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

Abstract

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.

Lightweight Triboelectric Nanogenerators Based on Hollow Stellate Cellulose Films Derived from Juncus effusus L. Aerenchyma

“…[ 10 ] Although many materials have been studied or used as friction parts, [ 7,11–20 ] the replacement of petroleum‐based, nonrecyclable organic friction materials with renewable, natural materials that are fully biocompatible, biodegradable, or recyclable is still crucial in the current energy crisis and environmental pollution situation. [ 21,22 ]…”

“…[10] Although many materials have been studied or used as friction parts, [7,[11][12][13][14][15][16][17][18][19][20] the replacement of petroleum-based, nonrecyclable organic friction materials with renewable, natural materials that are fully biocompatible, biodegradable, or recyclable is still crucial in the current energy crisis and environmental pollution situation. [21,22] Cellulose-based triboelectric nanogenerators have had the most significant achievements among reported biomass-derived nanogenerators. This is due to the outstanding advantages of cellulose, which include widespread availability, renewability, biodegradability, biocompatibility, low cost, versatility, and frictional electrical activity.…”

Synthesis, Characterization, and Proton Conductivity of Muconic Acid-Based Polyamides Bearing Sulfonated Moieties

“…This compound is a high valueadded product because it can be polymerized by different routes. The double bonds present in its structure make it possible to polymerize it by free radicals, while the presence of the two carboxylic acid groups allows polymerization by condensation in combination with diols or diamines [30]. In both types of polymerizations, the polymer backbone presents unsaturations, making it possible for these renewable-based materials to possess improved functionality in terms of their tunable chemical and mechanical properties [24,25,30,31].…”

Single-Atom Ru-zeolite isomerization catalysis for a bio-based route towards terephthalates from muconic acid

“…adipic acid, terephthalic acid, and caprolactam), or serve directly as a bulk (co-)monomer in polymers. [24][25][26][27][28] The diacid owns a diene functionality and thus MA has three isomeric forms: cis,cis-muconic acid (ccMA) and cis,trans-muconic acid (ctMA) -both industrially produced in the biochemical fermentation of glucose, [29] while the most valuable trans,trans-muconic acid (ttMA) can only be accessed by isomerization of cc(ct)MA or via complex lab-scale chemical synthesis. [24,30,31] A full overview of routes to and from MA can be found in our recent review.…”