Bio-based Feedstocks Research Articles

Domestication and engineering of pennycress (Thlaspi arvense L.): challenges and opportunities for sustainable bio-based feedstocks.

Pennycress, as an emerging oilseed crop with high oil content, faces challenges but offers potential for sustainable bioproducts; ongoing research aims to enhance its traits and quality. Pennycress (Thlaspi arvense L.) is an emerging oilseed crop with many advantages, such as high seed oil (27-39%) and monounsaturated fatty acid (55.6%) content, making it an attractive candidate to produce sustainable bioproducts. However, several challenges are associated with domesticating pennycress, including high silicle shatter, which reduces seed yield during harvest, non-uniformed germination rate and high contents of erucic acid and glucosinolates, which have adverse health effects on humans and animals. Pennycress, which can be easily and rapidly transformed using the floral dip method under vacuum, can achieve trait improvements. Ongoing research for pennycress domestication using mutation breeding, including ethylmethylsulfonate treatment and genome editing, aims to improve its quality. Pennycress can be used as an excellent platform for producing industrially important fatty acids such as hydroxy and epoxy fatty acids and docosahexaenoic acid. In conclusion, pennycress is a promising oilseed crop with multiple advantages and potential applications. Continuous improvements in quality and engineering for producing high-value bio-based feedstocks in pennycress will establish it as a sustainable and economically valuable crop.

Green Chemistry in Pharmaceutical Synthesis: Sustainable Strategies for Drug Production

The world is shifting from traditional synthetic or chemical technologies towards greener methods due to increasing concerns about maintaining a clean and sustainable environment. The development of eco-friendly products through processes that support environmental sustainability is referred to as a "green approach." In the pharmaceutical industry, there is growing attention to green synthesis of chemicals and materials, both in research and applied science, because green chemistry eliminates harmful processes and materials while promoting innovation in drug and therapeutic agent development. Green chemistry encompasses chemical reactions that minimize environmental impact and reduce toxicity. This field is rapidly evolving within pharmaceutical synthesis, focusing on the creation of sustainable medicines. This review explores the principles and practical applications of this innovative strategy within the pharmaceutical sector. By using environmentally friendly chemical processes, green chemistry reduces hazardous materials and pollution. Its aim is to mitigate the environmental footprint of drug production without compromising the quality and effectiveness of medicines. The approach also emphasizes the use of renewable and sustainable resources, such as shifting from petrochemical-based to bio-based feedstocks, allowing pharmaceutical companies to reduce their greenhouse gas emissions

Cross-Linked Polyolefins: Opportunities for Fostering Circularity Throughout the Materials Lifecycle.

Cross-linked polyolefins (XLPOs) constitute a significant portion of the plastics commercial market, with a market size of a similar order of magnitude to those of polystyrene and polyethylene terephthalate. However, few aspects of XLPO materials circularity have been examined relative to thermoplastic polyolefins. The cross-linking of polyolefins imparts superior performance properties, such as impact strength, chemical and electrical resistance, and thermal stability vs thermoplastic analogues, but it also makes the reprocessing of XLPOs to valuable products more challenging, as XLPOs cannot be molten. Thus, most XLPOs are incinerated or landfilled at the end of the first lifecycle, even though XLPO products are commonly collected as a relatively clean waste stream-providing a unique opportunity for valorization. In this review, we discuss approaches to improve XLPO circularity throughout the entire materials lifecycle by examining biobased feedstocks as alternative olefinic monomer sources and by assessing both traditional mechanical and advanced XLPO recycling methods based on industrial feasibility and potential product value. We also consider how advancing materials longevity can reduce environmental impacts and lifecycle costs and how recyclable-by-design strategies can enable better end-of-life opportunities for future generations of XLPO materials. Throughout this review, we highlight XLPO circularity routes that have the potential to balance the performance, circularity, and scalability necessary to impart economic and environmental viability at an industrial scale.

