球磨双金属氰催化剂催化CO_2/环氧丙烷/四氯苯酐三元共聚

由于共聚配合剂的加入有利于提高双金属氰催化剂(DMC)的催化活性,因此本文通过加入不同的共聚配合剂,采用绿色高效的机械球磨法制备了Zn-Co DMC催化剂体系,然后将DMC用于制备CO2、环氧丙烷和四氯苯酐(THPA)的三元共聚物聚碳酸亚丙酯四氯苯酐(PPCPA)。通过傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)、多晶X射线衍射(XRD)、凝胶渗透色谱(GPC)和热重分析(TG)等技术手段表征了催化剂和PPCPA的结构和性能。结果表明,共聚配合剂辅助球磨Zn-Co DMC催化聚合反应转化数25.67~141.80,PPCPA数均相对分子量2.21×10~3~3.15×10~3,多分散指数1.04~1.24,呈现窄分布。PPCPA的热稳定性要高于聚碳酸亚丙酯(PPC),热分解温度提高了129.8℃。

Synthesis of Terpolymers Derived from CO2, Propylene Oxide and Tetrachlorophthalic Anhydride Using Double Metal Cyanide Catalysts by Ball Milling

The addition of co-complexing agent is beneficial to improve the catalytic activity of the double metal cyanide(DMC) catalyst. In this paper poly(propylene carbonate tetrachlorophthalic phthalate)(PPCPA) terpolymers were successfully synthesized from carbon dioxide, propylene oxide and tetrachlorophthalic anhydride catalyzed by ball milling synthesized Zn-Co DMC catalysts. The properties and structures of Zn-Co DMC catalysts and the resulting terpolymers were characterized by Fourier transform infrared spectroscopy(FTIR), scanning electron microscope(SEM), X-ray diffraction(XRD), gel permeation chromatography(GPC) and thermogravimetric analysis(TG). The results show that the turnover number of Zn-Co DMC catalysts is up to 25.67~141.80, and the number-average relative molecular mass of PPCPA is up to 2.21×10³~3.15×10³ with a narrow polydispersity index of 1.04~1.24. Compared with polypropylene carbonate(PPC), PPCPA shows a higher thermal stability, and the thermal decomposition temperature of PPCPA is increased by 129.8 ℃.