Synthesis and Assessment of Novel Sustainable Antioxidants with Different Polymer Systems.

Antioxidants are essential to the polymer industry. The addition of antioxidants delays oxidation and material degradation during their processing and usage. Sustainable phenolic acids such as 4-hydroxybenzoic acid or 3,4-dihydroxybenzoic acid were selected. They were chemically modified by esterification to obtain various durable molecules, which were tested and then compared to resveratrol, a biobased antioxidant, and Irganox 1076, a well-known and very efficient fossil-based antioxidant. Different sensitive matrices were used, such as a thermoplastic polyolefin (a blend of PP and PE) and a purposely synthesized thermoplastic polyurethane. Several formulations were then produced, with the different antioxidants in varying amounts. The potential of these different systems was analyzed using various techniques and processes. In addition to antioxidant efficiency, other parameters were also evaluated, such as the evolution of the sample color. Finally, an accelerated aging protocol was set up to evaluate variations in polymer properties and estimate the evolution of the potential of different antioxidants tested over time and with aging. In conclusion, these environmentally friendly antioxidants make it possible to obtain high-performance materials with an efficiency comparable to that of the conventional ones, with variations according to the type of matrix considered.

Study of the water sorption and barrier performances of potato starch nano-biocomposites based on halloysite nanotubes.

The barrier performances, in terms of water vapor sorption properties, gas and water barrier performances were analyzed on different starch-based nano-biocomposites. These multiphase systems were elaborated by melt blending starch and halloysite nanotubes at different contents with different plasticizers (glycerol, sorbitol and a mix of both polyols). The influence of the composition was investigated onto the structure, morphology, water sorption and barrier performances. As recently reported, halloysite nanoclay is a promising clay to enhance the properties of plasticized starch matrix. The barrier performances of nanofilled starch-based films were examined through gas and water permeabilities, diffusivity and water affinity. Glycerol-plasticized starch films give fine and more homogeneous nanofiller dispersion with good interfacial interactions, compared to sorbitol ones (alone or mixed), due to stronger and more stable hydrogen bonds. Tortuosity effects linked to the halloysite nanotubes were evidenced by gas transfer analysis, and exacerbated by the good interactions at interfaces and the resulting good filler dispersion. The influence of morphology and interfacial interactions towards water affinity was highlighted by moisture barrier properties. This was a key factor on the reduction of water diffusion and uptake with nanoclay content. A preferential water transfer was observed as a function of a plasticizer type in relation with the phenomenon of water plasticization in the nanocomposite systems.

Ferulic Acid as Building Block for the Lipase-Catalyzed Synthesis of Biobased Aromatic Polyesters.

Enzymatic synthesis of aromatic biobased polyesters is a recent and rapidly expanding research field. However, the direct lipase-catalyzed synthesis of polyesters from ferulic acid has not yet been reported. In this work, various ferulic-based monomers were considered for their capability to undergo CALB-catalyzed polymerization. After conversion into diesters of different lengths, the CALB-catalyzed polymerization of these monomers with 1,4-butanediol resulted in short oligomers with a DPn up to 5. Hydrogenation of the double bond resulted in monomers allowing obtaining polyesters of higher molar masses with DPn up to 58 and Mw up to 33,100 g·mol-1. These polyesters presented good thermal resistance up to 350 °C and Tg up to 7 °C. Reduction of the ferulic-based diesters into diols allowed preserving the double bond and synthesizing polyesters with a DPn up to 19 and Mw up to 15,500 g·mol-1 and higher Tg (up to 21 °C). Thus, this study has shown that the monomer hydrogenation strategy proved to be the most promising route to achieve ferulic-based polyester chains of high DPn. This study also demonstrates for the first time that ferulic-based diols allow the synthesis of high Tg polyesters. Therefore, this is an important first step toward the synthesis of competitive biobased aromatic polyesters by enzymatic catalysis.

MIXed plastics biodegradation and UPcycling using microbial communities: EU Horizon 2020 project MIX-UP started January 2020.