Unlocking sustainable solutions: wood waste as a novel substrate for polyhydroxybutyrate (PHB) production to combat plastic pollution

ABSTRACT Polyhydroxybutyrate (PHB) is considered as a hope for bioplastic production, which can serve as a sustainable alternative. Utilizing feedstock as substrate is widely explored for the production but wood waste, which is abundant in cellulose, hemicellulose and lignocellulose, has limited studies for PHB production. Herein, wood waste is used as a biobased feedstock Hydrolyses of wood waste was done using sulphuric acid (H2SO4) to break down of cellulose and hemicellulose into simple carbon forms. The hydrolysed product was analysed for sugar presence by quantitative and qualitative methods. Pseudomonas fluorescens bacterial strain was used for the production purpose using hydrolysed wood waste as substrate media. The Plackett-Burman design (PBD) and response surface methodology (RSM) were applied to optimize the growth media. The results of PBD were used to identify significant factors influencing PHB production, which were then further optimized using RSM. The work’s results conclusively demonstrated that P. fluorescens possesses the capability to effectively utilize wood waste and wastewater as substrate media up to production rate of 13–14 mg mL−1 of PHB. Fourier Transformed Infra-Red (FTIR) spectroscopic peaks confirm the produced product is PHB, which is a type of polyhydroxyalkanoate (PHA), classified within the polyester family highlighting wood waste potential as a sustainable solution to address plastic pollution.

Comparative life cycle assessment of PBAT from fossil-based and second-generation generation bio-based feedstocks

With the increasing demand for plastics, plastic pollution is growing rapidly. A significant amount of plastic has leaked into the environment, leading to severe environmental issues. Biodegradable plastics are considered promising alternatives to conventional durable plastics, and the environmental impacts of biodegradable plastics have received increasing attention. Poly (butylene adipate-co-terephthalate) (PBAT) is a commercial and cost-competitive biodegradable polymer and has been applied in the packaging and agriculture sectors. The environmental performances of PBAT with second-generation feedstocks from forestry waste have been rarely investigated. Since China is the leading global producer and exporter of PBAT polymer, Chinese cradle-to-gate life cycle inventories of PBAT were compiled in this study. A comparative life cycle assessment (LCA) was conducted to explore the potential for environmental performance of PBAT with second-generation bio-based feedstock compared to fossil-based PBAT and conventional plastics. The results showed that feedstocks contributed to more than 70 % of 18 environmental impact categories of fossil-based PBAT. In comparison, PBAT with second-generation bio-based feedstock reduces the environmental loads in 16 impact categories by 15–85 %, and renewable energy substitution has the potential to reduce environmental impacts by 10 %. Bio-based PBAT performs better than PVC, PP, HDPE, LDPE, and PET in 16 impact categories by 15–80 %. Bio-based PBAT has GWP of 3.72 kg CO2 eq, which is 37 % lower than fossil-based PBAT (5.89 kg CO2 eq) and 18–32 % lower than conventional plastics. Since feedstock dominates the environmental performance of PBAT, the development of biomanufacturing technologies for bio-based polymers and chemicals could significantly improve environmental performance of biodegradable plastics and promote the sustainable development of the plastic industry. Results could serve as the basis for environmental impact and mitigation strategies for biodegradable plastics with bio-based feedstocks, as well as the sustainable development of the PBAT industry.

Biomass to biofuel: Palm kernel shells as catalyst supports for enhanced biodiesel production

AbstractThe use of agricultural biomass fibers, specifically palm kernel shell (PKS), has significant potential to enhance biodiesel production. This approach overcomes economic barriers and contributes to sustainability by repurposing agricultural biomass. This study explores the effectiveness of PKS as a cost‐effective and sustainable catalyst support. Palm kernel shell was chosen due to its high carbon content, low ash presence, and abundance as a byproduct in the palm oil industry, making it an economically viable and environmentally friendly option. In this study, an optimized activated carbon from PKS biomass was fabricated as catalyst support to enhance biodiesel production efficiency. Using response surface methodology (RSM), the PKS was impregnated with phosphoric acid and synthesized at various acid concentrations, impregnation times, and activation times to enhance porosity for catalytic support capabilities. The experimental design included a central composite design (CCD) to vary these factors systematically and determine their optimal levels. Scanning electron microscopy (SEM) and Brunauer–Emmett–Teller (BET) analysis revealed significant development of porosity, affirming the efficient activation process. Energy dispersive X‐ray (EDX) analysis confirmed phosphorus incorporation during activation, indicating the formation of an intricate pore structure. Fourier transform infrared (FTIR) spectroscopy highlighted the presence of functional groups pertinent to the biodiesel reaction process. The transesterification process employing PKS as a catalyst with different biobased feedstocks, such as waste frying oils from corn, palm, and sunflower, led to biodiesel yields of varying efficiencies. Notably, corn oil had the highest yield at 94.92%. This study highlights the potential of PKS as a biobased catalyst support and contributes to the broader biorefinery concept by integrating biomass utilization into renewable fuel production.

