Catalytic living ROMP: block copolymers from macro-chain transfer agents

Vinyl ether based macro-chain transfer agents (m-CTAs) are used to produce different di or tri-block copolymers under catalytic living ROMP conditions. Polystyrene (PS) vinyl ether m-CTA and polycaprolactone (PCL) or polylactide vinyl ether (PLA) m-CTAs are synthesized straightforwardly via ATRP and ROP respectively. Regioselectivity as well as the high metathesis activity of these m-CTAs enabled us to synthesise a range of metathesis-based A–B diblock copolymers with controlled dispersities (Đ < 1.4). In this manner, PS-ROMP (here, ROMP refers to a poly(MNI-co-DHF) block), PCL-ROMP and PLA-ROMP were synthesized using substoichiometric amounts of ruthenium complex in a living fashion. Also, a more complex PEG-PCL-ROMP tri-block terpolymer was obtained catalytically. All block copolymers were characterized by SEC and DOSY NMR spectroscopy. We believe that this methodology of using macro-chain transfer agents to prepare degradable ROMP polymers under catalytic living ROMP conditions will find applications in biomedicine.