Abstract

Kinetic study of TBD Catalyzed d-Valerolactone Polymerization Via a Gas-Driven Droplet Flow Reactor

Kai Wang, Associate Professor, Tsinghua University

The reaction kinetics of aliphatic polyester synthesis is critical to understanding the mechanism of ring-opening polymerization and making the reaction more controllable. We therefore introduce a gas-driven droplet flow reactor to determine the reaction kinetics of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) catalyzed d-valerolactone polymerization. Only 2 mL reaction solution was used for each test, which significantly reduced the work in preparing the anhydrous reactants. The experiment results indicated that the orders of the catalyst and the alcohol in the kinetic model are close to 1 and 0 respectively, and the rate-determining step was confirmed to the activation reaction between monomer and catalyst. The activated monomer can quickly react with the end hydroxyl of the polymer chain. In the end, we calculated the activation energy of the rate-determining reaction, which is only 7.302 ± 0.047 kJ/mol. (Funding support from the National Key R&D Program of China 2017YFB0307102, and Tsinghua University Initiative Scientific Research Programs 20151080361)