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

在该项目中，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入，并揭示了固态反应机制，以控制有机固体的反应，结构和特性。由分层有机聚合物和来宾胺组成的有机插入系统的特征与大量已知的插入化合物不同，用作无机宿主。聚合物晶体作为有机插入宿主的羧酸以高密度沿聚合物链排列。宿主聚合物结构（例如战术性）可以实现客座分子的位置，构象和取向控制。首先，我们报告了通过晶体到晶体转化过程在固态聚合过程中粘液酯作为1,3-二烯基单体的聚合反应性。单晶结构ANA…对单体和相应的聚合物进行更多的裂解，揭示了与单体晶体中的分子堆叠距离密切相关的固态聚合动力学。粉末X射线衍射显示通过连续X射线照射在聚合过程中晶体结构发生了中间变化。接下来，W分别使用立体牙粒聚（粘辛酸）S和N-烷基胺作为宿主和来宾揭示了插入化合物的反应行为和分层结构。客体烷基胺的填料结构由X射线衍射以及红外和拉曼光谱法确定。我们发现，根据宿主聚合物战术性控制来宾分子的方向，具体取决于在晶体的聚合物片中形成的二维氢键网络的结构。此外，我们使用葡萄球菌和pyrene开发了一种双重介入方法，作为客人控制固态的荧光特性。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。该方法可以应用于显示独特的荧光特性的各种有机光功能材料。这是，我们的有机聚合物宿主有望发展成为互插性化学和材料科学领域的新领域。较少的

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

Stereocontrol of Diene Polymers by Topochemical Polymerization of Substituted Benzyl Muconates and Their Crystallization Properties

取代粘康酸苄酯拓扑化学聚合二烯聚合物的立体调控及其结晶性能

DOI：
发表时间：
2006
期刊：
J. Polym. Sci, Part A, Polym. Chem. 44
影响因子：
0
作者：
A. Matsumoto;D. Furukawa;H. Nakazawa
通讯作者：
H. Nakazawa

Molecular Stacking and Photoreactions of Fluorine-Substituted Benzyl Muconates in the Crystals

晶体中氟取代粘康酸苄酯的分子堆积和光反应

DOI：
发表时间：
2007
期刊：
Cryst. Growth Des. 7(2)
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