Polymers synthesized by RAFT as versatile macrophotoinitiators

An exploitation of the generally unwanted sensitivity to light of chain-end functions in polymers synthesized by reversible addition-fragmentation chain transfer (RAFT) is proposed. This reactivity can be purposely enhanced through the simple introduction of a strongly absorbing chromophore on the terminal monomer unit. The concept was validated on RAFT polymers with a xanthate chain-end function and a terminal monomer unit derived from N-vinylcarbazole (NVC). We demonstrate that such compounds can be considered as efficient and versatile macrophotoinitiators, being able to initiate both free radical and radical promoted cationic polymerizations under UV irradiation.