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

本文主要研究了合规聚苯乙烯（SPS）、合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物共晶的形成过程。重要结果如下：(1)SPTBS首次证明了光照射诱导的溶胶转化，表明这种新现象是聚合物-溶剂分子化合物与侧链立体规则聚合物发色团形成的物理凝胶中的一般反应过程。可以肯定的是，这种光诱导的溶胶转化只有在聚合物链呈纤维状网络时才会发生。这一过程可以用激发能来解释，激发能被侧链发色团吸收，并以非辐射方式转移到分子化合物中的溶剂分子，使分子化合物发生离解。光转化溶胶可以作为一种新的有效的光响应系统。(2)通过测定温度-浓度相图，对SPS、IPS和SPTBS等多种溶剂（包括香精）的物理凝胶进行了详细的研究，以研究其形态和稳定性。因此，这些凝胶中聚合物链的形态被澄清取决于(i)结晶速率和(H)溶剂分子与侧链苯基之间的相容性。(3)通过在激发光束周围旋转样品膜来测量偏振荧光的角分布，我们对客体分子高度定向的条件进行了检测和监测。最后，我们成功地展示了包合物共晶薄膜的制备方法，其中客体分子在整个薄膜上几乎具有相同的排列方式，这表明我们可以制备功能分子高度定向的新型薄膜。

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.