The Crucial Role of Diffusional Limitations in Controlled Radical Polymerization

被引：128

作者：

D'hooge, Dagmar R. ^{[1
]}

Reyniers, Marie-Francoise ^{[1
]}

Marin, Guy B. ^{[1
]}

机构：

[1] Univ Ghent, Chem Technol Lab, B-9000 Ghent, Belgium

来源：

MACROMOLECULAR REACTION ENGINEERING | 2013年 / 7卷 / 08期

关键词：

ATRP; diffusion; modeling; NMP; RAFT polymerization; NITROXIDE MEDIATED POLYMERIZATION; FRAGMENTATION CHAIN TRANSFER; TERMINATION RATE COEFFICIENTS; LENGTH-DEPENDENT TERMINATION; METHYL-METHACRYLATE; SOLVENT SYSTEMS; HIGH CONVERSION; CFD ANALYSIS; SEMIBATCH; ATRP;

D O I：

10.1002/mren.201300006

中图分类号：

TQ [化学工业];

学科分类号：

0817 ;

摘要：

The importance of diffusional limitations in controlled radical polymerization at laboratory scale and in homogeneous medium is highlighted using different diffusion models. In particular, a coupled 'parallel' encounter pair model is introduced which allows a rigorous description of the influence of diffusional limitations on the activation/deactivation process. Diffusional limitations on termination have a significant influence, whereas those on the activation/deactivation process can disturb the regular growth pattern at high conversion if the mediating agent is a sufficiently bulky species. Diffusional limitations on initiation are only important in case radical initiator is still present at high conversion.

引用

页码：362 / 379

页数：18

共 93 条

[1] A review of modeling of diffusion controlled polymerization reactions [J].

Achilias, Dimitris S. .

MACROMOLECULAR THEORY AND SIMULATIONS, 2007, 16 (04) :319-347

[2] DEVELOPMENT OF A GENERAL MATHEMATICAL FRAMEWORK FOR MODELING DIFFUSION-CONTROLLED FREE-RADICAL POLYMERIZATION REACTIONS [J].

ACHILIAS, DS ;

KIPARISSIDES, C .

MACROMOLECULES, 1992, 25 (14) :3739-3750

[3] STEADY-STATE MULTIPLICITY DURING SOLUTION POLYMERIZATION OF METHYL-METHACRYLATE IN A CSTR [J].

ADEBEKUN, AK ;

KWALIK, KM ;

SCHORK, FJ .

CHEMICAL ENGINEERING SCIENCE, 1989, 44 (10) :2269-2281

[4]

Asua JM, 2007, POLYMER REACTION ENGINEERING, P1, DOI 10.1002/9780470692134

[5] Chain-length-dependent termination in radical polymerization: Subtle revolution in tackling a long-standing challenge [J].

Barner-Kowollik, Christopher ;

Russell, Gregory T. .

PROGRESS IN POLYMER SCIENCE, 2009, 34 (11) :1211-1259

[6]

BarnerKowollik C., 2008, Handbook of RAFT Polymerization

[7] Kinetic modeling of miniemulsion nitroxide mediated polymerization of styrene: Effect of particle diameter and nitroxide partitioning up to high conversion [J].

Bentein, L. ;

D'hooge, D. R. ;

Reyniers, M. -F. ;

Marin, G. B. .

POLYMER, 2012, 53 (03) :681-693

[8] Kinetic Modeling as a Tool to Understand and Improve the Nitroxide Mediated Polymerization of Styrene [J].

Bentein, Lien ;

D'hooge, Dagmar R. ;

Reyniers, Marie-Francoise ;

Marin, Guy B. .

MACROMOLECULAR THEORY AND SIMULATIONS, 2011, 20 (04) :238-265

[9] MODELING OF TERMINATION IN INTERMEDIATE AND HIGH CONVERSION FREE-RADICAL POLYMERIZATIONS [J].

BUBACK, M ;

HUCKESTEIN, B ;

RUSSELL, GT .

MACROMOLECULAR CHEMISTRY AND PHYSICS, 1994, 195 (02) :539-554

[10] Kinetics of "living" free radical polymerization [J].

Butté, A ;

Storti, G ;

Morbidelli, M .

CHEMICAL ENGINEERING SCIENCE, 1999, 54 (15-16) :3225-3231

← 1 2 3 4 5 6 7 8 9 10 →