球磨Zn-Co DMC催化二氧化碳、环氧丙烷和琥珀酸酐的三元共聚反应及热稳定性

摘要

通过添加不同的共聚络合剂聚乙二醇(PEG)、聚丙二醇(PPG)、聚四氢呋喃(PTMEG)和聚乙二醇-聚丙二醇-聚乙二醇(PEG-PPG-PEG),以快速高效的球磨法合成了Zn-Co双金属催化剂(DMC) 体系.采用红外(IR)、元素分析(EA)、扫描电镜(SEM)和多晶X射线衍射(XRD)测试表征Zn-Co DMC的结构和形貌.在此基础上,证明了Zn-Co DMC有效地催化二氧化碳、环氧丙烷和琥珀酸酐的三元共聚反应,并通过IR、核磁共振谱(1H NMR和13C NMR)、凝胶渗透色谱(GPC)和热重分析(TG)等方法对聚合产物的结构和热性能进行测试表征.结果表明,在聚合反应中,添加了共聚络合剂的DMC催化剂具有良好的催化活性且聚合物含量较高.聚合物聚碳酸亚丙酯琥珀酸酐(PPCSA)的数均分子量可达到2.2~3.9 K,分子量分布指数PDI较窄为1.05~1.08.在聚合物分子链中引入丁二酰基致使PPCSA的热分解温度相比PPC提高了60.9~70.1 ℃.%Zn-Co double metal cyanide (DMC) catalysts were successfully synthesized by fast and efficient ball millng by blending with co-complexing agents, such as polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene ether glycol (PTMEG) and polyethylene glycol-polypropylene glycol-polyethylene glycol (PEG-PPG-PEG) during the grinding process.Variety of Zn-Co double metal cyanide (DMC) catalysts were characterized by Fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA), scanning electron microscope (SEM)and X-ray diffraction (XRD).On this basis, the DMC catalysts were proven to be effective for the terpolymerization of carbon dioxide, propylene oxide and succinic anhydride.The structure and thermal properties of the terpolymers were confirmed by IR, NMR spectrometer (1H NMR and 13C NMR), gel permeation chromatography (GPC) and thermogravimetric analysis (TG).The results show that the DMCs showed relatively high activity and higher polymer content for copolymerization.The number-average molecular weight (Mn) of the terpolymer PPCSA was up to 2.2-3.9 K with a narrow polydispersity index (PDI) of 1.05-1.08.The thermal decomposition temperature of PPCSA were dramatically increased by 60.9-70.1 ℃ in comparison with PPC, due to the introduction of succinyl into the backbone of terpolymer.