A Step Towards High-Molecular-Weight Living/Controlled Polystyrene Using SG1-Mediated Polymerization

被引：13
作者：
Lansalot, Muriel [1 ,2 ,3 ]
Guillaneuf, Yohann [1 ,2 ,3 ]
Luneau, Benoit [1 ,2 ,3 ]
Acerbis, Sebastien [1 ,2 ,3 ]
Dufils, Pierre-Emmanuel [1 ,2 ,3 ]
Gaudel-Siri, Anouk [1 ,2 ,3 ]
Gigmes, Didier [1 ,2 ,3 ]
Marque, Sylvain R. A. [1 ,2 ,3 ]
Tordo, Paul [1 ,2 ,3 ]
Bertin, Denis [1 ,2 ,3 ]
机构：
[1] Univ Aix Marseille 2, F-13397 Marseille 20, France
[2] Univ Aix Marseille 3, CNRS, F-13397 Marseille 20, France
[3] Univ Aix Marseille 1, UMR 6264, Lab Chim Prov, F-13397 Marseille 20, France
来源：
MACROMOLECULAR REACTION ENGINEERING | 2010年 / 4卷 / 6-7期
关键词：
computer modeling; controlled radical polymerization (CRP); high molecular weight; living polymerization; polystyrene; FREE-RADICAL POLYMERIZATION; ABSOLUTE RATE CONSTANTS; NITROXIDE-MEDIATED POLYMERIZATION; CHAIN-LENGTH DEPENDENCE; N-BUTYL ACRYLATE; ACETIC-ANHYDRIDE; STYRENE; KINETICS; ALKOXYAMINES; MECHANISM;
D O I：
10.1002/mren.200900074
中图分类号：
TQ [化学工业];
学科分类号：
0817 ;
摘要：
The synthesis of high-molecular-weight living/controlled polystyrene by NMP was studied. The combination of Ac2O and alkoxyamines based on nitroxides TEMPO, TIPNO, and SG1 was tested at 130 degrees C. With TEMPO and TIPNO, dipole/dipole interactions led to a decrease in nitroxide concentration and an acceleration of the reaction. To minimize thermal auto-initiation and thus obtain high-(M) over bar (n) PS, the temperature was lowered. At 90 degrees C, the use of BlocBuilder yielded PS of (M) over bar (n) = 210 000 g.mol(-1) with a living fraction of 60%. Finally, new SG1-based nitroxides were used to perform the polymerization at 75 degrees C. Since these nitroxides were too constrained, the decrease in k(c) caused a loss of control and livingness for high-(M) over bar (n) polymers.
引用
收藏
页码：403 / 414
页数：12
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