Expanding Poly(lactic acid) (PLA) and Polyhydroxyalkanoates (PHAs) Applications: A Review on Modifications and Effects

The high price of petroleum, overconsumption of plastic products, recent climate change regulations, the lack of landfill spaces in addition to the ever-growing population are considered the driving forces for introducing sustainable biodegradable solutions for greener environment. Due to the harmful impact of petroleum waste plastics on human health, environment and ecosystems, societies have been moving towards the adoption of biodegradable natural based polymers whose conversion and consumption are environmentally friendly. Therefore, biodegradable biobased polymers such as poly(lactic acid) (PLA) and polyhydroxyalkanoates (PHAs) have gained a significant amount of attention in recent years. Nonetheless, some of the vital limitations to the broader use of these biopolymers are that they are less flexible and have less impact resistance when compared to petroleum-based plastics (e.g., polypropylene (PP), high-density polyethylene (HDPE) and polystyrene (PS)). Recent advances have shown that with appropriate modification methods—plasticizers and fillers, polymer blends and nanocomposites, such limitations of both polymers can be overcome. This work is meant to widen the applicability of both polymers by reviewing the available materials on these methods and their impacts with a focus on the mechanical properties. This literature investigation leads to the conclusion that both PLA and PHAs show strong candidacy in expanding their utilizations to potentially substitute petroleum-based plastics in various applications, including but not limited to, food, active packaging, surgical implants, dental, drug delivery, biomedical as well as antistatic and flame retardants applications.

Unveiling the Enzymatic Degradation Process of Biobased Thiophene Polyesters

In the past 20 years, scientific research focused on the identification of valid alternatives to materials of fossil origin, in particular, related to biobased polymers. Recently, the efforts led to the synthesis of thiophene-based polymers (TBPs), a new class of polyesters based on 2,5-thiophenedicarboxylic acid (TPCA) that can be industrially produced using biomass-derived molecules. In this study, TBPs were synthesized using diols with different chain length (from C4 to C6) leading to poly(butylene 2,5-thiophenedicarboxylate) (PBTF), poly(pentamethylene 2,5-thiophenedicarboxylate) (PPeTF), and poly(hexamethylene 2,5-thiophenedicarboxylate) (PHTF), respectively, that were processed to thin films. To investigate enzymatic hydrolysis of these polymer films, cutinase 1 (Thc_cut1) and cutinase 2 (Thc_cut2) from Thermobifida cellulosilytica were recombinantly expressed in the host E. coli and purified. After 72 h of incubation at 65°C with 5 µM Thc_cut1, weight loss and HPLC analysis indicated 9, 100, and 80% degradation of PBTF, PPeTF, and PHTG with a concomitant release of 0.12, 2.70, and 0.67 mM of TPCA. The SEM analysis showed that tiny holes were formed on the surface of the films and after 72 h PPeTF was completely degraded. The LC-TOF/MS analysis indicated that Thc_cut2 in particular released various oligomers from the polymer during the reaction. In addition, the FTIR analysis showed the formation of novel acid and hydroxyl groups on the polymer surfaces. The results showed that the two used thermostable cutinases are promising biocatalysts for the environmentally friendly degradation of TPCA-based polyesters, in view of a possible sustainable recycling of plastic waste through resynthesis processes.

Assessment of Toxicity and Biodegradability of Poly(vinyl alcohol)-Based Materials in Marine Water

Due to the continuous rise in conventional plastic production and the deficient management of plastic waste, industry is developing alternative plastic products made of biodegradable or biobased polymers. The challenge nowadays is to create a new product that combines the advantages of conventional plastics with environmentally friendly properties. This study focuses on the assessment of the potential impact that polyvinyl alcohol (PVA)-based polymers may have once they are released into the marine environment, in terms of biodegradation in seawater (assessed by the percentage of the Theoretical Oxygen Demand, or % ThOD, of each compound) and aquatic toxicity, according to the standard toxicity test using Paracentrotus lividus larvae. We have tested three different materials: two glycerol-containing PVA based ones, and another made from pure PVA. Biodegradation of PVA under marine conditions without an acclimated inoculum seems to be negligible, and it slightly improves when the polymer is combined with glycerol, with a 5.3 and 8.4% ThOD achieved after a period of 28 days. Toxicity of pure PVA was also negligible (<1 toxic units, TU), but slightly increases when the material included glycerol (2.2 and 2.3 TU). These results may contribute to a better assessment of the behavior of PVA-based polymers in marine environments. Given the low biodegradation rates obtained for the tested compounds, PVA polymers still require further study in order to develop materials that are truly degradable in real marine scenarios.

Chemical Recycling of PET in the Presence of the Bio-Based Polymers, PLA, PHB and PEF: A Review

