Enzymatic Synthesis of Muconic Acid-Based Polymers: Trans, Trans-Dimethyl Muconate and Trans, β-Dimethyl Hydromuconate.

The vast majority of commodity polymers are acquired from petrochemical feedstock, and these resources will plausibly be depleted within the next 100 years. Therefore, the utilization of carbon-neutral renewable resources for the production of polymers is crucial in modern green chemistry. Herein, we report an eco-friendly strategy that uses enzyme catalysis to design biobased unsaturated (co)polyesters from muconic acid derivatives. This method is an attractive pathway for the production of well-defined unsaturated polyesters with minimum side reactions. A suite of characterization techniques was performed to probe the reaction mechanism and properties of the obtained polyesters. It is rationalized that the alkene functionality of the muconate monomers plays an important role in the enzyme catalysis mechanism. The rendered polyesters possessed excellent thermal stabilities and unreacted alkene functionality that can consecutively undergo chain extension, copolymerization, or act as an anchor for other functional groups. These properties open new avenues in the fields of unsaturated polyester resins and photosensitive coatings.