer but rather as an end-capper, providing a functional end group. Most surprising, was the observation that the epoxidised CCTP-derived (macro)monomers significantly catalyse the homopolymerisation of THF.