Development of Cyclic Propagation Kinetics for Modeling the Nitroxide-mediated Radical Copolymerization of Styrene-Divinylbenzene

被引：15

作者：

Aguiar, Leandro G. ^{[1
]}

Goncalves, Miguel A. D. ^{[2
]}

Pinto, Virginia D. ^{[2
]}

Dias, Rolando C. S. ^{[2
]}

Costa, Mario Rui P. F. N. ^{[3
]}

Giudici, Reinaldo ^{[1
]}

机构：

[1] Univ Sao Paulo, Escola Politecn, Dept Engn Quim, BR-05508010 Sao Paulo, Brazil

[2] LSRE Inst Politecn Braganca, P-5300 Braganca, Portugal

[3] Univ Porto, LSRE Fac Engn, P-4200456 Oporto, Portugal

来源：

MACROMOLECULAR REACTION ENGINEERING | 2014年 / 8卷 / 04期

基金：

巴西圣保罗研究基金会;

关键词：

crosslinking; gelation; kinetics (polym; living polymerization; modeling; NETWORK FORMATION; GEL FORMATION; POLYMERIZATION; CYCLIZATION; STYRENE/DIVINYLBENZENE;

D O I：

10.1002/mren.201300105

中图分类号：

TQ [化学工业];

学科分类号：

0817 ;

摘要：

A kinetic model including the cyclic propagation (cyclization) is proposed for the nitroxide-mediated radical copolymerization of styrene-divinylbenzene. The method involves a balance of sequences of units, which connect a radical center and a pendant double bond present in the same polymer chain. The rate constant for cyclization was considered a function of the sequence length. Good agreement between the model predictions and experimental data for solution and suspension controlled copolymerizations was found. The rate constant of cyclization for the smallest ring (3 monomeric units) was estimated to be 700s(-1) at 90 degrees C, and the activation energy was estimated to be 32500calmol(-1).

引用

页码：282 / 294

页数：13

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