Add time:08/19/2019 Source:sciencedirect.com
The application of living cationic polymerization suffers from complex and costly additives as well as low productivity. In this work, we attempted to develop fast living cationic polymerization of Isobutyl vinyl ether (cas 109-53-5) (IBVE) tailored by reduced single nucleophile in microflow system. Living polymers were successful obtained for the systems of IBVE-HCl/FeCl3·DO/DO and IBVE-HCl/FeCl3·DOL/DOL. The kinetic behavior of IBVE polymerizations at various concentration of nucleophiles revealed that a microflow system could afford living characteristics as the time to reach 50% conversion (t1/2) is as short as 0.22 s. Using single nucleophile can avoid the negative cooperativity of multi-nucleophiles in stabilizing carbocations, allow the decrement of nucleophile, and enhance the controllability of polymerization process. DFT simulations indicate that only the nucleophile with relatively higher binding energy could endow the system with living characteristic. From this point of view, the addition of other nucleophile with relatively lower binding energy may have no positive effect. These recognitions are meaningful for the development of living cationic polymerization towards commercial application.
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