Orientation of Crystals and Novel Functionality Produced by Control of Polymer-Solvent Molecular Compounds

研究了间规聚苯乙烯（SPS）、间规聚对叔丁基苯乙烯（SPTBS）和等规聚苯乙烯（IPS）中形成的聚合物-溶剂分子化合物的凝胶和笼形共晶的形成过程。（1）首次证明了SPTBS在光照下发生溶胶转化，这一新现象是物理凝胶中的一个普遍反应过程，是通过聚合物-溶剂分子化合物与有规立构聚合物的侧链发色团形成的。它已被保证，这种光诱导的溶胶转化发生只有当聚合物链采取纤维状网络。这一过程可以用激发能被侧链发色团吸收后非辐射地传递到分子化合物中的溶剂分子上，使分子化合物发生解离来解释。溶胶光转化可作为一种新型的有效的光响应体系。(2)通过测定温度-浓度相图，详细研究了SPS、IPS和SPTBS与包括香料在内的各种溶剂的物理凝胶的形态和稳定性。因此，这些凝胶中的聚合物链的形态被澄清为取决于（i）结晶速率和（H）溶剂分子与侧链苯基之间的相容性。(3)客体分子高度取向的条件已被检查和监测，通过我们的方法测量偏振荧光的角分布，通过旋转样品膜周围的激发光束。最后，我们成功地展示了笼形物共晶薄膜的制备方法，其中客体分子在整个薄膜中具有几乎相同的排列，这表明我们可以制备功能分子高度取向的新型薄膜。

The formation processes of gels and clathrate cocrystals have been studied by focusing on polymer-solvent molecular compounds formed in syndiotactic polystyrene (SPS), syndiotactic poly(p-tert-butylstyrene)(SPTBS), and isotactic polystyrene (IPS). The important results are as follows: (1) SPTBS was first proved to show sol conversion induced by light irradiation, suggesting that this novel phenomenon is a general reaction process in physical gels formed by way of the formation of polymer-solvent molecular compounds with side-chain chromophores of stereoregular polymers. It has been assured that this photo-induced sol conversion takes place only when polymer chains take fibrillar networks. The process can be explained by the excitation energy, which was absorbed by side-chain chromophore and was transferred non-radiatively to the solvent molecule in a molecular compound, swaying the molecular compound to dissociate. The sol conversion by light can be used as a new effective photo-responsive system. (2) Many physical gels of SPS, IPS and SPTBS with various solvents including fragrance have been examined in detail by determining temperature-concentration phase diagrams in order to study on morphology and stabilization. Consequently the morphology of polymer chains in these gels is clarified to depend on (i) rate of crystallization and (H) compatibility between solvent molecules and side-chain phenyl groups. (3) The conditions where guest molecules are highly oriented have been examined and monitored by our method of measuring angular distribution of polarized fluorescence by rotating sample films around the excitation light beam. Finally we have succeeded to show the preparation method of clathrate cocrystalline films where guest molecules have nearly the same arrangements all over the film, suggesting that we can prepare the novel films where functional molecules are highly oriented.