Kim Hyungwoo, Chang Ji Young
Department of Materials Science and Engineering, College of Engineering, Seoul National University , Seoul 151-744, Korea.
Langmuir. 2014 Nov 18;30(45):13673-9. doi: 10.1021/la502932x. Epub 2014 Nov 6.
We report a reversible thermochromic nanocomposite polymer film composed of fluorescent organogel fibers and a highly cross-linked polymer matrix. A series of cyano-substituted oligo(p-phenylenevinylene) (CN-OPV) derivatives were synthesized by the reaction of dialdehydes with phenyl or naphthyl acetonitrile under basic conditions. Among the CN-OPV derivatives, NA-DBA having naphtyl moieties and dodecyloxy chains formed a stable organogel in a cross-linkable monomeric solvent (ethylene glycol dimethacrylate). The organogel showed a thermoreversible sol-gel transition, accompanying the emission color change. A nanocomposite polymer film obtained by photopolymerization of the organogel between two quartz plates also exhibited reversible thermochromism. Under 365 nm irradiation, the orange color of the film at 25 °C became yellowish green at 120 °C. The fluorescence spectroscopy, DSC, and microscopy results determined that the thermally reversible self-assembly of NA-DBA occurred in the polymer matrix, resulting in reversible thermochromism. The melted gelator molecules at 120 °C did not diffuse into the polymer matrix probably because of poor interactions of the gelator molecules with the polymer matrix. The NA-DBA molecules dispersed in poly(methyl methacrylate), without forming a supramolecular structure, did not show thermochromism.
我们报道了一种由荧光有机凝胶纤维和高度交联的聚合物基质组成的可逆热致变色纳米复合聚合物薄膜。通过二醛与苯基或萘基乙腈在碱性条件下反应合成了一系列氰基取代的寡聚(对苯撑乙烯撑)(CN-OPV)衍生物。在CN-OPV衍生物中,具有萘基部分和十二烷氧基链的NA-DBA在可交联单体溶剂(乙二醇二甲基丙烯酸酯)中形成了稳定的有机凝胶。该有机凝胶表现出热可逆的溶胶-凝胶转变,并伴随着发射颜色的变化。通过在两个石英板之间对有机凝胶进行光聚合得到的纳米复合聚合物薄膜也表现出可逆热致变色。在365nm光照下,25℃时薄膜的橙色在120℃时变为黄绿色。荧光光谱、差示扫描量热法和显微镜结果表明,NA-DBA在聚合物基质中发生了热可逆自组装,从而导致可逆热致变色。120℃时熔化的凝胶剂分子可能由于凝胶剂分子与聚合物基质之间的相互作用较弱而没有扩散到聚合物基质中。分散在聚甲基丙烯酸甲酯中且未形成超分子结构的NA-DBA分子没有表现出热致变色。