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Polymers 2011, 3(3), 1398-1422; doi:10.3390/polym3031398

Synthesis of Stimuli-responsive, Water-soluble Poly[2-(dimethylamino)ethyl methacrylate/styrene] Statistical Copolymers by Nitroxide Mediated Polymerization

Department of Chemical Engineering, McGill University, 3610 University Street, Montreal, QC H3A 2B2, Canada
Author to whom correspondence should be addressed.
Received: 20 July 2011 / Revised: 15 August 2011 / Accepted: 25 August 2011 / Published: 26 August 2011
(This article belongs to the Special Issue Water-Soluble Polymers)
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2-(Dimethylamino)ethyl methacrylate/styrene statistical copolymers (poly(DMAEMA-stat-styrene)) with feed compositions fDMAEMA = 80–95 mol%, (number average molecular weights Mn = 9.5–11.2 kg mol−1) were synthesized using succinimidyl ester-functionalized BlocBuilder alkoxyamine initiator at 80 °C in bulk. Polymerization rate increased three-fold on increasing fDMAEMA = 80 to 95 mol%. Linear Mn increases with conversion were observed up to about 50% conversion and obtained copolymers possessed monomodal, relatively narrow molecular weight distributions (polydispersity = 1.32–1.59). Copolymers with fDMAEMA = 80 and 90 mol% were also cleanly chain-extended with DMAEMA/styrene mixtures of 95 and 90 mol% DMAEMA, respectively, confirming the livingness of the copolymers. Copolymer phase behavior in aqueous solutions was examined by dynamic light scattering and UV-Vis spectroscopy. All copolymers exhibited lower critical solution temperature (LCST)-type behavior. LCST decreased with increasing styrene content in the copolymer and with increasing solution concentration. All copolymers were completely water-soluble and temperature insensitive at pH 4 but were more hydrophobic at pH 10, particularly copolymers with fDMAEMA = 80 and 85 mol%, which were water-insoluble. At pH 10, LCST of copolymers with fDMAEMA = 90 and 95 mol% were more than 10 °C lower compared to their solutions in neutral, de-ionized water. Block copolymers with two statistical blocks with different DMAEMA compositions exhibited a single LCST, suggesting the block segments were not distinct enough to exhibit separate LCSTs in water. View Full-Text
Keywords: stimuli-responsive; 2-(dimethylamino)ethyl methacrylate; nitroxide mediated polymerization stimuli-responsive; 2-(dimethylamino)ethyl methacrylate; nitroxide mediated polymerization

This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

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MDPI and ACS Style

Zhang, C.; Maric, M. Synthesis of Stimuli-responsive, Water-soluble Poly[2-(dimethylamino)ethyl methacrylate/styrene] Statistical Copolymers by Nitroxide Mediated Polymerization. Polymers 2011, 3, 1398-1422.

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