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Design of Thermoresponsive Polymers with Aqueous LCST, UCST, or Both: Modification of a Reactive Poly(2-vinyl-4,4-dimethylazIactone) Scaffold

Zhu, Y, Batchelor, R, Lowe, AB and Roth, PJ (2016) Design of Thermoresponsive Polymers with Aqueous LCST, UCST, or Both: Modification of a Reactive Poly(2-vinyl-4,4-dimethylazIactone) Scaffold Macromolecules, 49 (2). pp. 672-680.

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Abstract

The synthesis and aqueous solution properties of a family of zwitterionic homo-, co-, and terpolymers derived from poly(2-vinyl-4,4-dimethylazlactone) (pVDMA) with tunable lower and upper critical solution temperatures (LCST and UCST) are presented. A RAFT-made pVDMA precursor was reacted with mixtures of zwitterionic sulfopro-pylbetaine (SPB) amine or sulfobutylbetaine (SBB) amine, tetrahydrofurfurylamine (THF amine), and benzylamine (Bz amine) in varying molar ratios. Products were characterized by variable temperature (VT) NMR spectroscopy, FT-IR spec-troscopy, size exclusion chromatography, turbidity, and VT dynamic light scattering in order to confirm quantitative postpolymerization modification, determine molar compositions, and elucidate structure−property relationships. Polymers comprising large molar fractions of THF groups showed LCST behavior due to a polarity change of the THF-functional segments, while SPB/SBB-rich samples, including the zwitterionic homopolymers, showed UCST behavior in ultrapure water based on electrostatic polymer−polymer attractions. Binary SPB−THF copolymers were water-soluble between 0 and 90 °C for a large compositional range. Terpolymers comprising molar SPB:THF:Bz ratios of approximately 50:25:25 showed a low LCST and a high UCST (LCST < UCST) with a miscibility gap in which the SPB groups and THF groups were not fully hydrated. In the one-phase regions below the LCST and above the UCST, polymer chains were presumed to be unimerically dissolved with partially solvated domains undergoing intrachain associations. Addition of NaCl caused LCST and UCST behavior to disappear, resulting in temperature-independent solubility. Molecular insights presented herein are anticipated to aid in the development of smart materials with double LCST < UCST or UCST < LCST thermoresponsiveness.

Item Type: Article
Subjects : subj_Chemistry
Divisions : Faculty of Engineering and Physical Sciences > Chemistry
Authors :
AuthorsEmailORCID
Zhu, YUNSPECIFIEDUNSPECIFIED
Batchelor, RUNSPECIFIEDUNSPECIFIED
Lowe, ABUNSPECIFIEDUNSPECIFIED
Roth, PJUNSPECIFIEDUNSPECIFIED
Date : 5 January 2016
Identification Number : 10.1021/acs.macromol.5b02056
Copyright Disclaimer : Copyright © 2016 American Chemical Society
Uncontrolled Keywords : Science & Technology, Physical Sciences, Polymer Science, CRITICAL SOLUTION TEMPERATURES, INSOLUBLE-SOLUBLE TRANSITIONS, PHASE-BEHAVIOR, HYDROPHOBIC POLYELECTROLYTE, RAFT POLYMERIZATION, POLY(N,N-DIMETHYLAMINOETHYL METHACRYLATE), POSTPOLYMERIZATION MODIFICATION, RADICAL POLYMERIZATION, ZWITTERIONIC POLYMERS, N-ISOPROPYLACRYLAMIDE
Related URLs :
Depositing User : Symplectic Elements
Date Deposited : 19 Apr 2016 08:36
Last Modified : 09 Nov 2016 17:56
URI: http://epubs.surrey.ac.uk/id/eprint/810458

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