Ring-Opening Copolymerization of L-Lactide and Epsilon-Caprolactone in Supercritical Carbon Dioxide Using Triblock Oligomers of Caprolactone and Peg As Stabilizers

In this study, the use of triblock (A-B-A) oligomers of epsilon-caprolactone (epsilon-CL) (A) and PEG400 (B) as stabilizers (SB) for the copolymerization of L-lactide (LLA) and epsilon-CL in supercritical carbon dioxide (scCO(2)) was investigated. To determine the effect of CO2-philic and polymer-philic segments on copolymerization, oligomers with three different average molecular weights (M-w=2000-6000 Da) were synthesized by changing the PEG400/epsilon-CL ratio. Copolymerizations were confirmed by H-1-nuclear magnetic resonance (NMR), C-13-NMR and differential scanning calorimeter data. It was possible to copolymerize LLA and e-CL in scCO(2) without any SB; however, the polymerization yields and average molecular weights were low, and significant aggregate formations were detected. Recipes featuring only 5% SB were successfully applied to reach high polymerization yields of similar to 85% and polymers with average molecular weights greater than 20 kDa. When the polymer-philic segment of the SB increased, both the yield and molecular weight of the copolymer also increased significantly, resulting in white powdery products. Polymer Journal (2011) 43, 785-791; doi: 10.1038/pj.2011.70; published online 27 July 2011Wo