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Synthesis of an Azobenzene-containing Main-chain Crystalline Polymer and Photodeformation Behaviors of Its Supramolecular Hydrogen-bonded Fibers

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Chinese Journal of Polymer Science 2020年第1期38卷 37-44,I0006页

作者： Zheng-Zheng Wang Hui-Qi Zhang State Key Laboratory of Medicinal Chemical Biology Key Laboratory of Functional Polymer Materials (Ministry of Education) Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) and College of Chemistry Nankai University

The synthesis of a new azobenzene(azo)-containing main-chain crystalline polymer with reactive secondary amino groups in its backbone and photodeformation behaviors of its supramolecular hydrogen-bonded fibers are described. This main-chain azo polymer(namely Azo-MP6) was prepared via first the synthesis of a diacrylate-type azo monomer and its subsequent michael addition copolymerization with trans-1,4-cyclohexanediamine under a mild reaction condition. Azo-MP6 was found to have a linear main-chain chemical structure instead of a branched one, as verified by comparing its ~1H-NMR spectrum with that of the azo polymer prepared via the polymer analogous reaction of AzoMP6 with acetic anhydride. The thermal stability, phase transition behavior, and photoresponsivity of Azo-MP6 were characterized with TGA,DSC, POM, XRD, and UV-Vis spectroscopy. The experimental results revealed that it had good thermal stability, low glass transition temperature,broad crystalline phase temperature range, and highly reversible photoresponsivity. Physically crosslinked supramolecular hydrogen-bonded fibers with good mechanical properties and a high alignment order of azo mesogens were readily fabricated from Azo-MP6 by using the simple melt spinning method, and they could show "reversible" photoinduced bending under the same UV light irradiation and good anti-fatigue properties.

关键词： Main-chain azobenzene polymer Crystalline polymer michael addition polymerization Physically crosslinked network Photodeformation

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