  Here, the synthesis of polyglobalide (PGl) by enzymatic ring-opening
polymerization (e-ROP) is investigated, using pressurized carbon dioxide (CO2),
pressurized CO2 + dichloromethane (DCM), and pressurized propane as solvents.
Particularly, the effects of phase equilibrium on the course of e-ROP and PGl
final properties are discussed. The partition coefficients of CO2, DCM,
propane, globalide and PGl were calculated with help of thermodynamic models,
providing proper understanding of monomer partitioning in the reaction system.
Reactions performed in pure CO2 resulted in monomer conversions of 100%.
Besides, when only one liquid phase was present inside the reactor, PGl samples
presented low polydispersities and high average molecular weights. When carried
out in CO2 + DCM, e-ROP resulted in lower monomer conversions and PGl samples
with higher polydispersities and lower average molecular weights. Finally,
reactions carried out in pressurized propane (200 bar) produced PGl samples
with the highest average molecular weights among the analyzed products.
