Glycerol Copolyesters: Control of Branching and Molecular Weight Using a Lipase Catalyst

Immobilized Lipase B from Candida antartica (Novozyme 435) catalyzed bulk polycondensations at 70 °C for 42 h that resulted in hyperbranched polyesters with octanediol-adipate and glycerol-adipate repeat units. Instead of using organic solvents, the monomers adipic acid (A2), 1,8-octanediol (B2), and glycerol (B‘B2) were combined to form monophasic ternary mixtures. During the first 18 h of a copolymerization with monomer feed ratio (A2 to B2 to B‘B2) 1.0:0.8:0.2 mol/mol, the regioselectivity of Novozyme 435 resulted in linear copolyesters. Extending the reaction to 42 h gave hyperbranched copolymers with dendritic glycerol units. The % regioselectivity for esterifications at the primary glycerol positions ranged from 77 to 82% and was independent of glycerol content in the monomer feed. Variation of glycerol in the monomer feed gave copolymers with degree of branching (DB) from 9 to 58%. In one example, a hyperbranched copolyester with 18 mol % glycerol−adipate units was formed in 90% yield, with Mw 75 6...