• biodegradable polymers;
  • poly(L-lactic acid);
  • catalyst;
  • melt polycondensation;
  • solid-state polycondensation


Melt/solid state polycondensation (MP/SSP) is a cost-effective route for synthesis of high molecular weight poly(L-lactic acid) (PLLA). However, the reaction rates in its four stages need to be enhanced greatly and the reaction times to be shortened largely before the MP/SSP technology can be industrialized. In this study, a new catalyst addition policy, i.e., adding TSA at the dehydration stage and SnCl2·2H2O at the MP stage, and more appropriate temperature and pressure programs were presented and applied in the MP process of LLA. The presence of TSA from dehydration appeared very effective for speeding up the dehydration and oligomerization stages as well as depressing racemization in the whole MP process. The polymerization degree (Xn) of oligomer was clearly increased, and the reaction time was shortened to a great extent. Direct using reduced pressure was also very helpful for intensifying the dehydration stage, only leading to LLA loss as little as 2%. A PLLA with Mw of 44,000 and optical purity of 96.8% suitable for subsequent SSP was produced after dehydration for 2 h, oligomerization for 2 h and MP for 4 h under appropriate conditions. And an interesting strong dependence of the Mw of final PLLA product on the Xn of the oligomer was observed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011