螺吡喃和介晶二丙烯酸酯混合物的光致变色和光聚合诱导的介相转变。

Photochromism and photopolymerization induced mesophase transitions in mixtures of spiropyran and mesogenic diacrylate.

机构信息

Department of Polymer Engineering, University of Akron, Akron, Ohio 44325-0301, United States.

出版信息

J Phys Chem B. 2010 Dec 16;114(49):16381-7. doi: 10.1021/jp108113b. Epub 2010 Nov 17.

Abstract

A phase diagram of a binary mixture of photochromic molecule (spiropyran) and mesogenic diacrylate monomer has been established by means of differential scanning calorimetry and polarized optical microscopy. Subsequently, a theoretical phase diagram has been calculated by self-consistently solving the combined Flory-Huggins free energy for isotropic mixing, Maier-Saupe free energy for nematic ordering, and phase field free energy for crystal solidification. The phase diagram thus obtained consists of various coexistence regions involving single-phase crystals, pure nematic, crystal + liquid, crystal + nematic, and crystal + crystal coexistence gaps. Under UV irradiation, both SP and SP/RM257 mixtures showed the lowering trend of the melting points, which may be attributed to the plasticization effect by the merocyanine isomers. When UV light is illuminated on the 2/98 SP/RM257 mixture for an extended period, mesogenic diacrylate in the mixtures gets polymerized, showing the permanent fixation of isotropic and nematic structures due to the network formation of RM257 caused by the biradicals in the merocyanine intermediate.

摘要

采用差示扫描量热法和偏光显微镜建立了光致变色分子(螺吡喃)和介晶二丙烯酸酯单体的二元混合物的相图。随后,通过自洽求解各向同性混合的 Flory-Huggins 自由能、向列有序的 Maier-Saupe 自由能和晶体凝固的相场自由能,计算出理论相图。得到的相图包含各种共存区域,涉及单相晶体、纯向列相、晶体+液体、晶体+向列相和晶体+晶体共存间隙。在紫外光照射下,SP 和 SP/RM257 混合物的熔点均呈现降低的趋势,这可能归因于中间产物的变色酸型螺吡喃异构体的增塑作用。当将紫外光长时间照射在 2/98 SP/RM257 混合物上时,混合物中的介晶二丙烯酸酯发生聚合,由于变色酸型螺吡喃中间产物的双自由基导致 RM257 形成网络,混合物的各向同性和向列结构得到永久固定。

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