This article introduces the EU Horizon 2020 research project MIX-UP, "Mixed plastics biodegradation and upcycling using microbial communities". The project focuses on changing the traditional linear value chain of plastics to a sustainable, biodegradable based one. Plastic mixtures contain five of the top six fossil-based recalcitrant plastics [polyethylene (PE), polyurethane (PUR), polypropylene (PP), polyethylene terephthalate (PET), polystyrene (PS)], along with upcoming bioplastics polyhydroxyalkanoate (PHA) and polylactate (PLA) will be used as feedstock for microbial transformations. Consecutive controlled enzymatic and microbial degradation of mechanically pre-treated plastics wastes combined with subsequent microbial conversion to polymers and value-added chemicals by mixed cultures. Known plastic-degrading enzymes will be optimised by integrated protein engineering to achieve high specific binding capacities, stability, and catalytic efficacy towards a broad spectrum of plastic polymers under high salt and temperature conditions. Another focus lies in the search and isolation of novel enzymes active on recalcitrant polymers. MIX-UP will formulate enzyme cocktails tailored to specific waste streams and strives to enhance enzyme production significantly. In vivo and in vitro application of these cocktails enable stable, self-sustaining microbiomes to convert the released plastic monomers selectively into value-added products, key building blocks, and biomass. Any remaining material recalcitrant to the enzymatic activities will be recirculated into the process by physicochemical treatment. The Chinese-European MIX-UP consortium is multidisciplinary and industry-participating to address the market need for novel sustainable routes to valorise plastic waste streams. The project's new workflow realises a circular (bio)plastic economy and adds value to present poorly recycled plastic wastes where mechanical and chemical plastic recycling show limits.

Breakthrough in polyurethane bio-recycling: An efficient laccase-mediated system for the degradation of different types of polyurethanes.

Development of green, efficient and profitable recycling processes for plastic material will contribute to reduce the expanding plastic pollution and microplastics accumulation in the environment. Polyurethanes (PU) are versatile polymers with a large range of chemical compositions and structures. This variability increases the complexity of PU waste management. Biological recycling researchers have recently demonstrated great interest in polyethylene terephthalate. The adaptation of this route towards producing polyurethanes requires the discovery of enzymes that are able to depolymerize a large variety of PU. A laccase mediated system (LMS) was tested on four representative PU models, with different structures (foams and thermoplastics), and chemical compositions (polyester- and polyether-based PU). Size exclusion chromatography was performed on the thermoplastics and this revealed a significant reduction in the molar masses after 18 days of incubation at 37 °C. Degradation of foams under the same conditions was demonstrated by microscopy and compression assay for both polyester- and polyether-based PU. This study represents a major breakthrough in PU degradation, as it is the first time that enzymatic degradation has been clearly demonstrated on a polyether-based PU foam. This work is a step forward in the development of a sustainable recycling pathway, adapted to a large variety of PU materials.

Towards bio-upcycling of polyethylene terephthalate.

Over 359 million tons of plastics were produced worldwide in 2018, with significant growth expected in the near future, resulting in the global challenge of end-of-life management. The recent identification of enzymes that degrade plastics previously considered non-biodegradable opens up opportunities to steer the plastic recycling industry into the realm of biotechnology. Here, the sequential conversion of post-consumer polyethylene terephthalate (PET) into two types of bioplastics is presented: a medium chain-length polyhydroxyalkanoate (PHA) and a novel bio-based poly(amide urethane) (bio-PU). PET films are hydrolyzed by a thermostable polyester hydrolase yielding highly pure terephthalate and ethylene glycol. The obtained hydrolysate is used directly as a feedstock for a terephthalate-degrading Pseudomonas umsongensis GO16, also evolved to efficiently metabolize ethylene glycol, to produce PHA. The strain is further modified to secrete hydroxyalkanoyloxy-alkanoates (HAAs), which are used as monomers for the chemo-catalytic synthesis of bio-PU. In short, a novel value-chain for PET upcycling is shown that circumvents the costly purification of PET monomers, adding technological flexibility to the global challenge of end-of-life management of plastics.

Green Recycling Process for Polyurethane Foams by a Chem-Biotech Approach.

