Journal
MACROMOLECULAR REACTION ENGINEERING
Volume 4, Issue 6-7, Pages 403-414Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/mren.200900074
Keywords
computer modeling; controlled radical polymerization (CRP); high molecular weight; living polymerization; polystyrene
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Funding
- ARKEMA
- University of Provence
- CNRS
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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.
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