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

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以及聚合物晶体的相变和插层，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有机插层体系具有与大量已知的作为无机主体的插层化合物不同的特点。聚合物晶体作为有机插层主体，羧酸沿聚合物链高密度有序排列。客体分子的位置、构象和取向控制可以通过宿主聚合物的结构来实现。首先，我们报道了作为1,3-二烯单体的黏稠酯在固态聚合过程中通过晶体到晶体的转化过程的聚合反应性。单晶结构和对单体及相应聚合物的更多裂解揭示了固态聚合动力学与单体晶体中的分子堆积距离密切相关。在连续的x射线照射下，粉末的x射线衍射显示了聚合过程中晶体结构的中间变化。接下来，我们揭示了以正规整聚黏液酸和正烷基胺为主体和客体的插层化合物的反应行为和层状结构。用x射线衍射、红外光谱和拉曼光谱测定了客体烷基胺的填充结构。我们发现客体分子的取向是根据主体聚合物的定向性来控制的，这取决于晶体聚合物片中形成的二维氢键网络的结构。此外，我们开发了一种以烷基胺和芘为客体的双插层方法来控制固态下的荧光性质。芳香化合物被单独地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，而不是准分子。该方法可应用于具有独特荧光特性的各种有机光功能材料。因此，我们的有机高分子主体有望在插层化学和材料科学的新领域得到发展。少

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