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Water‐soluble/dispersible carbazole‐containing random and block copolymers by nitroxide‐mediated radical polymerisation
Author(s) -
Lessard Benoît H.,
Marić Milan
Publication year - 2013
Publication title -
the canadian journal of chemical engineering
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.404
H-Index - 67
eISSN - 1939-019X
pISSN - 0008-4034
DOI - 10.1002/cjce.21676
Subject(s) - copolymer , polymer chemistry , nitroxide mediated radical polymerization , polymerization , carbazole , monomer , chemistry , styrene , emulsion polymerization , methacrylic acid , molar mass , methyl methacrylate , dispersity , solvent , materials science , radical polymerization , organic chemistry , polymer
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