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.

Pseudomonas umsongensis GO16 as a platform for the in vivo synthesis of short and medium chain length polyhydroxyalkanoate blends.

Polyhydroxyalkanoates (PHAs) are biological polyesters, viewed as a replacement for petrochemical plastic. However, they suffer from suboptimal physical and mechanical properties. Here, it was shown that a metabolically versatile Pseudomonas umsongensis GO16 can synthesise a blend of short chain length (scl) and medium chain length (mcl)-PHA. A defined mix of butyric (BA) and octanoic acid (OA) in different ratios was used. The PHA monomer composition varied depending on the feeding strategy. When OA and BA were fed at 80:20 ratio it showed 14, 8, 77 and 1 mol% of (R)-3-hydroxybutyrate, (R)-3-hydroxyhexanoate, (R)-3-hydroxyoctanoate and (R)-3-hydroxydecanoate respectively. The polymer characterisation clearly shows that polyhydroxybutyrate (PHB) and mcl-PHA are produced individually. The two polymers are blended on the PHA granule level, as demonstrated by fluorescence microscopy and yeast two-hybrid assay. The resulting blend has a specific viscoelasticity compared to PHB and PHO. Mcl-PHA acts as a plasticiser and reduces PHB brittleness.

From Lignins to Renewable Aromatic Vitrimers based on Vinylogous Urethane.

During the two last decades, covalent adaptable networks (CANs) have proven to be an important new class of polymer materials combining the main advantages of thermoplastics and thermosets. For instance, materials can undergo reprocessing cycles by incorporating dynamic covalent bonds within a cross-linked network. Due to their versatility, renewable resources can be easily integrated into these innovative systems to develop sustainable materials, which can be related to the context of the recent development of a circular bioeconomy. Lignins, the main renewable sources of aromatic structures, are major candidates in the design of novel and biobased stimuli-responsive materials such as vitrimers due to their high functionality and specific chemical architectures. In the aim of developing recyclable lignin-based vinylogous urethane (VU) networks, an innovative strategy was elaborated in which lignin was first modified into liquid polyols and then into polyacetoacetates. Resulting macromonomers were integrated into aromatic VU networks and fully characterized through thermal, mechanical, and rheological experiments. Viscoelastic behaviors of the different aromatic vitrimers exhibited fast stress-relaxations (e. g., 39 s at 130 °C) allowing easy and fast mechanical reprocessing. A thermomechanical recycling study was successfully performed. Then, the developed strategy enabled the fabrication of healable biobased aromatic vitrimers with tunable structures and properties.

Sustainable cycloaliphatic polyurethanes: from synthesis to applications.

Polyurethanes (PUs) are a versatile and major polymer family, mainly produced via polyaddition between polyols and polyisocyanates. A large variety of fossil-based building blocks is commonly used to develop a wide range of macromolecular architectures with specific properties. Due to environmental concerns, legislation, rarefaction of some petrol fractions and price fluctuation, sustainable feedstocks are attracting significant attention, e.g., plastic waste and biobased resources from biomass. Consequently, various sustainable building blocks are available to develop new renewable macromolecular architectures such as aromatics, linear aliphatics and cycloaliphatics. Meanwhile, the relationship between the chemical structures of these building blocks and properties of the final PUs can be determined. For instance, aromatic building blocks are remarkable to endow materials with rigidity, hydrophobicity, fire resistance, chemical and thermal stability, whereas acyclic aliphatics endow them with oxidation and UV light resistance, flexibility and transparency. Cycloaliphatics are very interesting as they combine most of the advantages of linear aliphatic and aromatic compounds. This original and unique review presents a comprehensive overview of the synthesis of sustainable cycloaliphatic PUs using various renewable products such as biobased terpenes, carbohydrates, fatty acids and cholesterol and/or plastic waste. Herein, we summarize the chemical modification of the main sustainable cycloaliphatic feedstocks, synthesis of PUs using these building blocks and their corresponding properties and subsequently present their major applications in hot-topic fields, including building, transportation, packaging and biomedicine.

Morphological Study of Bio-Based Polymers in the Consolidation of Waterlogged Wooden Objects.

The removal of water from archaeological wooden objects for display or storage is of great importance to their long-term conservation. Any mechanical instability caused during drying can induce warping or cracking of the wood cells, leading to irreparable damage of the object. Drying of an object is commonly carried out in one of three ways: (i) air-drying with controlled temperature and relative humidity, (ii) drying-out of a non-aqueous solvent or (iii) freeze-drying. Recently, there has been great interest in the replacement of the standard, but limited, polyethylene glycol with biopolymers for wood conservation; however, their behaviour and action within the wood is not completely understood. Three polysaccharides-low-molar-mass (Mw) chitosan (Mw ca. 60,000 g/mol), medium-molar-mass alginate (Mw ca. 100,000 g/mol) and cellulose nanocrystals (CNCs)-are investigated in relation to their drying behaviour. The method of drying reveals a significant difference in the morphology of these biopolymers both ex situ and within the wood cells. Here, the effect these differences in structuration have on the coating of the wood cells and the biological and thermal stability of the wood are examined, as well as the role of the environment in the formation of specific structures. The role these factors play in the selection of appropriate consolidants and drying methods for the conservation of waterlogged archaeological wooden objects is also investigated. The results show that both alginate and chitosan are promising wood consolidants from a structural perspective and both improve the thermal stability of the lignin component of archaeological wood. However, further modification would be necessary to improve the biocidal activity of alginate before it could be introduced into wooden objects. CNCs did not prove to be sufficiently suitable for wood conservation as a result of the analyses performed here.

