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Kinetics of Stable Free Radical Mediated Polymerization inside Submicron Particles
Author(s) -
Tobita Hidetaka
Publication year - 2007
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/mats.200700052
Subject(s) - polymerization , kinetics , nitroxide mediated radical polymerization , radical polymerization , polymer chemistry , chemistry , atom transfer radical polymerization , particle (ecology) , polymer , organic chemistry , physics , oceanography , quantum mechanics , geology
Controlled/living radical polymerization systems in which the active period is extremely small, ϕ A ≪ 1, such as the cases of stable free radical mediated polymerization (or nitroxide mediated polymerization) and atom transfer radical polymerization, are considered theoretically. The polymerization rate, R p , for such systems increases by lowering the trapping agent concentration [ X ]. When the polymerization is conducted inside small particles, R p decreases with D p 3below the diameter D p,SMC at which a single molecule concentration (SMC) is equal to [ X ] bulk . On the other hand, when the average number of trapping agents in a particle $\bar n_X$ is smaller than about 10, the fluctuation of n X among particles is significant, which leads to a larger R p than in the cases where all particles contain the same n X . Because of the effects of SMC and fluctuation, R p may show an acceleration window, D p,SMC < D p < D p,Fluct where R p is slightly larger than that in bulk.