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

采用阴离子活性聚合法制备了相对分子质量可控、分子量分布接近单分散、链端基团间可控的聚苯乙烯，得到了具有良好链状结构和端羧基的聚氧化乙烯。将含氨基端基的聚苯乙烯与端含羧基的聚环氧乙烷的混合物浇铸成薄膜，通过氨基和羧基之间的强相互作用，用透射电子显微镜和小角X射线散射(SAXS)研究发现，薄膜具有类似嵌段共聚物的微相分离层状结构。用透射电子显微镜和小角X射线光电子能谱测得的结构周期性与由遥爪聚合物的相对分子质量估算的结果吻合较好。此外，还考察了聚合物的混合摩尔比、浇注溶剂和聚合物的相对分子质量对微相分离结构的影响。无论远程螺旋聚合物的摩尔比是多少，在1：2到2：1的范围内都可以观察到层状结构。苯、二氧六环和四氢呋喃具有相似的周期性，而用氯仿浇注时观察到较小的微区尺寸。较大相对分子质量(3×10~(-4))的遥控聚苯乙烯疏松了周期性结构，但相对分子质量较低的遥控聚合物形成了更规则的结构，用氢氧化钾-甲醇清洗共混物的薄膜，去除了遥控聚氧乙烷，形成了多孔膜，并用SAXS、SEM和BET方法测量了其比表面积。

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.