Abstract
The enzymatic ring opening copolymerization of globalide and ε-caprolactone under supercritical conditions was investigated. Samples were evaluated in terms of molecular weight, thermal properties, ratio between repeating units, and production of cyclic oligomers. For the first time, poly(globalide-co-ε-caprolactone) (PGlCL) was synthesized by e-ROP using supercritical carbon dioxide (scCO2) and the mixture scCO2+dichloromethane (DCM) as solvents. The feed ratio between globalide and ε-caprolactone was evaluated. PGlCL synthesized in scCO2 showed the highest molecular weights, while the use of cosolvent caused a decrease on molecular weight values. For both scCO2 and scCO2+DCM, the increase on globalide content (relative to total monomers amount) increased molecular weight values. Thermal analysis indicated a non-isomorphic behavior, characteristic of random semi-crystalline copolymers, which is the case of the PGlCL produced. PGlCL synthesized on scCO2+DCM presented double melting point, which is related to a greater presence of cyclic oligomers, in comparison to PGlCL synthesized using only scCO2, being confirmed by MALDI-TOF analysis.
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