Enantiomer-Selective Radical Polymerization of Bis(4-vinylbenzoate)s with Chiral Atom Transfer Radical Polymerization Initiating Systems
Enantiomer-Selective Radical Polymerization of Bis(4-vinylbenzoate)s with Chiral Atom Transfer Radical Polymerization Initiating Systems
复制标题
DOI：
10.1021/ma071162j
复制
发表时间：
2007-11
期刊：
影响因子：
5.5
通讯作者：
A. Narumi;R. Sakai;So Ishido;M. Sone;T. Satoh;H. Kaga;Hiroshi Nakade;T. Kakuchi
中科院分区：
文献类型：
--
作者：
A. Narumi;R. Sakai;So Ishido;M. Sone;T. Satoh;H. Kaga;Hiroshi Nakade;T. Kakuchi
本文报道了一系列手性配体作用下的原子转移自由基聚合（ATRP）反应。通过外消旋双官能单体rac-2，4-戊二基双（4-乙烯基苯甲酸酯）（rac-1）的聚合，得到了具有手性性质的环化聚合物，并回收了对映体不平衡的双官能单体，为rac-1通过ATRP与手性配体介导的对映体选择性聚合提供了有力的证据。对映体纯单体（2 R，4 R）-2，4-戊二基双（4-乙烯基苯甲酸酯）（RR-1）和（2S，4S）-2，4-戊二基双（4-乙烯基苯甲酸酯）（SS-1）之间的比较揭示了它们在ATRP过程中均聚速率的显著差异。RR-1与SS-1的对映体共聚反应表明，对于含手性配体的ATRP，RR-1的单体竞聚率高于SS-1。均聚和共聚的结果都清楚地表明了……
We report a series of cyclopolymerizations of bis(4-vinylbenzoate) monomers through an atom transfer radical polymerization (ATRP) using chiral ligands. Cyclized polymers showing chiroptical properties were produced by polymerization of the racemic bifunctional monomer, rac-2,4-pentanediyl bis(4-vinylbenzoate) (rac-1), and enantiomerically unbalanced bifunctional monomers were recovered, providing substantial evidence for the enantiomer-selective polymerization of rac-1 mediated through the ATRP with chiral ligands. A comparison between the enantiomerically pure monomers, (2R,4R)-2,4-pentanediyl bis(4-vinylbenzoate) (RR-1) and (2S,4S)-2,4-pentanediyl bis(4-vinylbenzoate) (SS-1), revealed a drastic discrepancy in the rates of their homopolymerizations during the ATRP. The enantiomeric copolymerization of RR-1 and SS-1 indicated that the monomer reactivity ratio of RR-1 was higher than that of SS-1 for the ATRP with chiral ligands. The results of both homopolymerizations and copolymerizations clearly demons...