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.

在这个项目中，我们研究了不饱和有机化合物的拓扑化化聚合，二聚化，异构化以及所得聚合物晶体的相位转换和互嵌反应，并揭示了用于控制有机固体材料的反应，结构和特性的固态反应机制。我们首先研究了反应过程中晶体结构的变化和晶体中菌株的积累，以揭示托设聚合的机制，EZ-Photoisomerization和[2+2]将粘膜二聚态酯作为1,3-二烯酯通过晶体晶体转化作为1,3-二烯酯的循环映射。我们根据在聚合过程中原位X射线晶体结构分析的结果，提出了一种固态反应机制，以用于各种不饱和有机化合物的晶体晶格控制反应。接下来，我们通过固态聚合制备了四种定型多核酸盐，并揭示了互化化合物的反应行为和分层结构。根据宿主聚合物战术控制来宾分子的方向。我们已经制造了由结晶有机聚合物和细金属颗粒组成的纳米复合材料。此外，我们使用烷基胺和pyrene开发了一种双重介入方法，作为客人控制固态中的荧光特性。芳香化合物分别引入铵聚合物晶体的疏水层中，并显示单个分子的荧光发射，而不是准分子。我们还发现，在固体膜，聚合物基质和磁滞回路的溶液中，聚丙二乙烯的热色素与温度的关系。它们是由聚合物聚集体的形成和聚合物链的重组所解释的。