The kinetics of the transesterification of polylactic acid (PLA) with methanol to form methyl lactate catalyzed by Zn(II) complexes was studied experimentally and numerically. The complexes, Zn(1 Et) 2 and Zn(2 Pr) 2, were synthesized from ethylenediamine and propylenediamine Schiff bases, respectively. The temperature range covered was 313.2-383.2 K. An increase in the reaction rate with the increase in temperature was observed for the Zn(1 Et) 2-catalyzed reaction. The temperature relationship of the rate coefficients can be explained by a linear Arrhenius dependency with constant activation energy. The kinetics of Zn(2 Pr) 2, on the other hand, is only explained by non-Arrhenius kinetics with convex variable activation energy, resulting in faster methyl lactate production rates at 323.2 and 343.2 K. The formation of a new catalyst species, likely through reaction with protic reagents, appears to promote the formation of intermediate complexes, resulting in the nonlinear behavior. Stirring speed induced the stability of the intermediate complexes. Contrary to Zn(1 Et) 2, Zn(2 Pr) 2 was susceptible to the presence of air/moisture in solution. The kinetic parameters were obtained by fitting the experimental data to the mass and energy balance of a consecutive second step reversible reaction taking place in a jacketed stirred batch reactor. For the case of Zn(2 Pr) 2, the activation energy was fitted to a four-parameter equation. The kinetic parameters presented in this work are valuable for the design of processes involving the chemical recycling of PLA into green solvents.
ASJC Scopus subject areas
- Chemical Engineering(all)