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

1
Department of Chemical Engineering, McGill University, Montreal, QC H3A 0C5, Canada
2
AstenJohnson Inc., 50 Richardson Side Rd, Kanata, ON K2K 1X2, Canada
*
Author to whom correspondence should be addressed.
Academic Editor: Alexander Penlidis
Processes 2017, 5(1), 7; https://doi.org/10.3390/pr5010007
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)
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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MDPI and ACS Style

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. https://doi.org/10.3390/pr5010007

AMA Style

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(1):7. https://doi.org/10.3390/pr5010007

Chicago/Turabian Style

Marić, Milan, Chi Zhang, and Daniel Gromadzki. 2017. "Poly(methacrylic acid-ran-2-vinylpyridine) Statistical Copolymer and Derived Dual pH-Temperature Responsive Block Copolymers by Nitroxide-Mediated Polymerization" Processes 5, no. 1: 7. https://doi.org/10.3390/pr5010007

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