Water‐soluble/dispersible carbazole‐containing random and block copolymers by nitroxide‐mediated radical polymerisation

A series of carbazole‐containing water‐dispersible poly(acrylic acid)‐b‐(9‐(4‐vinylbenzyl)‐9H‐carbazole) block copolymers (poly(AA)‐b‐poly(VBK)) and water‐soluble poly(methacrylic acid‐ran‐(9‐(4‐vinylbenzyl)‐9H‐carbazole)) (poly(MAA‐ran‐VBK)) random copolymers were synthesised in a controlled manner (i.e. low polydispersities $(\overline {M_{{\rm w}} } /\overline {M_{n} } < 1.3)$ by nitroxide‐mediated polymerisation (NMP) using an SG1‐based alkoxyamine initiator, BlocBuilder. Poly(AA)‐b‐poly(VBK) block copolymers were most easily accessed by using poly(AA) in its protected form as the macroinitiator for the 9‐(4‐vinylbenzyl)‐9H‐carbazole (VBK) block. Controlled polymerisation of MAA was accomplished using an excess of 10 mol.% SG1 relative to BlocBuilder with VBK as controlling co‐monomer (initial molar feed content f_VBK,0 = 0.03–0.20) in dimethylformamide at 80°C. Poly(MAA‐ran‐VBK) copolymers with a final VBK molar composition of F_VBK < 0.30 resulted in water‐soluble copolymers. In addition, as macroinitiators, poly(MAA‐ran‐VBK)s were sufficiently pseudo‐living to reinitiate a second batch of monomer (90 mol.% methyl methacrylate with styrene) in organic solvent and by ab initio, surfactant‐free emulsion polymerisation. In both cases, low polydispersity, amphiphilic block copolymers resulted $(\overline {M_{{\rm w}} } /\overline {M_{{\rm n}} } < 1.3)$ . © 2012 Canadian Society for Chemical Engineering