Dipartimento di Chimica, Università di Perugia, Via Elce di Sotto 8, 06123 Perugia, Italy.
J Am Chem Soc. 2010 Oct 6;132(39):13651-3. doi: 10.1021/ja105965x.
Activation parameters for propene polymerization mediated by a bis(phenoxyamine)Zr-dibenzyl catalyst in combination with MAO have been measured experimentally and calculated by DFT; experiment and calculation consistently indicate that the entropic term is the most important reason for the low chain propagation rate with this system. Based on this finding and a review of literature data on a variety of olefin polymerization catalysts, we propose a strong correlation between the propagation rate and how catalysts deal with the entropy loss of monomer capture.
通过实验测量和 DFT 计算，研究了双（苯氧胺）Zr-二苄基催化剂与 MAO 共同引发丙烯聚合的活化参数；实验和计算结果一致表明，在该体系中，熵项是导致链增长速率低的最重要原因。基于这一发现以及对各种烯烃聚合催化剂文献数据的回顾，我们提出了增长速率与催化剂如何处理单体捕获熵损失之间的强相关性。