Exploiting Lignin Structure and Reactivity to Design Vitrimers with Controlled Ratio of Dynamic to Non-Dynamic Bonds.

Lignin is an abundant biobased feedstock, representing the first source of renewable aromatic structures. Thanks to its high functionality in aliphatic hydroxyls (Al-OH), phenolic hydroxyls (Ph-OH) and carboxylic acids (COOH), lignin is an attractive precursor to crosslinked polymer materials. Different biobased macromolecular architectures can be designed from lignins, whose end-of-life should also be considered in the context of a circular bioeconomy. To enhance recyclability of crosslinked polymer networks, the introduction of dynamic linkages to design vitrimers is a promising strategy. In this study, Kraft lignin was chemically modified with succinic anhydride, to prepare a series of modified lignins with a controlled COOH/Ph-OH ratio, exploiting the difference in reactivity between Al-OH and Ph-OH groups. Upon crosslinking with a diepoxy, mixed vitrimer networks with variable ratios between dynamic ester bonds and non-dynamic ether bonds were synthesized. The analysis of their properties evidenced the impact of the non-dynamic linkages on the materials behaviors, including their dynamicity and reprocessing ability. Although the activation energy for bond exchange is increased, non-dynamic linkages do not hinder the reprocessability of these adaptable materials, and provide them high creep resistance. The controlled introduction of non-dynamic linkages appears as a promising strategy to enhance the properties of lignin-based vitrimers.

Production of bio-based adipic acid using a combination of engineered Pseudomonas putida strains

Adipic acid is an industrially important dicarboxylic acid and an essential precursor in the synthesis of Nylon-6,6. Due to the environmental impact associated with the current synthetic methods for Nylon-6,6 production, greener alternatives based on renewable and bio-based feedstocks are needed. In the present study, the potential of two Pseudomonas putida strains engineered for muconic acid accumulation was used to produce adipic acid from the lignin-derived aromatic compound guaiacol. This was achieved by expressing genes enabling the conversion of guaiacol to catechol in the first strain, and the conversion of muconic acid to adipic acid via expression of the Bacillus coagulans enoate reductase gene in the second strain. Through process engineering, a 2-step production was designed in which 2.93 mM bio-adipic acid was produced, with a yield of 0.57 mol/mol. This is the first demonstration that process and strain engineering can be combined to obtain a complete bio-based route for adipic acid production from depolymerized lignin compounds using the robust P. putida chassis.

Assessing the circularity and sustainability of circular carpets — a demonstration of circular life cycle sustainability assessment

Abstract Purpose Robust assessments are needed to identify the best circular economy (CE) approaches related to their contribution to achieving a CE by simultaneously considering the complexity of the three pillars of sustainability (environmental, economic, social). In this regard, the circular life cycle sustainability assessment (C-LCSA) framework was recently developed. This study aimed to demonstrate its applicability and capability of identifying trade-offs and interlinkages between the different dimensions using a case study of different CE approaches to carpet tiles. Methods C-LCSA integrates circularity and life cycle sustainability assessments (LCSA). Thus, this study applied the material circularity indicator (MCI) in parallel to life cycle assessment (LCA), life cycle costing (LCC), and social life cycle assessment (S-LCA). The last technique was applied as social hotspot assessment. Five CE approaches of carpet tiles produced in the US, including strategies like reducing the consumption of primary materials through recycled and bio-based feedstock or replacing carpet tiles for a longer overall service life, as well as recycling, were assessed and compared to their mainly linear counterpart. Results and discussion The study revealed that recycling carpet tiles containing recycled and bio-based materials at the end-of-life (EoL) resulted in the lowest global warming potential (8.47 kg CO2 eq.) and the highest circularity (MCI value of 0.76, with 1 indicating the maximum level of circularity) compared to the other scenarios. However, this scenario had a trade-off with a higher acidification potential (0.039 kg SO2 eq.) and higher costs (US$19.98) compared to the disposal scenario. On the other hand, the scenario using primary, non-bio-based materials in production and disposing of the carpet tiles at their EoL performed the worst in circularity (MCI value of 0.11) and implied high environmental impacts while being more cost-effective (US$10.27). Conclusions C-LCSA transparently revealed interlinkages in terms of circularity and the overall sustainability performance of different CE approaches. While no significant differences in terms of social hotspots were identified, approaches associated with a higher circularity and improved environmental performance in most impact categories tended to result in higher costs. This emphasized the need for individual and holistic assessments of the new CE approach to identify and address trade-offs. To enhance and foster C-LCSA in academia and industry, further studies applying the framework to different sectors are encouraged.

