Theoretical study on the polymerization mechanism of substituted maleimides by using a chiral catalyst with Zn2+
Theoretical study on the polymerization mechanism of substituted maleimides by using a chiral catalyst with Zn2+
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DOI：
10.1016/s0040-4020(03)01014-7
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发表时间：
2003-08-11
期刊：
影响因子：
2.1
通讯作者：
Oishi, T
中科院分区：
文献类型：
--
作者：
Hori, K;Yoshimura, K;Oishi, T
用锌和N-二苯基甲基-1-苄基-2-吡咯烷基乙胺（DPhBP）的手性配合物合成聚（N-取代马来酰亚胺）是可能的。所得聚合物的旋光比旋光度[a] 25435取决于催化剂中配体的手性。在本研究中。采用密度泛函理论（DFT）方法对聚合反应机理进行了详细的研究。在手性配体中的庞大的二苯基甲基是有效的，以促进在引发反应中的产物的形成。与Zn催化剂中手性配体的吡咯烷环相关的几何形状负责决定聚合物的构型。还证实了N-取代马来酰亚胺的N原子上的庞大取代基是获得具有高[α]的聚合物的另一个因素（435）（25）。(C)2003爱思唯尔有限公司。保留所有权利。
It is possible to synthesize poly(N-substituted maleimide) by using a chiral complex consisting of a zinc and N-diphenylmethyl-1-benzyl-2-pyrrolidinoethanamine (DPhBP). The optical specific rotations [a]25 435 in obtained polymers depend on the chirality of ligands in the catalysts. In the present study. density functional theory (DFT) calculations were adopted to investigate the polymerization mechanism in detail. The bulky diphenylmethyl group in the chiral ligand is effective to enhance the formation of the product in the initiation reaction. The geometry related to the pyrrolidine ring of the chiral ligand in the Zn catalyst is responsible for determining the configuration of polymers. It was also confirmed that the bulky substituent on the N atom of the N-substituted maleimide is another factor for obtaining polymers with high [alpha](435)(25). (C) 2003 Elsevier Ltd. All rights reserved.