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.

Synthesis of Biobased and Hybrid Polyurethane Xerogels from Bacterial Polyester for Potential Biomedical Applications.

Organic-inorganic xerogel networks were synthesized from bacterial poly (3-hydroxybutyrate) (PHB) for potential biomedical applications. Since silane-based networks usually demonstrate increased biocompatibility and mechanical properties, siloxane groups have been added onto polyurethane (PU) architectures. In this work, a diol oligomer (oligoPHB-diol) was first prepared from bacterial poly(3-hydroxybutyrate) (PHB) with an environmentally friendly method. Then, hexamethylene diisocyanate or biobased dimeryl diisocyanate was used as diisocyanate to react with the short oligoPHB-diol for the synthesis of different NCO-terminated PU systems in a bulk process and without catalyst. Various PU systems containing increasing NCO/OH molar ratios were prepared. Siloxane precursors were then obtained after reaction of the NCO-terminated PUs with (3-aminopropyl)triethoxysilane, resulting in silane-terminated polymers. These structures were confirmed by different analytical techniques. Finally, four series of xerogels were prepared via a sol-gel process from the siloxane precursors, and their properties were evaluated depending on varying parameters such as the inorganic network crosslinking density. The final xerogels exhibited adequate properties in connection with biomedical applications such as a high in vitro degradation up to 15 wt% after 12 weeks.

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.

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.

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.

Biobased polyurethanes for biomedical applications.

Polyurethanes (PUs) are a major family of polymers displaying a wide spectrum of physico-chemical, mechanical and structural properties for a large range of fields. They have shown suitable for biomedical applications and are used in this domain since decades. The current variety of biomass available has extended the diversity of starting materials for the elaboration of new biobased macromolecular architectures, allowing the development of biobased PUs with advanced properties such as controlled biotic and abiotic degradation. In this frame, new tunable biomedical devices have been successfully designed. PU structures with precise tissue biomimicking can be obtained and are adequate for adhesion, proliferation and differentiation of many cell's types. Moreover, new smart shape-memory PUs with adjustable shape-recovery properties have demonstrated promising results for biomedical applications such as wound healing. The fossil-based starting materials substitution for biomedical implants is slowly improving, nonetheless better renewable contents need to be achieved for most PUs to obtain biobased certifications. After a presentation of some PU generalities and an understanding of a biomaterial structure-biocompatibility relationship, recent developments of biobased PUs for non-implantable devices as well as short- and long-term implants are described in detail in this review and compared to more conventional PU structures.

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.

Renewable Responsive Systems Based on Original Click and Polyurethane Cross-Linked Architectures with Advanced Properties.

A new chemical architecture from oleic acid, consisting of a diol structure containing pendant furan rings, denoted the furan oligomer (FO) was synthesized and fully characterized. The FO was integrated into a linear rapeseed-based polyurethane (PU) backbone and cross-linked through a Diels-Alder (DA) reaction by using pendant furan rings and a short polypropylene oxide-based bismaleimide. This is the first time that a thermoreversible PU network based on vegetable oil has been reported. The effects of varying proportions of FO in linear and cross-linked systems, by DA, were studied. These materials were analyzed by classic characterization techniques. The stability and recyclability of the cross-linked materials were shown by successive reprocessing cycles and reanalyzing the mechanical properties. Self-healing properties were macroscopically exhibited and investigated by tensile tests on healed materials. The resulting cross-linked materials present a large range of properties, such as tunable mechanical and thermoresponsive behavior, good thermal recyclability, and self-healing abilities.

New Insight on the Study of the Kinetic of Biobased Polyurethanes Synthesis Based on Oleo-Chemistry.

Nowadays, polyols are basic chemicals for the synthesis of a large range of polymers, such as polyurethane foams (PUF), which are produced with several other compounds, such as polyisocyanates. During the last decades, the oleo-chemistry has developed several routes from glycerides to polyols for the polyurethanes (PU) industry to replace mainly conventional fossil-based polyols. A large range of biobased polyols can be now obtained by epoxidation of the double bonds and ring-opening (RO) of the subsequent epoxides with different chemical moieties. In preliminary studies, the RO kinetics of an epoxidized model molecule (methyl oleate) with ethanol and acetic acid were investigated. Subsequently, polyols that were derived from unsaturated triglycerides were explored in the frame of e.g., PUF formulations. Different associations were studied with different mono-alcohols derived from epoxidized and ring-opened methyl oleate while using several ring-openers to model such systems and for comparison purposes. Kinetic studies were realized with the pseudo-first-order principle, meaning that hydroxyls are in large excess when compared to the isocyanate groups. The rate of isocyanate consumption was found to be dependent on the moiety located in ß-position of the reactive hydroxyl, following this specific order: tertiary amine >> ether > ester. The tertiary amine in ß-position of the hydroxyl tremendously increases the reactivity toward isocyanate. Consequently, a biobased reactive polyurethane catalyst was synthesized from unsaturated glycerides. These approaches offer new insights regarding the replacement of current catalysts often harmful, pungent, and volatile used in PU and PUF industry, in order to revisit this chemistry.