(Invited) Electrochemical Engineering Approaches for High-Performing Electrosynthesis of Polymer Precursors

The chemical industry accounts for ~5% of the US energy utilization and >30% of the US energy-derived industrial CO2 emissions. Amongst these processes, the production of organic chemical commodities, many of which are used as polymer precursors, account for the majority of the energy utilization (>1200 TBTU/y). The electrification of these processes via the implementation of electro-organic reactions could accelerate the decarbonization of the chemical industry, and bring additional sustainability advantages over their thermo-chemical counterparts. Currently, however, two major challenges prevent the deployment of electro-organic reactions: their low selectivity and their low production rates. To circumvent these barriers, our group deploys electrochemical reaction engineering principles to engineer electrode/electrolyte interfaces and design high-performing electro-organic processes. In this presentation, I will discuss how we implement this approach to understand and improve the performance of electro-organic reactions for the production of large-scale precursors for the production of Nylon 6,6 and polyethylene.The production of Nylon 6,6 involves the step-growth polymerization of 1,6-hexanediamine (HMDA) with adipic acid. HMDA is currently produced by the hydrogenation of adiponitrile (ADN). Here, I will present our insights into the electrohydrodimerization of acrylonitrile (AN) to adiponitrile (ADN). This is one of the largest electro-organic reaction deployed in industry and serves as a model process for the development of practical organic electrochemical processes. Our investigations on ADN uncovered relationships between the microenvironment at and near the electrical double layer (EDL) and reaction performance metrics (i.e., selectivity, efficiency, and productivity). I will discuss general guidelines for electrolyte formulation, dynamic electrochemical operation, the implementation of convective forces to mitigate transport limitations, ultimately leading in the conversion of AN to ADN at Faradaic efficiencies >80% and current densities of 100’s mA/cm2. Our learnings on ADN electrosynthesis helped us to engineer the electrocatalytic hydrogenation of ADN to HMDA, achieving the highest reported selectivity to date for this reaction (>95%). I will also show how similar electrochemical engineering approaches allowed us to elucidate factors that control performance in the electrochemical production of ADN from glutamic acid, an abundant and inexpensive bio-based feedstock, and of ethylene from bio-derived propionic acid. Through our studies, we aim to electrify and bring sustainability to chemical manufacturing, one reaction at a time.

Coprocessing of cashew nut shell liquid and phenol model compounds with VGO in a pilot-scale FCC riser

The feasibility of coprocessing of waste biomass resource cashew nut shell liquid (CNSL) with vacuum gas oil (VGO) to produce bio-based fuel has been demonstrated in a pilot riser. Herein, the effects of reaction temperature, catalyst to oil ratio (C/O), CNSL blending ratio, CNSL feed position and ZSM-5 addition on the product distribution and quality of CNSL coprocessing with VGO were analyzed in detail. CNSL was a suitable bio-based feedstock for coprocessing because any proportion of CNSL blended with VGO for coprocessing was feasible with no difficulties occurring in the system. The addition of CNSL could improve conversion and liquefied petroleum gas (LPG) yield in fluid catalytic cracking (FCC) while maintaining high gasoline yield. Compared to CNSL, phenol or guaiacol with a smaller kinetic diameter was more likely to cause catalyst deactivation. GCxGC-MS analysis of liquid products showed that the oxygenate content in the liquid products was low, and cashew phenol could be cracked, cyclized, dehydrogenated, and converted to naphthol, and further dehydrated and converted to naphthalenes. 14C analysis showed that the biocarbon content of LPG and gasoline produced from CNSL coprocessing was high, indicating that CNSL coprocessing was meaningful.

Unveiling the potential of self-healing and closed-loop recyclability in bio-based non-isocyanate polyurethane

The imperative shift towards sustainable production emphasizes the need for non-isocyanate polyurethanes (NIPUs) derived from biomass as a substitute for conventional petroleum-based polyurethanes. However, challenges persist in synthesizing NIPUs from renewable resources and addressing their recyclability post-service life. In this study, we report the synthesis of bio-based and closed-loop recyclable NIPU vitrimers using carbon dioxide (CO2), a vanillin derivative, and cystamine as bio-based feedstocks. The investigation examined the effect of the structure on the mechanical, thermal, and dynamic thermomechanical properties of bio-based NIPU vitrimers. The activation energy of the synthesized NIPUs was found to be relatively low (31.37 to 72.17 kJ/mol) after the incorporation of cystamine due to the presence of dual dynamic covalent bonds (disulfide and transcarbamoylation). As a result, the prepared bio-based NIPUs exhibited rapid self-healing and exceptional reprocessing efficiency (∼100 %). The mechanical properties of the reprocessed NIPUs could be restored to 99.5 % of their original values, highlighting remarkable reprocessing capabilities. The bio-based NIPU demonstrated closed-loop recyclability thanks to the dynamic disulfide bonds present in the vitrimer structure. This work offers an approach for the synthesis of bio-based NIPUS with closed-loop recyclability within the framework of sustainable materials.

