A Comprehensive Kinetic Investigation of the Ring Opening of L,L-Lactide in the Presence of Multifunctional Polyalcohols

Abstract In the present study, a comprehensive theoretical kinetic investigation of the ring opening polymerization of L,L-lactide in the presence of stannous octoate Sn(Oct) 2 as initiator for the synthesis of high molecular weight polylactide is carried out using both the method of moments and the stochastic Monte Carlo (MC) numerical methods. Via the implementation of the MC method, the dynamic evolution of a series of molecular properties (i.e., average molecular weights and molecular weight distributions) of the produced PLLA is accurately predicted. In addition, the effect of different polymerization conditions, such as the polymerization temperature and the monomer to initiator molar ratio on the final polymer properties is investigated. The developed stochastic model is also implemented to assess the effect of the presence of different multifunctional co-initiators (i.e., polyols with a different number of hydroxyl groups: 1,4-butanediol, glycerol, di(trimethylolpropane) (DTMP) and polyglycidol (PG) as co-initiators) in the reacting mixture, on the molecular weight distribution of the produced branched polylactides. The validity of the comprehensive kinetic model and the accuracy of the produced simulation results are verified via a direct comparison with available experimental data.