RAFT polymerisation of N-vinylformamide and the corresponding double hydrophilic block copolymers

Abstract

Reversible addition–fragmentation chain transfer (RAFT) homopolymerisation of N-vinylformamide (NVF) is reported for the first time. Reactions were conducted in DMSO at 35 °C using a xanthate RAFT agent. PNVFs of predetermined molar masses up to M_n ∼ 80 000 g mol⁻¹ and low dispersities (<1.4) were synthesized. Excellent chain-end fidelity was confirmed by ESI-TOF mass spectrometry. A series of double hydrophilic block copolymers comprising a PNVF segment were successfully synthesized and characterized via asymmetric flow field flow fractionation (AF4) and ¹H DOSY-NMR techniques. Finally, poly(N-vinylcaprolactam)-b-poly(N-vinylformamide) (PVCL-b-PNVF) was hydrolysed into the original dual responsive poly(N-vinylcaprolactam)-b-poly(N-vinylamine) (PVCL-b-PVAm), thus revealing the strong potential of this RAFT approach to develop PVAm-based complex architectures.