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    Thermoresponsive (Co)polymers through postpolymerization modification of poly(2-vinyl-4,4-dimethylazlactone)

    Access Status
    Fulltext not available
    Authors
    Zhu, Y.
    Quek, J.
    Lowe, Andrew
    Roth, P.
    Date
    2013
    Type
    Journal Article
    
    Metadata
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    Citation
    Zhu, Y. and Quek, J. and Lowe, A. and Roth, P. 2013. Thermoresponsive (Co)polymers through postpolymerization modification of poly(2-vinyl-4,4-dimethylazlactone). Macromolecules. 46 (16): pp. 6475-6484.
    Source Title
    Macromolecules
    DOI
    10.1021/ma401096r
    ISSN
    0024-9297
    School
    Nanochemistry Research Institute
    URI
    http://hdl.handle.net/20.500.11937/39560
    Collection
    • Curtin Research Publications
    Abstract

    Poly(2-vinyl-4,4-dimethylazlactone), pVDMA, is emerging as a versatile reactive platform in polymer chemistry. Herein, postpolymerization modification of pVDMA leading to thermoresponsive homo- and copolymers is investigated. VDMA was polymerized by reversible addition–fragmentation chain transfer (RAFT) polymerization. The resulting reactive scaffolds with molecular weights ranging from 3.0 to 12.5 kg/mol were converted with a selection of alcohols and amines of varying polarity into functional poly(2-acrylamido isobutyrate)s and poly(2-acrylamido isobutyramide)s with molecular weights ranging from Mn = 4.2–65.1 kg/mol and low polydispersity indices Mw/Mn < 1.37. Spectra obtained by 1H NMR and infrared spectroscopic measurements conformed to the expected structures. While alcohols and amines producing water-soluble or water insoluble VDMA-derived homopolymers were identified, seven homopolymers were found to show a lower critical solution temperature in aqueous solution; those formed by reacting pVDMA with N-ethylamine, N-isopropylamine, N,N-dimethylamine, N,N-diethylamine, N,N-diethylaminoethylamine, Jeffamine M-600, and tetrahydrofurfurylamine (THF amine). Cloud points increased with decreasing molecular weight. With a cloud point of 31 °C, the phase separation of poly(tetrahydrofurfuryl 2-acrylamido isobutyramide) (pTAI) occurred close to body temperature, was highly reproducible, and, above a concentration of 0.5 wt %, was largely concentration independent. The transition temperature of pTAI-based copolymers could easily be tuned by reacting pVDMA with a mixture of THF amine and varying amounts of pentylamine or di(ethylene glycol) methyl ether amine.

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