Investigations on the anionic polymerization of butadiene in capillaries by kinetic measurements and reactor simulation

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Abstract

For the first time the anionic polymerization of 1,3-butadiene (Bd) is successfully transferred from semibatch into a continuous microfluidic setup with comparable product properties. The molecular weight distribution described by the polydispersity index (PDI) is commonly used as a key criterion for product quality. The steady state and the local resolution of a continuous setup provide the opportunity to investigate the progress of the PDI during anionic polymerization. In this work, the influence of kinetics (statistics) and fluid dynamics (FD) on the PDI of the product is investigated. Therefore a dedicated setup was designed and erected to keep Bd in the liquid phase and provide a pulsation free constant liquid flow. With optimized parameter settings, a separation of initiation and propagation is obtained and the intrinsic kinetics of propagation are determined. To explain the experimental results, an ideal plug flow and an ideal laminar flow model are applied and compared to computational fluid dynamics (CFD) simulations. Finally, it is concluded which FD and statistical contributions lead to the very low PDI of 1.04 found in the experiments.

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Schulze, S., Cortese, B., Rupp, M., De Croon, M. H. J. M., Hessel, V., Couet, J., … Klemm, E. (2013). Investigations on the anionic polymerization of butadiene in capillaries by kinetic measurements and reactor simulation. Green Processing and Synthesis, 2(5), 381–395. https://doi.org/10.1515/gps-2013-0059

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