Abstract: A new route for hyperbranched aliphatic polyester by the prepolymerization of comonomers followed by the enzymatic condensation polymerization in organic media was developed using glycerol, 1,6-hexanediol, and adipic acid as comonomers and using immobilized lipase Novozym 435 as a biocatalyst. The organic solvents, such as isooctane, toluene, tert-butanol, tetrahydrofuran, and acetone, were used as the reaction medium for enzymatic condensation polymerization. The effects of reaction medium and reaction temperature on the enzymatic condensation polymerization were investigated. The molecular mass and the structure of the prepared polyesters were characterized by gel permeation chromatography and NMR. The results indicated that the hyperbranched aliphatic polyester could be successfully synthesized under the mild conditions by the combination of prepolymerization of comonomers with enzymatic condensation polymerization in organic media. Toluene was the best reaction medium among the examined ones, and the lipase Novozym 435 exhibited the highest activity at 70 ^oC within the temperature range from 50 to 90 ^oC. The polyester prepared by prepolymerization and the enzymatic condensation polymerization in toluene at 70 ^oC possessed the maximal molecular mass of up to 1.31×10⁴ and the branching degree of about 0.27.

Key words: prepolymerization, enzymatic condensation polymerization, hyperbranched polyester, branching degree, lipase