Chemical Engineering & Technology, Vol.42, No.10, 2154-2163, 2019
Practical Continuous-Flow Controlled/Living Anionic Polymerization
A continuous-flow reaction system was developed, allowing flow conditions of the entire system to be maintained at a predetermined constant level, which is one of the most significant factors for successful industrial application. Controlled/living anionic polymerization was selected as a model reaction since the characteristics of its polymer products, molecular weights, and molecular weight distributions are highly susceptible to changes in the relative flow rates of a monomer and initiator solutions. In flow microreactors, controlled/living anionic polymerization of styrene in tetrahydrofuran (THF)/hexane initiated by THF-diluted n-butyllithium (n-BuLi) was examined. Poly(styrenes) of larger molecule sizes such as Mn > 15 000 were successfully synthesized. After continuous operation for four hours, ca. 0.5 kg of the polymer was readily produced with narrow molecular weight distribution, demonstrating the applicability of this continuous-flow system for controlled/living anionic polymerization on considerably large scale with a view to its industrial usage in the future.