Synthesis and Evaluation of Functionality of Polymer Crystal Hybrid with Controlled Nanostructures

可控纳米结构聚合物晶体杂化物的合成与功能评价

基本信息

批准号：
16350067
负责人：
MATSUMOTO Akikazu
金额：
$ 7.42万
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 (B)
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 of unsaturated organic compounds as well as the phase transition and intercalation of the resulting polymer crystals, and revealed solid-state reaction mechanism in order to control reactions, structures, and properties of organic solids. The organic intercalation system consisting of layered organic polymers and guest amines has some characteristics different from a large number of known intercalation compounds used as inorganic hosts. The polymer crystals as the organic intercalation host have the carboxylic acid orderly arranged along the polymer chains in a high density. The positional, conformational and orientation control of the guest molecules is possible by the host polymer structure, such as tacticity. First, we have report the polymerization reactivity of muconic esters as the 1,3-diene monomers during solid-state polymerization via a crystal-to-crystal transformation process. Single crystals structure ana … More lysis for monomers and the corresponding polymers revealed the solid-state polymerization kinetics closely related to a molecular stacking distance in the monomer crystals. Powder X-ray diffractions have revealed an intermediate change in the crystal structure during the polymerization by continuous X-ray irradiation. Next, w revealed the reaction behavior and the layered structure of intercalation compounds using stereoregular poly(muconic acid)s and n-alkylamines as the host and guest, respectively. The packing structure of the guest alkylamines was determined by X-ray diffractions as well as infrared and Raman spectroscopies. We have found that the orientation of the guest molecules are controlled according to the host polymer tacticity, depending on the structure of the two-dimensional hydrogen bond network formed in the polymer sheets of the crystals. 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. This method can be applied to various organic photofunctional materials showing unique fluorescence properties. Thus, our organic polymer hosts are expected to be developed into new field of intercalation chemistry and material science. Less

在这个项目中，我们研究了不饱和有机化合物的拓扑化学聚合以及所得聚合物晶体的相变和插层，并揭示了固态反应机理，以控制有机固体的反应、结构和性质。由层状有机聚合物和客体胺组成的插层体系具有不同于大量已知用作无机主体的插层化合物的一些特征，作为有机插层主体的聚合物晶体具有沿有序排列的羧酸。高密度的聚合物链可以通过主体聚合物结构（例如立构规整度）进行位置、构象和取向控制。首先，我们报道了粘康酸酯作为1,3-二烯单体的聚合反应性。在固态聚合过程中，通过晶体到晶体的转变过程对单体和相应聚合物的单晶结构分析揭示了与分子堆积密切相关的固态聚合动力学。粉末 X 射线衍射揭示了连续 X 射线照射聚合过程中晶体结构的中间变化。接下来，我们揭示了使用立构聚粘康酸的插层化合物的反应行为和层状结构。）和正烷基胺分别作为主体和客体，通过X射线衍射以及红外和拉曼光谱测定了客体烷基胺的堆积结构。我们发现，客体分子的取向是根据主体聚合物策略控制的，具体取决于晶体聚合物片中形成的二维氢键网络的结构。此外，我们开发了一种使用双插层的方法。将烷基胺和芘作为客体来控制固态下的荧光性质，将芳香族化合物分别引入到铵聚合物晶体的疏水层中，并显示出单分子的荧光发射，但准分子则不显示这种方法。应用因此，我们的有机聚合物主体有望发展到插层化学和材料科学的新领域。

项目成果

期刊论文数量（88）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Photodimerization Mechanism of Bis(3,4,5-trifluorobenzyl) (E, E)-Muconate in a Columnar Assembly in the Crystalline State

双(3,4,5-三氟苄基)(E,E)-粘康酸酯在晶态柱状组装中的光二聚机制

DOI：
发表时间：
2007
期刊：
Chem.Lett. 36(4)
影响因子：
0
作者：
Y.Mori;A.Matsumoto
通讯作者：
A.Matsumoto

Reactions of 1,3-Diene Compounds in the Crystalline State

晶态 1,3-二烯化合物的反应

DOI：
发表时间：
2005
期刊：
Top. Curr. Chem. 254
影响因子：
0
作者：
K. Sada;K. Inoue;T. Tanaka;A. Epergyes;A. Tanaka;N. Tohnai;A. Matsumoto;M. Miyata;A. Matsumoto
通讯作者：
A. Matsumoto

Organic Intercalation with Layered Polymer Crystals Consisting of Diisotactic and Disyndiotactic Polymer Chains

由双全同立构和双间同立构聚合物链组成的层状聚合物晶体的有机插层