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OALib Journal期刊
ISSN: 2333-9721
费用：99美元
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双官能卟啉铝配合物催化二氧化碳与环氧化合物的共聚合
DOI: 10.11777/j.issn1000-3304.2014.14080, PP. 1017-1022
Keywords: 双官能化催化剂,卟啉铝,二氧化碳,环氧化物,二氧化碳共聚物
Abstract:
为解决聚合物中有毒金属残留问题，选择绿色环保的金属铝作为催化剂活性中心，并通过将助催化剂季铵盐接在卟啉配体上的方法，合成了新型双官能化卟啉铝配合物，通过1H-NMR、13C-NMR、MALDI-TOF等方法对其进行了表征和确认.该催化体系可在不加助催化剂的条件下高效催化CO2/环氧丙烷（PO）共聚合，其活性显著高于传统的卟啉铝配合物/季铵盐双组份催化体系.使用配合物1b详细考察了温度、压力等因素对聚合反应的影响，在90℃，3.0MPa的反应条件下，反应5h后TOF（单位时间内每摩尔催化剂转化的单体数）可达1152h-1，所得聚合物碳酸酯含量98%，数均分子量Mn=42×103，但聚合物选择性较低（68%）.配合物1b同样可以高效的催化CO2/环氧环己烷（CHO）共聚，在相同的反应条件下，TOF可达621h-1，聚合体系中无环状副产物生成，所得聚合物碳酸酯含量81%，数均分子量Mn=8.0×103.另外，通过改变配合物中的季铵盐阴离子和轴向配体，考察了不同引发基团对催化剂活性、聚合物选择性的影响.
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