Structure and Relaxation Characteristics, and Functionnalization of Liquid-Crystalline Glassy Materials Based on Mesomorphic Cholesterol Derivatives and Polysaccharides

本研究旨在阐明(a)胆固醇与脂肪胺配合物和(b)高取代纤维素和几丁质烷基酯形成液晶（LC）玻璃相的超分子结构和热光学性质。基于其他相关衍生物的光学功能材料也进行了设计。胆固醇衍生物与脂肪族单胺的配合物：(1)研究了胆固醇邻苯二甲酸氢盐（CHP）或琥珀酸盐（CHS）与正常脂肪族单胺（Cn-amine’s）的1:1配合物形成的LC玻璃的焓弛度随胺组分碳数的变化规律。采用CHIP或CHS与m≠n的两种等摩尔Cm-胺和Cn-胺组成的复合混合物作为LC玻璃样品。考虑到氨基烷基链长度分布的影响和分子排列类型的差异，对不同的LC玻璃进行了比较讨论。(2)离子。更多的CHS与含有光功能偶氮苯的胺类化合物的配合物被发现适用于利用可逆的各向异性-各向同性玻璃相转变的新记录系统。高取代纤维素和几丁质烷基酯：完成了n=4-20的纤维素三正酰基酯（Cn-ACells）和几丁质二正酰基酯（Cn-ACh）的热转变方案。DSC热分析观察到的聚合物干链和烷基侧链的复数亚晶态排列，通过控温x射线衍射更清晰。纤维素和甲壳素衍生物的其他相关衍生物：以乙烯基单体为溶剂，将纤维素和甲壳素衍生物的胆甾相LC溶液光聚合制备成薄膜形式的聚合物复合材料，并研究了固体膜的热学性能。研究了纤维素酯与乙烯共聚物的混相共混物作为双折射可控光学介质在功能薄膜上的适用性。少

The present research aimed at elucidating supramolecular structure and thermal and optical properties of (a) cholesteryl complexes with aliphatic amines and (b) highly substituted cellulose and chitin alkyl esters, both forming a liquid-crystalline (LC) glassy phase. Optically functional materials based on other related derivatives were also designed.1. Complexes of Cholesterol Derivatives with Aliphatic Monoamines:(1) Enthalpy relaxation of the LC glasses formed by 1:1 complex salts of cholesterol hydrogen phthalate (CHP) or succinate (CHS) with normal aliphatic monoamines (Cn-amine's) was studied as a function of the carbon number of the amine component. Complex mixtures composed of CHIP or CHS and two equimolar Cm- and Cn- amines of m≠n were also used as the LC glass samples. Comparative discussion was made by taking account of an effect of the distribution in length of the amino alkyl chain and a difference in the type of molecular arrangement in the respective LC glasses.(2) Ionic … More complexes of CHS with amine compounds containing a photo-functional azobenzene moiety were found to be applicable to a new recording system utilizing a reversible anisotroipic-isotropic glassy phase transition.2. Highly Substituted Cellulose and Chitin Alkyl Esters:Thermal transition schemes were completed for cellulose tri-normal acylates (Cn-ACells) and chitin di-normal acylates (Cn-ACh) of n=4-20. The arrangements of trunk-polymer chains and alkyl side-chains in the plural mesomorphic states observed by DSC thermal analysis were made clearer by a temperature-controlled X-ray diffractometry.3. Other Related Derivatives of Cellulose and Chitin:Polymer composites were prepared in film form from cholesteric LC solutions of cellulose and chitin derivatives via photo-polymerization of vinyl monomers as solvent, and the chiroptical properties of the solid films were investigated. Some miscible blends of cellulose esters with vinyl copolymers were evaluated for the applicability to functional films as a birefringence-controllable optical medium. Less