OALib Journal期刊
丙烯聚合中氢气对负载型Z-N催化剂活性中心的影响
DOI: 10.3724/SP.J.1105.2013.13127
Keywords: 丙烯聚合 ,氢气 ,负载型Z-N催化剂 ,活性中心
Abstract:
研究了氢气和硅烷类外给电子体对负载型Z-N催化剂催化丙烯聚合微观动力学的影响.通过噻吩酰氯淬灭法测定了聚合体系的活性中心浓度和链增长速率常数（kp）.通过聚合物的萃取分级，得到了生成无规聚丙烯、中等规度聚丙烯和等规聚丙烯的三类活性中心的数量及其kp值.结果表明，氢气提高聚合活性的效应源于活性中心浓度和kp值的同时增大.三类活性中心的氢气响应特性显著不同.生成无规聚丙烯的活性中心的数量在加入氢气后变化幅度最小，而生成中等规度聚丙烯的活性中心的kp值在加入氢气后增加幅度最大.改变外给电子体也显著影响三类活性中心的氢气响应特性.增加外给电子体的烷基取代基空间位阻一方面降低了发生区域选择性和立体选择性插入错误的几率，同时也降低了氢气影响kp值的程度，说明氢气活化效应与活性中心的区域选择性和立体选择性密切相关.根据实验结果提出了氢气活化效应的微观机理模型.
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