Initiation Kinetics in Free-Radical Polymerization: Prediction of Thermodynamic and Kinetic Parameters Based on ab initio Calculations

被引：32

作者：

Dossi, Marco ^{[1
]}

Storti, Giuseppe ^{[1
]}

Moscatelli, Davide ^{[1
]}

机构：

[1] Politecn Milan, Dipartimento Chim Mat & Ingn Chim Giulio Natta, I-20131 Milan, Italy

来源：

MACROMOLECULAR THEORY AND SIMULATIONS | 2010年 / 19卷 / 04期

关键词：

initiation; kinetics; modeling; polymerization; quantum chemistry; PROPAGATION RATE COEFFICIENTS; CHAIN-LENGTH DEPENDENCE; METHYL-METHACRYLATE; POTASSIUM PERSULFATE; ACRYLATE; TEMPERATURE; COPOLYMERIZATION; ACRYLONITRILE; DECOMPOSITION; TERMINATION;

D O I：

10.1002/mats.200900056

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

Initiation kinetics in free radical polymerization is investigated using density functional theory. Thermodynamic and kinetic parameters of the initiation reactions are predicted, and the role of the initiators in the polymerization process is evaluated. Methyl acrylate, methyl methacrylate, acrylonitrile, and styrene homo-polymerizations with different initiators are studied. Reaction enthalpy and activation energy for each reaction between monomer and the radical fragments arising from the initiators have been determined. The initiation kinetic constants for all of these initiation reactions are evaluated and compared with both computational and experimental propagation kinetic constants of each monomer.

引用

页码：170 / 178

页数：9

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