Enzymatic polymerization to polyesters in nonaqueous solvents

Aliphatic polyesters are thermoplastic and biodegradable polymers with promising potentials to substitute synthetic polymers derived from petrochemicals. In particular, polylactides (PLAs) and other polylactones can be renewable and biocompatible. A more benign approach for polyester synthesis is the enzymatic polycondensation or ring-opening polymerization (ROP) reactions, whose outcomes largely depend on the reaction conditions including solvents, water content and temperature. This chapter illustrates several examples of enzymatic polymerization to polyesters using various solvents (i.e., organic solvents, supercritical fluids, ionic liquids, and aqueous biphasic systems). Hydrophobic solvents containing little water tend to promote the enzymatic polymerization and lead to high molecular masses of polyesters. Since some enzymatic polymerization reactions are performed at high temperatures (such as ring-opening polymerization of lactide at >100°C), these processes demand solvents with high boiling points (such as many ionic liquids). Supercritical fluids (such as supercritical CO₂) can be "green" solvents, but their compatibility with enzymes and their practicability of scaling up remain as challenges. On the other hand, ionic liquids can be tailored to be compatible with enzymes and to have high thermal stability although the studies of their uses in enzymatic polycondensation and ROP reactions are still at an early stage.