Polycondensation of L-Lactic Acid: A Deeper Look into Solid State Polycondensation

Abstract

L-lactic acid (LA) was condensed in the presence of SnCl2 or 4-toluenesulfonic acid (TSA) at 140 °C, and chain growth without cyclization was observed. In addition, poly(l-lactic acid)s (PLAs) with a degree of polymerization (DP) of 25, 50 or 100 were prepared by water-initiated ring-opening polymerization (ROP). These PLAs were annealed in the solid state at 140 °C and 160 °C in the presence of tin (II) 2-ethylhexanoate (SnOct2), tin (II) chloride (SnCl2) or toluene sulfonic acid (TSA). The changes in the molecular weight distribution and in the topology were characterized by means of matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry and gel permeation chromatography (GPC). With increasing time, fewer side reactions caused higher molecular weights and increasing fractions of cyclic polylactides (cPLA) were obtained. Their “saw tooth” pattern in the MALDI-TOF mass spectra indicated the formation of extended ring crystallites in the solid state. TSA was the most active catalyst and caused fewer side reactions than SnCl2, which was the least reactive catalyst. Acetylation of the CH-OH end groups hindered polycondensation and prevented the formation of cPLAs. Reaction mechanisms will be discussed.