Polyurethanes (PUs) are highly resistant materials used for building insulation or automotive seats. The polyurethane end-of-life issue must be addressed by the development of efficient recycling techniques. Since conventional recycling processes are not suitable for thermosets, waste management of PU foam is particularly questioning. By coupling biological and chemical processes, this study aimed at developing a green recycling pathway for PU foam using enzymes for depolymerization. For instance, enzymatic degradation of a PU foam synthesized with polycaprolactone and toluene diisocyanate led to a weight loss of 25 % after 24 h of incubation. The corresponding degradation products were recovered and identified as 6-hydroxycaproic acid and a short acid-terminated diurethane. An organometallic-catalyzed synthesis of second-generation polymers from these building blocks was carried out. A polymer with a high average molar mass of 74000 (Mw ) was obtained by mixing 50 % of recycled building blocks and 50 % of neat 6-hydroxycaproic acid. A poly(ester urethane) was synthesized without the use of toxic and decried polyisocyanates. It is the first time that a study offers the vision of a recycling loop starting from PU wastes and finishing with a second-generation polymer in a full circular approach.

Characterization of the enzymatic degradation of polyurethanes.

For decades, polyurethanes (PUR) have mainly been synthesized for long-term applications and are therefore highly persistent in the environment. Proper waste disposal approaches, including recycling techniques, must be developed to limit the accumulation of PUR in the environment. Evaluation of enzymatic polyurethane degradation is needed for the development of enzymatic recycling. A series of techniques has been carefully implemented to monitor the biotic and abiotic degradation of PUR. Both the degraded polymer and the degradation products are analyzed to obtain a complete overview of the degradation.

Isolation of Low Dispersity Fractions of Acetone Organosolv Lignins to Understand their Reactivity: Towards Aromatic Building Blocks for Polymers Synthesis.

Two organosolv lignins extracted during pilot runs of the Fabiola process were analyzed, fractionated and chemically modified with ethylene carbonate (EC) to produce building blocks suitable for polymer synthesis. Isolation of low dispersity fractions relied on the partial solubility of the lignins in organic solvents. Lignins solubility was first evaluated and analyzed with Hansen and Kamlet-Taft solubility parameters, showing a good correlation with the solvents dipolarity/polarizability parameter π*. The results were then used to select a sequence of solvents able to fractionate the lignins into low dispersity fractions of increasing molar masses, which were analyzed by 31 P NMR, SEC and DSC. The lignins were then reacted with EC, to convert the phenolic OH groups into primary aliphatic OH groups. The reactivity of the organosolv lignins was high, and milder reaction conditions than previously reported were sufficient to fully convert the phenolic OH groups. A gradual reduction in reactivity with increasing molar mass was evidenced and attributed to reduced solubility of high molar mass fragments in EC. Undesirable crosslinking side reactions were evidenced by SEC, but were efficiently limited thanks to a fine control of the reaction conditions, helping to maximize the benefits of the developed lignin modification with EC.

Morphology and properties of thermoplastic starch blended with biodegradable polyester and filled with halloysite nanoclay.

The incorporation of halloysite clay nanotubes (HNTs) into thermoplastic starch/poly(butylene adipate-co-terephthalate) (TPS/PBAT) blends has been investigated with the aim of improving the compatibility and properties of the matrix. TPS/PBAT/HNTs nano-biocomposites with different TPS/PBAT weight fractions and HNTs contents were elaborated using a melt blending process, and their morphology and properties were investigated. The TPS80/PBAT20 and TPS20/PBAT80 blends exhibited dispersed phases of small droplets of PBAT or TPS, respectively, whereas the TPS50/PBAT50 blend presented a more homogeneous structure. Elongation at break of the TPS/PBAT/HNTs biocomposites with 5 wt% of HNTs significantly increased with increasing PBAT proportion, i.e., 6.5 %, 41.3 %, and 351.5 % for the composites based on TPS80/PBAT20, TPS50/PBAT50, and TPS20/PBAT80, respectively. The incorporation of 5 wt% of HNTs improved compatibility and increased Young's modulus of the TPS80/PBAT20, TPS50/PBAT50, and TPS20/PBAT80 blends approx. 350 %, 142 %, and 18 %, respectively. These results demonstrate that HNTs are promising nanofillers to improve properties of TPS-based blends.

