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采用两性离子型的催化剂Rh+[η-C6H5(nbd)B-(C6H5)3]实现了含手征性中心和硫代乙酸酯基的苯乙炔单体的聚合,用红外光谱、核磁共振氢谱和紫外-可见吸收光谱表征了聚合物的结构,证实得到了预期产物.聚合物的重均分子量达到了73200,在氯仿、四氢呋喃、二氯甲烷等有机溶剂中有良好的溶解性能.聚合物热稳定性高,在氮气氛围下热分解温度为336℃,在900℃的高温下有31%的重量残留.用扫描电子显微镜观察发现,在浓度为5.0mg/mL的聚合物氯仿溶液形成的薄膜中有微米长度的棒状有序结构;由浓度为0.5mg/mL的聚合物氯仿稀溶液形成的薄膜表面有晶体析出.用透射电子显微镜观察聚合物在氯仿溶液中缓慢形成的微结构,发现当浓度高于1.0mg/mL时,聚合物在碳膜上形成铺展的薄膜,薄膜由纳米尺寸的丝带状结构取向排列而成;当浓度低于0.5mg/mL时,聚合物形成具有规则几何形态的微晶体.在聚合物热稳定性的显著提高和有序微结构的形成过程中,聚苯乙炔侧链中的手征性中心发挥了关键的作用.
The polymerization of phenylacetylene monomer with chiral center and thioacetate groups was achieved by the zwitterionic catalyst Rh + [η-C6H5 (nbd) B- (C6H5) 3] The structure of the polymer was characterized by UV-Vis and UV-Vis absorption spectroscopy, and the expected product was confirmed. The weight average molecular weight of the polymer reached 73,200, which showed good solubility in organic solvents such as chloroform, tetrahydrofuran and dichloromethane. High thermal stability, a thermal decomposition temperature of 336 ° C in a nitrogen atmosphere, and a 31% weight residual at a high temperature of 900 ° C. It was observed with a scanning electron microscope that a polymer solution formed in a polymer chloroform solution having a concentration of 5.0 mg / mL The film has a rod-like ordered structure with a length of micrometer, and a crystal is formed on the surface of the film formed from a diluted solution of a polymer of chloroform at a concentration of 0.5 mg / mL The microstructure of the polymer slowly formed in a chloroform solution was observed with a transmission electron microscope When the concentration is higher than 1.0mg / mL, the polymer forms a spreading film on the carbon film, and the films are arranged in a nanosized ribbon structure orientation. When the concentration is lower than 0.5mg / mL, the polymer forms a regular geometric Micro form Thereof. In the formation of ordered and significantly increased the thermal stability of microstructure of the polymer, polyphenylene vinylene side chain chiral centers play a key role.