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Processes 2017, 5(1), 7;

Poly(methacrylic acid-ran-2-vinylpyridine) Statistical Copolymer and Derived Dual pH-Temperature Responsive Block Copolymers by Nitroxide-Mediated Polymerization

Department of Chemical Engineering, McGill University, Montreal, QC H3A 0C5, Canada
AstenJohnson Inc., 50 Richardson Side Rd, Kanata, ON K2K 1X2, Canada
Author to whom correspondence should be addressed.
Academic Editor: Alexander Penlidis
Received: 19 January 2017 / Revised: 8 February 2017 / Accepted: 13 February 2017 / Published: 21 February 2017
(This article belongs to the Special Issue Water Soluble Polymers)
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Nitroxide-mediated polymerization using the succinimidyl ester functional unimolecular alkoxyamine initiator (NHS-BlocBuilder) was used to first copolymerize tert-butyl methacrylate/2-vinylpyridine (tBMA/2VP) with low dispersity (Đ = 1.30–1.41) and controlled growth (linear number average molecular Mn versus conversion, Mn = 3.8–10.4 kg·mol−1) across a wide composition of ranges (initial mol fraction 2VP, f2VP,0 = 0.10–0.90). The resulting statistical copolymers were first de-protected to give statistical polyampholytic copolymers comprised of methacrylic acid/2VP (MAA/2VP) units. These copolymers exhibited tunable water-solubility due to the different pKas of the acidic MAA and basic 2VP units; being soluble at very low pH < 3 and high pH > 8. One of the tBMA/2VP copolymers was used as a macroinitiator for a 4-acryloylmorpholine/4-acryloylpiperidine (4AM/4AP) mixture, to provide a second block with thermo-responsive behavior with tunable cloud point temperature (CPT), depending on the ratio of 4AM:4AP. Dynamic light scattering of the block copolymer at various pHs (3, 7 and 10) as a function of temperature indicated a rapid increase in particle size >2000 nm at 22–27 °C, corresponding to the 4AM/4AP segment’s thermos-responsiveness followed by a leveling in particle size to about 500 nm at higher temperatures. View Full-Text
Keywords: nitroxide-mediated polymerization; poly(ampholytes); stimuli-responsive polymers nitroxide-mediated polymerization; poly(ampholytes); stimuli-responsive polymers

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).
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Marić, M.; Zhang, C.; Gromadzki, D. Poly(methacrylic acid-ran-2-vinylpyridine) Statistical Copolymer and Derived Dual pH-Temperature Responsive Block Copolymers by Nitroxide-Mediated Polymerization. Processes 2017, 5, 7.

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