Chain-length dependent termination in pulsed-laser polymerization, 3 -: On the prospects of determining the bimolecular termination constant kt from rate data

被引：23

作者：

Olaj, OF ^{[1
]}

Kornherr, A ^{[1
]}

Zifferer, G ^{[1
]}

机构：

[1] Univ Vienna, Inst Phys Chem, A-1090 Vienna, Austria

来源：

MACROMOLECULAR RAPID COMMUNICATIONS | 1998年 / 19卷 / 02期

关键词：

D O I：

10.1002/marc.1998.030190202

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

The correct (event-weighted) average of k(t), [k(t)], has been calculated from simulation data for pseudostationary laser-induced polymerization for a kinetic scheme with chain-length dependent termination and compared to the average (k) over bar(t) which is obtained by employing the formal procedures, originally designed for the evaluation of individual rate constants from rate data in the case of chain-length independent termination. Satisfactory (and in fact excellent) results are obtained only if the complete equation for the conversion per laser pulse is solved for (k) over bar(t). This leads to an almost perfect recovery of the power-law governing the dependence of k(t) on chain-length, especially the exponent.

引用

收藏

页码：89 / 96

页数：8

相关论文

共 22 条

[1]

[Anonymous], HDB MATH FUNCTIONS F

[2] Determination of free-radical propagation rate coefficients of butyl, 2-ethylhexyl, and dodecyl acrylates by pulsed-laser polymerization [J].

Beuermann, S ;

Paquet, DA ;

McMinn, JH ;

Hutchinson, RA .

MACROMOLECULES, 1996, 29 (12) :4206-4215

[3] Critically evaluated rate coefficients for free-radical polymerization .2. Propagation rate coefficients for methyl methacrylate [J].

Beuermann, S ;

Buback, M ;

Davis, TP ;

Gilbert, RG ;

Hutchinson, RA ;

Olaj, OF ;

Russell, GT ;

Schweer, J ;

vanHerk, AM .

MACROMOLECULAR CHEMISTRY AND PHYSICS, 1997, 198 (05) :1545-1560

[4] KINETICS OF FREE-RADICAL SOLUTION POLYMERIZATION OF METHYL-METHACRYLATE OVER AN EXTENDED CONVERSION RANGE [J].

BEUERMANN, S ;

BUBACK, M ;

RUSSELL, GT .

MACROMOLECULAR CHEMISTRY AND PHYSICS, 1995, 196 (08) :2493-2516

[5] CRITICALLY EVALUATED RATE COEFFICIENTS FOR FREE-RADICAL POLYMERIZATION .1. PROPAGATION RATE COEFFICIENT FOR STYRENE [J].

BUBACK, M ;

GILBERT, RG ;

HUTCHINSON, RA ;

KLUMPERMAN, B ;

KUCHTA, FD ;

MANDERS, BG ;

ODRISCOLL, KF ;

RUSSELL, GT ;

SCHWEER, J .

MACROMOLECULAR CHEMISTRY AND PHYSICS, 1995, 196 (10) :3267-3280

[6] Modeling of molecular weight distribution in pulsed laser free-radical homopolymerizations [J].

Buback, M ;

Busch, M ;

Lammel, RA .

MACROMOLECULAR THEORY AND SIMULATIONS, 1996, 5 (05) :845-861

[7] CONSISTENT VALUES OF RATE PARAMETERS IN FREE-RADICAL POLYMERIZATION SYSTEMS .2. OUTSTANDING DILEMMAS AND RECOMMENDATIONS [J].

BUBACK, M ;

GILBERT, RG ;

RUSSELL, GT ;

HILL, DJT ;

MOAD, G ;

ODRISCOLL, KF ;

SHEN, J ;

WINNIK, MA .

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 1992, 30 (05) :851-863

[8] CONSISTENT VALUES OF RATE PARAMETERS IN FREE-RADICAL POLYMERIZATION SYSTEMS [J].

BUBACK, M ;

GARCIARUBIO, LH ;

GILBERT, RG ;

NAPPER, DH ;

GUILLOT, J ;

HAMIELEC, AE ;

HILL, D ;

ODRISCOLL, KF ;

OLAJ, OF ;

SHEN, JC ;

SOLOMON, D ;

MOAD, G ;

STICKLER, M ;

TIRRELL, M ;

WINNIK, MA .

JOURNAL OF POLYMER SCIENCE PART C-POLYMER LETTERS, 1988, 26 (07) :293-297

[9]

GRADSTEIN I, 1981, SUMMEN PRODUKT INTEG, V1, P95

[10] DETERMINATION OF PROPAGATION RATE COEFFICIENTS BY PULSED-LASER POLYMERIZATION FOR SYSTEMS WITH RAPID CHAIN GROWTH - VINYL-ACETATE [J].

HUTCHINSON, RA ;

RICHARDS, JR ;

ARONSON, MT .

MACROMOLECULES, 1994, 27 (16) :4530-4537