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Ultra-fine Structure Control of Organic Crystals Using Solid-State Polymerization Reactions

利用固态聚合反应控制有机晶体的超精细结构

基本信息

批准号：
16072215
负责人：
MATSUMOTO Akikazu
金额：
$ 15.87万
依托单位：
Osaka City University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2006
项目状态：
已结题

项目摘要

In this project, we have investigated the topochemical polymerization, dimerization, isomerization of unsaturated organic compounds as well as the phase transition and the intercalation reactions of the resulting polymer crystals, and revealed solid-state reaction mechanisms for controlling the reactions, structures, and properties of organic solid materials. We first investigated a change in the crystal structures and the accumulation of a strain in the crystals during the reaction to reveal the mechanism of the topochemical polymerization, EZ-photoisomerization, and [2+2] cyclodimerization of muconic esters as the 1,3-diene monomers via a crystal-to-crystal transformation. We proposed a solid-state reaction mechanism for the crystal-lattice controlled reactions of various unsaturated organic compound based on the results of in situ X-ray crystal structure analysis during the polymerization. Next, we prepared four kinds of stereoregular polymuconates by solid-state polymerization and revealed the reaction behavior and the layered structure of intercalation compounds. The orientation of the guest molecules is controlled according to the host polymer tacticity. We have fabricated the nanocomposite consisting of a crystalline organic polymer and fine metal particles. Furthermore, we developed a double-intercalation method using alkylamine and pyrene as the guests to control the fluorescence property in the solid state. An aromatic compound is separately introduced into the hydrophobic layers of the ammonium polymer crystals and shows a fluorescence emission from the single molecule, but not the excimer. We also found the thermochromism of polydiacetylenes in a solid film, polymer matrix, and solutions with a hysteresis loop as a function of temperature. They are accounted for by the formation of polymer aggregates and reorganization of the polymer chains.

在本项目中，我们研究了不饱和有机化合物的拓扑化学聚合、二聚、异构化以及所产生的聚合物晶体的相变和插层反应，并揭示了控制有机固体材料的反应、结构和性质的固态反应机理。我们首先研究了晶体结构的变化和反应过程中晶体中应变的积累，以揭示作为1，3-二烯单体的粘康酸酯通过晶体到晶体转化的拓扑化学聚合、EZ-光异构化和[2+2]环二聚的机理。根据原位X射线晶体结构分析结果，提出了一种固相反应机理，用于描述各种不饱和有机化合物的晶格控制反应。其次，我们利用固相聚合法制备了四种有规立构的聚粘酸酯，并对其反应行为和插层结构进行了研究。客体分子的取向根据主体聚合物的立构规整度来控制。我们已经制造了纳米复合材料组成的结晶有机聚合物和精细的金属颗粒。此外，我们还发展了一种以烷基胺和芘为客体的双重插层法来调控固体荧光性质。将芳香族化合物单独引入到铵聚合物晶体的疏水层中，并显示来自单分子的荧光发射，而不是激基缔合物。我们还发现了热致变色的聚二乙炔在固体膜，聚合物基体，和解决方案的滞后回线作为温度的函数。它们由聚合物聚集体的形成和聚合物链的重组来解释。