The great increase in the production and consumption of plastics has resulted in large amounts of plastic wastes, creating a serious problem in terms of their environmentally friendly disposal. The need for the production of more environmentally friendly polymers gave birth to the production of biodegradable, and more recently, biobased polymers, used in the production of biodegradable or biobased plastics. Although the percentage of currently produced bioplastics is rather small, almost 1% compared to petrochemical-based plastics, inevitably is going to significantly increase in the near future due to strict legislation recently posed by the European Union and other countries’ Governments. Thus, recycling strategies that have been developed could be disturbed and the economic balance of this sector could be destabilized. In the present review, the recycling of the polymer mainly used in food plastic packaging, i.e., poly(ethylene terephthalate), PET is examined together with its counterparts from the biobased polymers, i.e., poly(lactic acid), PLA (already replacing PET in several applications), poly(3-hydroxybutyrate), PHB and poly(ethylene furanoate), PEF. Methods for the chemical recycling of these materials together with the chemical products obtained are critically reviewed. Specifically, hydrolysis, alcoholysis and glycolysis. Hydrolysis (i.e., the reaction with water) under different environments (alkaline, acidic, neutral), experimental conditions and catalysts results directly in the production of the corresponding monomers, which however, should be separated in order to be re-used for the re-production of the respective polymer. Reaction conditions need to be optimized with a view to depolymerize only a specific polymer, while the others remain intact. Alcoholysis (i.e., the reaction with some alcohol, methanol or ethanol) results in methyl or ethyl esters or diesters that again could be used for the re-production of the specific polymer or as a source for producing other materials. Glycolysis (reaction with some glycol, such as ethylene, or diethylene glycol) is much studied for PET, whereas less studied for the biopolymers and seems to be a very promising technique. Oligomers having two terminal hydroxyl groups are produced that can be further utilized as starting materials for other value-added products, such as unsaturated polyester resins, methacrylated crosslinked resins, biodegradable polyurethanes, etc. These diols derived from both PET and the bio-based polymers can be used simultaneously without the need for an additional separation step, in the synthesis of final products incorporating biodegradable units in their chemical structure.

Are Biobased Plastics Green Alternatives?—A Critical Review

Environmental sustainability is driving an intense search for “green materials”. Biobased plastics have emerged as a promising alternative. Their building blocks can now be obtained from diverse biomass, by-products, and organic residues due to the advances in biorefineries and bioprocessing technologies, decreasing the demand for fossil fuel resources and carbon footprint. Novel biobased polymers with high added value and improved properties and functionalities have been developed to apply diverse economic sectors. However, the real opportunities and risks of such novel biobased plastic solutions have raised scientific and public awareness. This paper provides a critical review on the recent advances in biobased polymers chemistry and emerging (bio)technologies that underpin their production and discusses the potential for biodegradation, recycling, environmental safety, and toxicity of these biobased solutions.

Mechanochemical and thermal succinylation of softwood sawdust in presence of deep eutectic solvent to produce lignin-containing wood nanofibers

In this study, the effect of the deep eutectic solvent (DES) based on triethylmethylammonium chloride and imidazole on the mechanochemical succinylation of sawdust was investigated. The sawdust was ball milled in the presence of succinic anhydride and the effects of different amounts of the DES on the carboxylic acid content and particle size were studied with and without post-heating. The carboxylic acid content significantly increased with the addition of the DES and by using 1.5 mass excess of the DES compared to sawdust; milled sawdust with 3.5 mmol/g of carboxylic acid groups was obtained using 60 min post-heating at 100 °C. The particle size was found to depend strongly on DES-to-wood ratio and a change in size-reduction characteristics was observed related to fiber saturation point. After mechanochemical milling, three succinylated sawdust samples with different carboxylic acid contents were disintegrated into wood nanofibers and self-standing films were produced. Although the mechanical properties of the films were lower than the cellulose nanofibers, they were higher or in line with oil- and biobased polymers such as polypropene and polylactic acid, respectively. Because of their amphiphilic nature, wood nanofibers were found to be effective stabilizers of water–oil emulsions.

Recent Developments in Smart Food Packaging Focused on Biobased and Biodegradable Polymers

Food packaging has a crucial function in the modern food industry. New food packaging technologies seek to meet consumers and industrial's demands. Changes related to food production, sale practices and consumers' lifestyles, along with environmental awareness and the advance in new areas of knowledge (such as nanotechnology or biotechnology), act as driving forces to develop smart packages that can extend food shelf-life, keeping and supervising their innocuousness and quality and also taking care of the environment. This review describes the main concepts and types of active and intelligent food packaging, focusing on recent progress and new trends using biodegradable and biobased polymers. Numerous studies show the great possibilities of these materials. Future research needs to focus on some important aspects such as possibilities to scale-up, costs, regulatory aspects, and consumers' acceptance, to make these systems commercially viable.

Concerning Synthesis of New Biobased Polycarbonates with Curcumin in Replacement of Bisphenol A and Recycled Diphenyl Carbonate as Example of Circular Economy

Curcumin (CM) is a natural polyphenol well-known for its antioxidant and pharmaceutical properties, that can represent a renewable alternative to bisphenol A (BPA) for the synthesis of bio-based polycarbonates (PC). In the presented strategy, preparation of the CM-based PC was coupled with chemical recycling of the fossil-based BPA polycarbonate (BPA-PC) conducting a two-steps trans-polymerization that replaces BPA monomer with CM or its tetrahydrogenated colorless product (THCM). In the first step of synthetic strategy, depolymerization of commercial BPA-PC was carried out with phenol as nucleophile, according to our previous procedure based on zinc derivatives and ionic liquids as catalysts, thus producing quantitatively diphenyl carbonate (DPC) e BPA. In the second step, DPC underwent a melt transesterification with CM or THCM monomers affording the corresponding bio-based polycarbonates, CM-PC and THCM-PC, respectively. THCM was prepared by reducing natural bis-phenol with cyclohexene as a hydrogen donor and characterized by 1H-NMR and MS techniques. Polymerization reactions were monitored by infrared spectroscopy and average molecular weights and dispersity of the two biobased polymers THCM-PC and CM-PC were determined by means of gel permeation chromatography (GPC). Optical properties of the prepared polymers were also measured.