Aqueous Copper-Mediated Living Radical Polymerisation of N-Acryloylmorpholine, SET-LRP in Water

The polymerisation of N‐acryloylmorpholine in water is reported utilising Cu(0)‐mediated living radical polymerisation (SET‐LRP). The inherent instability of [CuI(Me6‐Tren)Br] in aqueous solution is exploited via rapid disproportionation to prepare Cu(0) particles and [CuII(Me6‐Tren)Br2] in situ prior to addition of monomer and initiator. Quantitative conversion is attained within 30 min for various degrees of polymerisation (DPn = 20–640) with SEC showing symmetrical narrow molecular weight distributions (Đ < 1.18) in all cases. Optimised conditions are subsequently applied for the preparation of a diblock copolymer poly(NIPAm)‐b‐(N‐acryloylmorpholine), illustrating the versatility of this approach. Copper‐mediated controlled poly­merisation of N‐acryloylmorpholine in pure aqueous media is reported for the first time. The recently developed aqueous SET‐LRP protocol is exploited for the preparation of biocompatible poly(N‐acyloylmorpholine) with a range of molecular weights and the formation of biocompatible double‐hydrophilic block copolymers is also demonstrated.