Harnessing Enhanced Flame Retardancy in Rigid Polyurethane Composite Foams through Hemp Seed Oil-Derived Natural Fillers.

Over the past few decades, polymer composites have received significant interest and become protagonists due to their enhanced properties and wide range of applications. Herein, we examined the impact of filler and flame retardants in hemp seed oil-based rigid polyurethane foam (RPUF) composites' performance. Firstly, the hemp seed oil (HSO) was converted to a corresponding epoxy analog, followed by a ring-opening reaction to synthesize hemp bio-polyols. The hemp polyol was then reacted with diisocyanate in the presence of commercial polyols and other foaming components to produce RPUF in a single step. In addition, different fillers like microcrystalline cellulose, alkaline lignin, titanium dioxide, and melamine (as a flame retardant) were used in different wt.% ratios to fabricate composite foam. The mechanical characteristics, thermal degradation behavior, cellular morphology, apparent density, flammability, and closed-cell contents of the generated composite foams were examined. An initial screening of different fillers revealed that microcrystalline cellulose significantly improves the mechanical strength up to 318 kPa. The effect of melamine as a flame retardant in composite foam was also examined, which shows the highest compression strength of 447 kPa. Significantly better anti-flaming qualities than those of neat foam based on HSO have been reflected using 22.15 wt.% of melamine, with the lowest burning time of 4.1 s and weight loss of 1.88 wt.%. All the composite foams showed about 90% closed-cell content. The present work illustrates the assembly of a filler-based polyurethane foam composite with anti-flaming properties from bio-based feedstocks with high-performance applications.

Solar-Driven Biomass Reforming for Hydrogen Generation: Principles, Advances, and Challenges.

Hydrogen (H2) has emerged as a clean and versatile energy carrier to power a carbon-neutral economy for the post-fossil era. Hydrogen generation from low-cost and renewable biomass by virtually inexhaustible solar energy presents an innovative strategy to process organic solid waste, combat the energy crisis, and achieve carbon neutrality. Herein, the progress and breakthroughs in solar-powered H2 production from biomass are reviewed. The basic principles of solar-driven H2 generation from biomass are first introduced for a better understanding of the reaction mechanism. Next, the merits and shortcomings of various semiconductors and cocatalysts are summarized, and the strategies for addressing the related issues are also elaborated. Then, various bio-based feedstocks for solar-driven H2 production are reviewed with an emphasis on the effect of photocatalysts and catalytic systems on performance. Of note, the concurrent generation of value-added chemicals from biomass reforming is emphasized as well. Meanwhile, the emerging photo-thermal coupling strategy that shows a grand prospect for maximally utilizing the entire solar energy spectrum is also discussed. Further, the direct utilization of hydrogen from biomass as a green reductant for producing value-added chemicals via organic reactions is also highlighted. Finally, the challenges and perspectives of photoreforming biomass toward hydrogen are envisioned.

Comparative life cycle assessment for the sustainable production of fermentation-based L-methionine

Methionine, essential for human and animal growth, faces increasing demand, contributing significantly to greenhouse gas emissions through animal digestion and nitrogen excretion. This study introduces L-methionine (L-Met) produced biologically from CJ CheilJedang Corp., offering a sustainable alternative to the conventional petroleum-based DL-methionine (DL-Met) due to its higher bioavailability and reduced environmental impact. One of the most important aspects for the sustainable lifecycle of L-Met is to reduce environmental impact during the production stage. Consequently, the aim of this study is to evaluates the environmental impact of L-Met and its environmentally improved product, L-Met Eco, through a life cycle assessment compared to DL-Met. We employed scenario analysis to consider uptake CO2 by bio-based feedstock, bioavailability of methionine, and system expansion of co-products. Our findings indicate that L-Met and L-Met Eco have lower global warming potentials of 0.92 and 0.79 kg CO2/kg Met, respectively, than DL-Met (2.60−3.32 kg CO2/kg Met). Sensitivity analysis further suggests that optimizing renewable energy use and production location can significantly enhance the sustainability of L-Met production. This comprehensive study offers valuable insights for stakeholders in the bio-based material sector, promoting environmentally sustainable practices.

