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A Monte Carlo simulation model for the kinetics of emulsion polymerization is proposed. In the present model, the formation of each polymer molecule is simulated by the use of only a couple of probability functions; therefore, the calculation can be handled well even on personal computers. It is straightforward to account for virtually any kinetic event, such as the desorption of oligomeric radicals and chain length dependence of kinetic parameters, and as a consequence very detailed information such as the full distributions of the dead polymer molecular weights and the macroradicals among various polymer particles can be obtained. When bimolecular terminations are the dominant chain stoppage mechanism, the instantaneous molecular weight distribution (produced in a very small time interval) becomes broader than that for homogeneous polymerizations due to a higher possibility that short and long polymer radicals react with each other if bimolecular reactions are fast enough. The increase in the polydispersity of the MWD is fairly large, especially when bimolecular termination by disproportionation is significant; however, the gel permeation chromatography (GPC) may not be a suitable analytical technique to detect such broadening since oligomeric peaks may not be observed in the elution curve. The present simulation method provides greater insight into the complicated phenomena of emulsion polymerizations. © 1995 John Wiley & Sons, Inc.

A purification method for raw single-walled carbon nanotubes (SWCNTs) without damage to their intrinsic structures has been desired in many applications. We investigated the purification of SWCNTs based on high-speed centrifugation of water-dispersed SWCNTs using the photoreactive dispersant we previously investigated. SWCNTs wrapped with the dispersant were separated from impurities, such as an amorphous carbon and metal particles by centrifugation, similarly to conventional physical purification using surfactants. In contrast to general surfactants that form micelles to disperse SWCNTs in aqueous solutions, the photoreactive dispersant did not form micelles. Therefore, an excess amount of the dispersant, which did not adsorb onto the SWCNT surfaces, was removable by dialysis of the supernatant. Since the amount of the dispersant was minimized by dialysis, we tuned the UV-irradiation time to eliminate the dispersibility of SWCNTs in water to as low a value as ∼2 h. The SWCNT precipitates were collected, and their chemical and structural purity were evaluated using thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and resonance Raman spectroscopy. It was found that present methods combining high-speed centrifugation and photoreactive dispersant provided an effective procedure to purify SWCNTs without any apparent changes to their intrinsic properties.

We describe the application of photodetachable and recyclable dispersants for single-walled carbon nanotubes (SWNTs) in the fabrication of photopatterned SWNT thin films. Because adsorption and desorption of the dispersants on the SWNT surfaces affect not only their dispersibility in water but also their solubility, SWNT photopatterns were obtained on glass substrates in only three steps, i.e., casting the SWNT/dispersant solution, UV-light exposure of the casted SWNT/dispersant films through a photomask, and subsequent rinsing with neutral water. This patterning procedure is simple and scalable and will enable us to prepare microfabricated SWNT thin films.

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