A DFT INVESTIGATION OF THE MECHANISM FOR ALTERNATINGCOPOLYMERIZATION OF STYRENE WITH CARBON MONOXIDE CATALYZED BY Pd(Ⅱ) COMPLEXES

作     者：Zi-dan Zhang 何学浩 Shi-chun Jiang 

作者机构：Department of Polymer Science and EngineeringSchool of Chemical Engineering and TechnologyTianjin UniversityTianjin300072China Department of ChemistrySchool of ScienceTianjin UniversityTianjin300072China School of Material Science&EngineeringTianjin UniversityTianjin300072China 

出 版 物：《Chinese Journal of Polymer Science》 (高分子科学（英文版）)

年 卷 期：2012年第30卷第5期

页      面：744-758页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：financially supported by the NSFC(Nos.91127046 and 20974078) KPCME(No.109043) SRFDP (No.200800561006) High Performance Computing Center of Tianjin University,China and National Supercomputer Center in Tianjin,China 

主　　题：DFT CO Styrene Polyketone Mechanism. 

摘      要：Density functional theory has been employed to study the homogeneous catalytic copolymerization of styrene with carbon monoxide. The copolymerization reaction is catalyzed by Pd（II） coordinated with 2,2＇-bipyridine, a conventional nitrogen-containing bidentate ligand with achiral C2v symmetry. The chain propagation mechanism for the alternating copolymerization as well as the side reactions, including multiple insertions of CO and homopolymerization of styrene, has been investigated. This study focused exclusively on regioisomerism and stereoisomerism. We have demonstrated that the strictly alternating copolymerization is kinetically and thermodynamically favored over the side reactions （i.e., multiple insertions of CO and homopolymerization of styrene）. The regiochemistry study indicates the 2,1 type. Furthermore, the stereochemistry study shows that the syndiotactic conformation is preferred over the isotactic or atactic conformations.