Efficient biotransformation of biobased raw materials into novel polyesters/polyesteramides; comparative investigation of enzymatic synthesis of block and random copolymers and terpolymers

Within the context of paving the way for a sustainable bioeconomy, there is a strong emphasis on utilizing bio-based raw materials as substitutes for fossil fuels in the production of polymers. When designing the synthesis of novel polymeric materials from bio-based building blocks, a promising green approach consists in utilizing enzymes as biocatalysts. This aspect is particularly important when aiming to obtain products from the class of polyesters and polyesteramides with biocompatible and biodegradable properties, as enzymes facilitate the synthesis of polymers that align closely with biological systems. Lipases have been proven to be very effective in the synthesis of polymers, particularly in the ring-opening polymerization of ε-caprolactone. Considering the possibility of performing the copolymerization of ε-caprolactone for obtaining random and block structures, this is the first comparative study of the enzymatic polymer synthesis utilizing an innovative approach of combining ring-opening polymerization with polycondensation. Terpolymers derived from ε-caprolactone and dimethyl itaconate or dimethyl adipate with either 1,8-octanediol or 1,8-octanediamine were obtained at 85 °C in a solventless systems, yielding products with a copolymer content of >85 % and weight-average molecular weight (M_w) up to 40,000 Da. The thermal properties and biodegradation behavior of the synthetized terpolymers were assessed.