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Synthesis of Polymers with Amino and Carboxy Terminals and Ordered Structure of the Polymer Assemble

氨基和羧基端基聚合物的合成及聚合物组装体的有序结构

基本信息

批准号：
63470094
负责人：
NAKAHAMA Seiichi
金额：
$ 0.51万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1988
资助国家：
日本
起止时间：
1988 至 1989
项目状态：
已结题

项目摘要

Polystyrenes having controlled molecular weights, nearly monodisperse molecular weight distributions, and among group at the chain terminal were prepared by anionic living polymerization.Similarly, polyethylene oxides with well defined chain structure and the terminal carboxy group were obtained. A mixture of the polystyrene with amino terminal and the polyethlene oxide with carboxy end group was cast into a thin film, which was found to have microphase separated lamellar structure like a block copolymer through the strong interaction between amino and carboxy groups by using transmission electron micrography(TEM) and small angle X-ray scattering(SAXS). The periodicities of the structure measured by TEM and SAXS agreed reasonably with the one estimated from the molecular weights of the telechelic polymers. Furthermore, the effects of the mixing molar ratio of the polymers, casting solvents, and the molecular weights of the polymers on the microphase separated structure were investigated. Regardless of the molar ratio of the telechelic polymers, the lame1lar structure was observed in the range of 1:2 to 2:1. Benzene, dioxane, and tetrahydrofurane gave similar periodicities, whereas small domain size was observed when cast from chloroform. The telechelic polymers of lower molecular weights form more regular structure although the telechelic polystyrene with larger molecular weight( 3 x 10^4 ) looses the periodic structure.The film of the polymer blend was rinsed with KOH-methanol to remove the telechelic polyethylene oxide resulting in the porous membrane, which was substrantiated by SAXS, SEM, and measurement of surface area by BET method.

通过阴离子活性聚合制备了具有可控分子量、近单分散分子量分布和链端基团之间的聚苯乙烯。同样，得到了具有明确链结构和端羧基的聚环氧乙烷。将端氨基聚苯乙烯和端羧基聚环氧乙烷的混合物浇铸成薄膜，通过透射电子显微术（TEM）和小角X射线散射（SAXS）发现，通过氨基和羧基之间的强相互作用，薄膜具有类似嵌段共聚物的微相分离层状结构。通过 TEM 和 SAXS 测量的结构周期性与根据遥爪聚合物分子量估计的结构周期性相当一致。此外，还研究了聚合物的混合摩尔比、浇铸溶剂和聚合物的分子量对微相分离结构的影响。无论遥爪聚合物的摩尔比如何，在1:2至2:1范围内观察到层状结构。苯、二恶烷和四氢呋喃具有相似的周期性，而当用氯仿浇铸时观察到小域尺寸。尽管分子量较大（3 x 10^4）的遥爪聚苯乙烯失去了周期性结构，但较低分子量的遥爪聚合物形成了更规则的结构。用KOH-甲醇冲洗聚合物共混物的薄膜，去除遥爪聚环氧乙烷，形成多孔膜，并通过SAXS、SEM和BET法测量表面积证实。