Simulation, controlled radical polymerization

Turgman-Cohen, S. and J. Genzer, Computer simulation of controlled radical polymerization Effect of chain confinement due to initiator grafting density and solvent quality in "grafting from Method. Macromolecules, 2010. 43(22) p. 9567-9577. 

Tobita, H., Yanase, F., 2007. Monte Carlo simulation of controlled/living radical polymerization in emulsified systems. Macromol. Theory Simul. 16, 476-488. 

Greszta, D., and Matyjaszewski, K. (1996). Mechanism of controlled/ living radical polymerization of styrene in the presence of nitroxyl radicals. Kinetics and simulations. Macromolecules, 29(24) 7661-7670. 

Shipp, D. A., and Matyjaszewski, K. (1999). Kinetic analysis of controUed/Miving radical polymerizations by simulations. 1. The importance of diffusion-controlled reactions. Macromolecules, 52(9) 2948-2955. 

Wang R, Luo Y, Li B, Sun X, Zhu S. Design and control of copolymer composition distribution in living radical polymerization using semi-batch feeding policies a model simulation. Macromol Theor Simul 2006 15 356-368. 

Matyjaszewki et al. [229,236] pointed out the importance of the bimolecular exchange reaction (Eq. 19) to control the molecular weight and its distribution. Simulation revealed a decrease in the Mw/Mn values during polymerization, but the contribution in the actual polymerization is still ambiguous [237-240]. Reports have also addressed the importance of the decomposition of the alkoxyamine such as the disproportionation of the propagating radical and the nitroxide for the control of the polymerization [229,236,241 ]. 

Super-swelhng was postulated as a cause of instabihty in controlled free radical miniemulsion polymerization. Asua [312] thought that the interfacial tension used in the simulations was too high and the droplet size was too smaU. However, it is turned out that the question about droplet size is due to a misunderstanding. It is weh accepted that a well-performed miniemulsion has... 

Chern [42] developed a mechanistic model based on diffusion-controlled reaction mechanisms to predict the kinetics of the semibatch emulsion polymerization of styrene. Reasonable agreement between the model predictions and experimental data available in the literature was achieved. Computer simulation results showed that the polymerization system approaches Smith-Ewart Case 2 kinetics (n = 0.5) when the concentration of monomer in the latex particles is close to the saturation value. By contrast, the polymerization system under the monomer-starved condition is characterized by the diffusion-con-trolled reaction mechanisms (n > 0.5). The author also developed a model to predict the effect of desorption of free radicals out of the latex particles on the kinetics of the semibatch emulsion polymerization of methyl acrylate [43]. The validity of the kinetic model was confirmed by the experimental data for a wide range of monomer feed rates. The desorption rate constant for methyl acrylate at 50°C was determined to be 4 x 10 cm s ... 

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