Abstract
Particle formation during the initial stages of emulsifier-free organotellurium-mediated living radical emulsion polymerization (emulsion TERP) of styrene at 60°C was investigated at two stirring rates (220 and 1000 r.p.m.), in which the styrene phase floated as a layer on an aqueous phase at 220 r.p.m. or became dispersed as droplets at 1000 r.p.m. A water-soluble TERP agent, poly(methacrylic acid) (PMAA)-methyltellanyl (PMAA30-TeMe) and a water-soluble thermal initiator, 4,4′-azobis(4-cyanovaleric acid), at alkaline pH were used. The control/livingness was better at 1000 r.p.m. than at 220 r.p.m., and the particle size distribution was also affected by the stirring rate: both nanometer-sized and submicrometer-sized particles were observed at 220 r.p.m., and mainly nanometer-sized particles were observed at 1000 r.p.m. Because the percentage of PMAA30-TeMe consumed in the initial stage was much higher at 1000 r.p.m. than at 220 r.p.m., self-assembly nucleation preferentially occurred at 1000 r.p.m., resulting in nanometer-sized particles and good control/livingness. Stirring at 1000 r.p.m. only in the initial stage of the emulsion TERP followed by 220 r.p.m. induced good control/livingness and the formation of mainly nanometer-sized particles. It is concluded that a high stirring rate in the initial stage is important for the emulsion TERP of styrene to obtain good control/livingness and to control the particle formation mechanism.
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Acknowledgements
We are grateful to Otsuka Chemical Co., Ltd. for supplying the organotellurium compounds. This work was partially supported by Grant-in-Aid for Scientific Research (A) (Grant 21245050) from the Japan Society for the Promotion of Science (JSPS) and by Research Fellowship of JSPS for Young Scientists (given to YK).
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Moribe, H., Kitayama, Y., Suzuki, T. et al. Effect of stirring rate on particle formation in emulsifier-free, organotellurium-mediated living radical emulsion polymerization (emulsion TERP) of styrene. Polym J 44, 205–210 (2012). https://doi.org/10.1038/pj.2011.115
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DOI: https://doi.org/10.1038/pj.2011.115
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