Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5190779 | Polymer | 2005 | 11 Pages |
Abstract
Cumyl dithiobenzoate (CDB) mediated methyl acrylate (MA) bulk polymerizations at 80 °C, using CDB concentrations between 1.5Ã10â2 and 5.0Ã10â2 mol Lâ1, were modeled via a novel Monte Carlo simulation procedure with respect to experimental time-dependent conversions, X, number average molecular weights, Mn, and weight average molecular weights, Mw. The simulations were based upon individual treatment of 5Ã108 discrete molecules in accordance to their actual reaction pathways. The kinetic scheme employed includes termination reactions of intermediate RAFT radicals with propagating radicals and reaction steps of the RAFT pre-equilibrium, which are different from those of the RAFT main equilibrium. The equilibrium constant of the main equilibrium of the CDB/MA system at 80 °C was found to be K=1.2Ã104 L molâ1, indicating a relatively stable intermediate radical. The concentration of the intermediate RAFT radical, although not employed as experimental input data for the modeling, was calculated by using the obtained set of kinetic parameters as being in excellent agreement with experimental electron spin resonance spectroscopic data.
Keywords
Related Topics
Physical Sciences and Engineering
Chemistry
Organic Chemistry
Authors
Marco Drache, Gudrun Schmidt-Naake, Michael Buback, Philipp Vana,