Optimized Bioproduction of Itaconic and Fumaric Acids Based on Solid-State Fermentation of Lignocellulosic Biomass.

The bioproduction of high-value chemicals such as itaconic and fumaric acids (IA and FA, respectively) from renewable resources via solid-state fermentation (SSF) represents an alternative to the current bioprocesses of submerged fermentation using refined sugars. Both acids are excellent platform chemicals with a wide range of applications in different market, such as plastics, coating, or cosmetics. The use of lignocellulosic biomass instead of food resources (starch or grains) in the frame of a sustainable development for IA and FA bioproduction is of prime importance. Filamentous fungi, especially belonging to the Aspergillus genus, have shown a great capacity to produce these organic dicarboxylic acids. This study attempts to develop and optimize the SSF conditions with lignocellulosic biomasses using A. terreus and A. oryzae to produce IA and FA. First, a kinetic study of SSF was performed with non-food resources (wheat bran and corn cobs) and a panel of pH and moisture conditions was studied during fermentation. Next, a new process using an enzymatic cocktail simultaneously with SSF was investigated in order to facilitate the use of the biomass as microbial substrate. Finally, a large-scale fermentation process was developed for SSF using corn cobs with A. oryzae; this specific condition showed the best yield in acid production. The yields achieved were 0.05 mg of IA and 0.16 mg of FA per gram of biomass after 48 h. These values currently represent the highest reported productions for SSF from raw lignocellulosic biomass.

Evaluation of biological degradation of polyurethanes.

Polyurethanes (PU) are a family of versatile synthetic polymers intended for diverse applications. Biological degradation of PU is a blooming research domain as it contributes to the design of eco-friendly materials sensitive to biodegradation phenomena and the development of green recycling processes. In this field, an increasing number of studies deal with the discovery and characterization of enzymes and microorganisms able to degrade PU chains. The synthesis of short lifespan PU material sensitive to biological degradation is also of growing interest. Measurement of PU degradation can be performed by a wide range of analytical tools depending on the architecture of the materials and the biological entities. Recent developments of these analytical techniques allowed for a better understanding of the mechanisms involved in PU biodegradation. Here, we reviewed the evaluation of biological PU degradation, including the required analytics. Advantages, drawbacks, specific uses, and results of these analytics are largely discussed to provide a critical overview and support future studies.

Enzymatic recycling of thermoplastic polyurethanes: Synergistic effect of an esterase and an amidase and recovery of building blocks.

Biological recycling of polyurethanes (PU) is a huge challenge to take up in order to reduce a large part of the environmental pollution from these materials. However, enzymatic depolymerization of PU still needs to be improved to propose valuable and green solutions. The present study aims to identify efficient PU degrading enzymes among a collection of 50 hydrolases. Screenings based on model molecules were performed leading to the selection of an efficient amidase (E4143) able to hydrolyze the urethane bond of a low molar mass molecule and an esterase (E3576) able to hydrolyze a waterborne polyester polyurethane dispersion. Degradation activities of the amidase, the esterase and a mix of these enzymes were then evaluated on four thermoplastic polyurethanes (TPU) specifically designed for this assay. The highest degradation was obtained on a polycaprolactone polyol-based polyurethane with weight loss of 33% after 51 days measured for the esterase. Deep cracks on the polymer surface observed by scanning electron microscopy and the presence of oligomers on the remaining TPU detected by size exclusion chromatography evidenced the polymer degradation. Mixing both enzymes led to an increased amount of urethane bonds hydrolysis of the polymer. 6-hydroxycaproic acid and 4,4'-methylene dianiline were recovered after depolymerization as hydrolysis products. Such building blocks could get a second life with the synthesis of new macromolecular architectures.

Isolation and characterization of different promising fungi for biological waste management of polyurethanes.

