On a score sheet for plastics, bioplastics have a medium score for combined mechanical performance and a high score for biodegradability with respect to counterpart petroleum-based plastics. Analysis quickly confirms that endeavours to increase the mechanical performance score for bioplastics would be far more achievable than delivering adequate biodegradability for the recalcitrant plastics, while preserving their impressive mechanical performances. Key architectural features of both bioplastics and petroleum-based plastics, namely, molecular weight (M_w) and crystallinity, which underpin mechanical performance, typically have an inversely dependent relationship with biodegradability. In the case of bioplastics, both macro and micro strategies with dual positive correlation on mechanical and biodegradability performance, are available to address this dilemma. Regarding the macro approach, processing using selected fillers, plasticisers and compatibilisers have been shown to enhance both targeted mechanical properties and biodegradability within bioplastics. Whereas, regarding the micro approach, a whole host of bio and chemical synthetic routes are uniquely available, to produce improved bioplastics. In this review, the main characteristics of bioplastics in terms of mechanical and barrier performances, as well as biodegradability, have been assessed—identifying both macro and micro routes promoting favourable bioplastics’ production, processability and performance.

Effective interfacing of energy-efficient and biobased technologies presents an all-green route to achieving continuous circular production, utilization, and reproduction of plastics. Here, we show combined ultragreen chemical and biocatalytic depolymerization of polyethylene terephthalate (PET) using deep eutectic solvent (DES)-based low-energy microwave (MW) treatment followed by enzymatic hydrolysis. DESs are emerging as attractive sustainable catalysts due to their low toxicity, biodegradability, and unique biological compatibility. A green DES with triplet composition of choline chloride, glycerol, and urea was selected for PET depolymerization under MW irradiation without the use of additional depolymerization agents. Treatment conditions were studied using Box-Behnken design (BBD) with respect to MW irradiation time, MW power, and volume of DES. Under the optimized conditions of 20 mL DES volume, 260 W MW power, and 3 min MW time, a significant increase in the carbonyl index and PET percentage weight loss was observed. The combined MW-assisted DES depolymerization and enzymatic hydrolysis of the treated PET residue using LCC variant ICCG resulted in a total monomer conversion of ≈16% (w/w) in the form of terephthalic acid, mono-(2-hydroxyethyl) terephthalate, and bis-(2-hydroxyethyl) terephthalate. Such high monomer conversion in comparison to enzymatically hydrolyzed virgin PET (1.56% (w/w)) could be attributed to the recognized depolymerization effect of the selected DES MW treatment process. Hence, MW-assisted DES technology proved itself as an efficient process for boosting the biodepolymerization of PET in an ultrafast and eco-friendly manner.

Most plastic degradation methods are currently inefficient and are limited by processing difficulties, quality loss, and diminished value. This research focuses on the development of novel mechano-chemical disintegration processes for the breakdown of waste plastics. The outputs will be biocatalyzed and used as building blocks for new polymers or other bioproducts. For the purpose of this research, microwave pre-treatment technology was used. Microwave technology is an ideal pre-treatment process for the degradation of plastics due to its lower treatment times under lower energy inputs. In the previous work, extensive research has been carried out utilizing different solvents and catalysts to develop efficient degradation mechanisms under microwave irradiations. A new class of ionic liquids (deep eutectic solvents) were used as catalysts to make a suspension with poly(ethylene terephthalate) (PET) and develop an alcoholysis reaction. Certain degradation parameters like crystallinity index, weight loss, and carbonyl index were depicted using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and Fourier-transform infrared spectroscopy (FTIR) characterization techniques. Furthermore, enhanced enzymatic degradation using LCC variant ICCG proved that microwave technology is an efficient process for the alcoholysis reaction and degradation of PET under mild conditions into its monomers.