Computation-Assisted Investigation of Polymer Kinetics: Mechanism of the Hybridization of Cobalt-Mediated Radical Polymerization and Atom Transfer Radical Polymerization

被引：4
作者：
Wang, Fu-Sheng [1 ,2 ]
Tsai, Ya-Wen [1 ,2 ]
Xie, Meng-Qin [1 ,2 ]
Peng, Chi-How [1 ,2 ]
机构：
[1] Natl Tsing Hua Univ, Dept Chem, Hsinchu 30013, Taiwan
[2] Natl Tsing Hua Univ, Frontier Res Ctr Fundamental & Appl Sci Matters, Hsinchu 30013, Taiwan
来源：
MACROMOLECULES | 2020年 / 53卷 / 24期
关键词：
CHAIN TRANSFER; VINYL-ACETATE; BIMETALLIC CATALYSIS; POLY(VINYL ACETATE); BLOCK-COPOLYMERS; RATE CONSTANTS; ATRP; RAFT; REVERSE; COMBINATION;
D O I：
10.1021/acs.macromol.0c02255
中图分类号：
O63 [高分子化学（高聚物）];
学科分类号：
070305 ; 080501 ; 081704 ;
摘要：
In this study, we combined the kinetic measurement and the computational simulation to build a kinetic model for the hybridization of cobalt-mediated radical polymerization (CMRP) and atom transfer radical polymerization (ATRP), which is a novel method for the one-pot synthesis of block copolymers of less activated monomers and more activated monomers, such as PVAc-b-PMMA and PVAc-b-PSty. The rate constants of the two most important reactions for PVAc radical, the dissociation of PVAc-Co-III(acac)(2) and the deactivation with Cu-III(PMDETA)Br-2, have been evaluated at 40 degrees C as 4.99 X 10(-3) s(-1) and 4.19 X 10(6) M-1 s(-1), respectively. These two kinetic parameters associated with other rate constants allowed us to build a quantitative model that can simulate the polymerization behavior observed in the hybridization of CMRP and ATRP and thus rationalize the mechanism more precisely.
引用
收藏
页码：10855 / 10865
页数：11
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