As a highly resistant polymer family, polyurethanes (PU) are responsible for increasing environmental issues. Then, PU biodegradation is a challenging way to develop sustainable waste management processes based on biological recycling. Since the metabolic diversity of fungi is a major asset for polymer degradation, nearly thirty strains were isolated from sampling on six different PU wastes-containing environments. A screening of the fungi on four thermoplastic PU (TPU) with different macromolecular architectures led to the selection of three strains able to use two polyester PU as sole carbon source: Alternaria sp., Penicillium section Lanata-Divaricata and Aspergillus section flavi. Weight loss, FT-IR, Scanning Electron Microscopy and Size Exclusion Chromatography analyses revealed that these three fungi degrade slightly and similarly a fatty acid dimer-based TPU while variability of degradation was noticed on a polycaprolactone-based TPU. On this last TPU, robust analysis of the degraded polymers showed that the Penicillium strain was the best degrading microorganism. Membrane enzymes seemed to be involved in this degradation. It is the first time that a strain of Penicillium of the section Lanata-Divaricata displaying PU biodegradation ability is isolated. These newly discovered fungi are promising for the development of polyester PU waste management process.

Original Macromolecular Architectures Based on poly(ε-caprolactone) and poly(ε-thiocaprolactone) Grafted onto Chitosan Backbone.

Polyester and/or polythioester grafted chitosan copolymers were synthesized. For that, poly(ε-caprolactone) (PCL), poly(ε-thiocaprolactone) (PTCL), and their copolymers were first synthesized by ring opening polymerization. Copolymers with caprolactone:thiocaprolactone (CL:TCL) molar ratios of 2:1, 1:1, 1:2 were synthesized. All of the synthesized macromolecular architectures were characterized using different spectral (Fourier transform infrared (FTIR), proton nuclear magnetic resonance (¹H-NMR), X-Ray diffraction (XRD)) and thermal (Differential scanning calorimetry (DSC), Thermogravimetric analysis (TGA)) methods. Grafting was then performed according two distinct routes: (i) using a blend of both homopolymers (PCL and PTCL) or (ii) using pre-synthesized copolymers with controlled CL:TCL ratios. Hexamethylene diisocyanate was used as a grafting/coupling agent through urethane bonds with high yield. Grafting preferentially occurred at sulfur sites. The results indicated that PTCL is more reactive and favorable than PCL for grafting onto chitosan. With the homopolymers blend grafting route, the corresponding materials mostly had a higher PTCL portion than expected. To obtain polyester grafted chitosan with a determined CL:TCL ratio, the copolymer grafting route would yield better results.

Biotic and Abiotic Synthesis of Renewable Aliphatic Polyesters from Short Building Blocks Obtained from Biotechnology.

Biobased polymers have seen their attractiveness increase in recent decades thanks to the significant development of biorefineries to allow access to a wide variety of biobased building blocks. Polyesters are one of the best examples of the development of biobased polymers because most of them now have their monomers produced from renewable resources and are biodegradable. Currently, these polyesters are mainly produced by using traditional chemical catalysts and harsh conditions, but recently greener pathways with nontoxic enzymes as biocatalysts and mild conditions have shown great potential. Bacterial polyesters, such as poly(hydroxyalkanoate)s (PHA), are the best example of the biotic production of high molar mass polymers. PHAs display a wide variety of macromolecular architectures, which allow a large range of applications. The present contribution aims to provide an overview of recent progress in studies on biobased polyesters, especially those made from short building blocks, synthesized through step-growth polymerization. In addition, some important technical aspects of their syntheses through biotic or abiotic pathways have been detailed.

Enzymatic Synthesis of Amino Acids Endcapped Polycaprolactone: A Green Route Towards Functional Polyesters.

