Synthesis of Poly(Lactic Acid--Glycolic Acid) Copolymers with High Glycolide Ratio by Ring-Opening Polymerisation.

The rise in demand for biodegradable plastic packaging with high barrier properties has spurred interest in poly(lactic acid--glycolic acid) (PLGA) copolymers with a relatively high glycolide content. In this work, we examined how reaction conditions affect the synthesis of PLGA25 (L:G 25:75) through the ring-opening polymerisation of d-l-lactide (L) and glycolide (G), using tin 2-ethylhexanoate (Sn(Oct)) as the catalyst and 1-dodecanol as the initiator. The effects of varying the initiator concentration, catalyst concentration, reaction time, and temperature on the molecular weight, monomer conversion, and thermal properties of PLGA25 were investigated. Increasing the reaction temperature from 130 to 205 °C significantly reduced the time required for high monomer conversions but caused greater polymer discolouration. Whilst increasing the [M]:[C] from 6500:1 to 50,000:1 reduced polymer discolouration, it also resulted in longer reaction times and higher reaction temperatures being required to achieve high conversions. High M and M values of 136,000 and 399,000 g mol were achieved when polymerisations were performed in the solid state at 150 °C using low initiator concentrations. These copolymers were analysed using high temperature SEC at 80 °C, employing DMSO instead of HFIP as the eluent.