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Synthesis of Highly Selective Polymer Materials with Solid-Solution Phases and Multiphase-Structure Analysis under Functioning State

高选择性固溶相高分子材料的合成及功能状态下的多相结构分析

基本信息

批准号：
59430016
负责人：
URYU Toshiyuki
金额：
$ 22.4万
依托单位：
Institute of Industrial Science, University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (A)
财政年份：
1984
资助国家：
日本
起止时间：
1984 至 1986
项目状态：
已结题

项目摘要

Dextran-type polysaccharides containing sulfamide and sulfate groups at regio-selective positions were synthesized by a series of reactions starting from the ring-opening polymerization of 1,6-anhydro-azido sugars. The sulfamide group exhibted almost the same anticoagulant activity as that of the sulfate group, and the former had a function to decrease the acute toxicity <LD_(50)> . 1,5- <alpha> -Linked furanan-type polysaccharides which were prepared by the ring-opening polymerization of 1,4-anhydro-ribose and -xylose were sulfated to give sulfated furanan-type polysaccharides. These heparinoids showed the highest anticoagulant activity of the so-far prepared heparinoids. The structure analysis of synthetic polysaccharides and sulfated ones was performed by using ordinary NMR and 2D NMR spectroscopy as well as the elemental analysis, indicating the position of sulfate group.Chloromethylated polystyrene beads were reacted with various alkylamines to provide the stationary phase of high … More perfomance liquid chromatography. The obtained chloromethylated polystyrene beads can be used in a wide pH range. In addition, the selective separation of halobenzenes and alkylbenzenes was possible by properly choosing the alkyl chain length, for example, by using a <C_(14)> stationary phase. Functionalization of crosslinked poly(chloromethylstyrene) beads was carried out by the reaction with sodium nitrite in the presence of phase transfer catalyst to afford the beads having carboxyl and hydroxyl groups.Thermotropic aromatic polyesters and low-molecular-weight model compounds were synthesized. They consisted of aromatic mesogens and flexible alkylene spacers. The structure of aromatic polyesters most of which were hardly soluble in solvents were analyzed with solid state CP/MAS <^(13)C> NMR spectroscopy. In the polyester prepared at low temperature, the alkoxy group bonded to the aromatic ring had a fixed orientation, which provides a guide to the molecular design of liquid crystalline polymers with excellent mechanical properties. Less

以1,6-脱水叠氮糖的开环聚合为起始点，通过一系列反应合成了在区域选择性位置含有磺酰胺和硫酸基团的葡聚糖型多糖。磺酰胺基表现出与硫酸基几乎相同的抗凝血活性，并且前者具有降低急性毒性<LD_(50)>的功能。将通过1，4-脱水核糖和β-木糖的开环聚合制备的1，5-α-连接的呋喃型多糖硫酸化，得到硫酸化呋喃型多糖。这些类肝素在迄今为止制备的类肝素中表现出最高的抗凝血活性。利用普通核磁共振和二维核磁共振波谱以及元素分析对合成多糖和硫酸化多糖进行结构分析，指示硫酸基的位置。氯甲基化聚苯乙烯珠与各种烷基胺反应，提供高效液相色谱的固定相。所得氯甲基化聚苯乙烯珠可在较宽的pH范围内使用。此外，通过适当选择烷基链长度，例如通过使用<C_(14)>固定相，可以选择性分离卤代苯和烷基苯。在相转移催化剂存在下，通过与亚硝酸钠反应，对交联聚氯甲基苯乙烯珠粒进行官能化，得到具有羧基和羟基的珠粒。合成了热致性芳香族聚酯和低分子量模型化合物。它们由芳香族介晶和柔性亚烷基间隔基组成。用固态CP/MAS 1 (13) C NMR光谱分析了大部分难溶于溶剂的芳香族聚酯的结构。在低温制备的聚酯中，与芳环键合的烷氧基具有固定的取向，这为具有优异机械性能的液晶聚合物的分子设计提供了指导。较少的