ε-caprolactone (CL) has been enzymatically polymerized using α-amino acids based on sulfur (methionine and cysteine) as (co-)initiators and immobilized lipase B of Candida antarctica (CALB) as biocatalyst. In-depth characterizations allowed determining the corresponding involved mechanisms and the polymers thermal properties. Two synthetic strategies were tested, a first one with direct polymerization of CL with the native amino acids and a second one involving the use of an amino acid with protected functional groups. The first route showed that mainly polycaprolactone (PCL) homopolymer could be obtained and highlighted the lack of reactivity of the unmodified amino acids due to poor solubility and affinity with the lipase active site. The second strategy based on protected cysteine showed higher monomer conversion, with the amino acids acting as (co-)initiators, but their insertion along the PCL chains remained limited to chain endcapping. These results thus showed the possibility to synthesize enzymatically polycaprolactone-based chains bearing amino acids units. Such cysteine endcapped PCL materials could then find application in the biomedical field. Indeed, subsequent functionalization of these polyesters with drugs or bioactive molecules can be obtained, by derivatization of the amino acids, after removal of the protecting group.

Preparation and Characterization of Thermoplastic Potato Starch/Halloysite Nano-Biocomposites: Effect of Plasticizer Nature and Nanoclay Content.

Nano-biocomposites based on halloysite nanoclay and potato starch were elaborated by melt blending with different polyol plasticizers such as glycerol, sorbitol or a mixture of both. The effects of the type of plasticizer and clay content on potato starch/halloysite nano-biocomposites were studied. SEM analyses combined with ATR-FTIR results showed that a high content of sorbitol had a negative effect on the dispersion of the halloysite nanoclay in the starchy matrix. XRD results demonstrated that incorporation of halloysite nanoclay into glycerol-plasticized starch systems clearly led to the formation of a new crystalline structure. The addition of halloysite nanoclay improved the thermal stability and decreased the moisture absorption of the nano-biocomposites, whatever the type of plasticizer used. Halloysite addition led to more pronounced improvement in mechanical properties for glycerol plasticized system compared to nanocomposites based on sorbitol and glycerol/sorbitol systems with a 47% increase in tensile strength for glycerol-plasticized starch compared to 10.5% and 11% for sorbitol and glycerol/sorbitol systems, respectively. The use of a mixture of polyols was found to be a promising way to optimize the mechanical properties of these starch-based nanocomposites.

Original method for synthesis of chitosan-based antimicrobial agent by quaternary ammonium grafting.

Functionalized high molar mass chitosan derivatives with increased antibacterial properties were prepared by the reaction of chitosan with different quaternary ammonium salts. Benzalkonium bromide, pyridinium bromide and triethyl ammonium bromide were synthesized by a quaternization reaction between 1,4-dibromobutane and the respective tertiary amines (N, N-dimethylbenzylamine, triethylamine and pyridine) to obtain three ammonium salts with a bromide end-group capable of reacting with a functional group from the chitosan backbone. The ammonium salts were chemically grafted along the chitosan macromolecular chains. Four different chitosan derivatives were obtained and their chemical structures analyzed and confirmed by 1H NMR and FT-IR. The corresponding thermal stability was analyzed by TGA. Antibacterial activity has been assessed by determining their minimal inhibitory concentration upon Escherichia coli and Staphylococcus aureus. Furthermore, the antibiogram method was used to complement the antibacterial analysis. The bacteria inhibitory property of the chitosan derivatives exhibited a remarkable improvement compared to unmodified chitosan.

Innovative plasticized alginate obtained by thermo-mechanical mixing: Effect of different biobased polyols systems.

Plasticized alginate films with different biobased polyols (glycerol and sorbitol) and their mixtures were successfully prepared by thermo-mechanical mixing instead of the usual casting-evaporation procedure. The microstructure and properties of the different plasticized alginate formulations were investigated by SEM, FTIR, XRD, DMTA and uniaxial tensile tests. SEM and XRD results showed that native alginate particles were largely destructured with the plasticizers (polyols and water), under a thermo-mechanical input. With increasing amount of plasticizers, the samples showed enhanced homogeneity while their thermal and mechanical properties decreased. Compared to sorbitol, glycerol resulted in alginate films with a higher flexibility due to its better plasticization efficiency resulting from its smaller size and higher hydrophilic character. Glycerol and sorbitol mixtures seemed to be an optimum to obtain the best properties. This work showed that thermo-mechanical mixing is a promising method to produce, at large scale, plasticized alginate-based films with improved properties.