© WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
November 17, 2009
POLYMER DESIGN: Nitroxide-Mediated Radical Polymerization in Dispersed Systems: Compartmentalization and Nitroxide Partitioning
Per B. Zetterlund
Compartmentalization and nitroxide partitioning in NMP in dispersed systems have been investigated by modeling and simulations. Compartmentalization comprises the segregation effect on termination and the confined space effect on deactivation. Under certain conditions, it is possible to obtain an improvement in both control and livingness. The particle size threshold for compartmentalization, decreases with any system change that leads to a decrease in the number of propagating radicals and/or nitroxides per particle, and vice versa. There is direct competition between the confined space effect on deactivation and nitroxide exit-the more water-soluble the nitroxide, the weaker the confined space effect. Nitroxide partitioning leads to an increase in polymerization rate and loss in control/livingness.
Macromol. Theory Simul. DOI: 10.1002/mats.200900051
Other contributions to the article series on modeling for polymer design can be found at: http://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1521-3919/2262_des.html