Revisiting the Potential of Group VI Inorganic Precatalysts for the Ethenolysis of Fatty Acids through a Mechanochemical Approach.

The utilization of biobased feedstocks to prepare useful compounds is a pivotal trend in current chemical research. Among a varied portfolio of naturally available starting materials, fatty acids are abundant, versatile substrates with multiple applications. In this context, the ethenolysis of unsaturated fatty acid esters such as methyl oleate is an atom-economical way to prepare functional C10 olefins with a biobased footprint. Despite the existence of a variety of metathesis catalysts for the latter process, there is a lack of readily available, efficient, and inexpensive catalytic systems based on earth-abundant metals (Mo, W) whose preparation does not require sophisticated syntheses and manipulations. Here, a systematic exploration of homogeneous and heterogeneous inorganic Mo, W (oxy)halides shows that MoOCl4, while inactive as a homogeneous species, forms active and selective silica-supported ethenolysis precatalysts able to reach equilibrium conversion of methyl oleate within a few minutes upon activation with SnMe4. Such heterogeneous MoOCl4-based precatalysts were easily accessed through mechanochemical solvent-free procedures and found to contain, upon characterization by elemental analysis and Raman spectroscopy, isolated (≡SiO)Mo(=O)Cl3 units or polymeric silica-supported [-O(≡SiO)nMoCl4-nO-]m (n = 1, 2) complexes depending on the molybdenum loading. The former isolated species exhibited a higher catalytic performance. The developed heterogeneous precatalysts could be applied to the ethenolysis of various substrates, including polyunsaturated fatty acid esters and industrial fatty acid methyl ester (FAME) mixtures from palm oil transesterification.

A Comparative Study on the Influence of N‐Doped Primary and Secondary Hydrochars on the Electrochemical Performance of Biobased Carbon Electrodes for Energy Storage Application

AbstractThe hydrothermal carbonization (HTC) technique and subsequent pyrolysis were applied. Herein, two different types of biobased feedstocks, sucrose (Suc) and Miscanthus (Mis), were chosen. Urea served as N precursor for the in situ doping. HTC of Suc and Mis with urea leads to N‐doped hydrochars (N‐HCs). Suc and Mis decompose in different, complex degradation pathways, which leads to the emergence of N‐HCs consisting of distinct ratios of N‐containing primary chars (N‐PCs) and secondary chars (N‐SCs). After pyrolysis, maximum N contents of 5.6 wt % and 4.8 wt % of the N‐doped pyrolyzed hydrochar (N‐PHC) electrodes from Suc and Mis, respectively were reached. The role of PC and SC formation on the impact of N‐doping in the context of physicochemical properties of the N‐PHCs was compared with each other. In this study, they were tested with respect to the influence of N‐PCs and N‐SCs on their electrochemical performance in energy storage application. It turned out that the electrical conductivity (EC) and specific capacitances increased. Highest EC value of 129.1 S ⋅ cm−1 was obtained with N‐PHC based on Suc. Simultaneously, enhanced average specific capacitances of 47.0 F ⋅ g−1 at 5 mV ⋅ s−1 and 3.5 F ⋅ g−1 at 100 mV ⋅ s−1 are ascertained with N‐PHCs from Suc and Mis, respectively.

Bio-Based Thermosetting Resins: From Molecular Engineering to Intrinsically Multifunctional Customization.

Recent years have witnessed a growing interest in bio-based thermosetting resins in terms of environmental concerns and the desire for sustainable industrial practices. Beyond sustainability, utilizing the structural diversity of renewable feedstock to craft bio-based thermosets with customized functionalities is very worthy of expectation. There exist many bio-based compounds with inherently unique chemical structures and functions, some of which are even difficult to synthesize artificially. Over the past decade, great efforts are devoted to discovering/designing functional properties of bio-based thermosets, and notable progress have been made in antibacterial, antifouling, flame retardancy, serving as carbon precursors, and stimuli responsiveness, among others, largely expanding their application potential and future prospects. In this review, recent advances in the field of functional bio-based thermosets are presented, with a particular focus on molecular structures and design strategies for discovering functional properties. Examples are highlighted wherein functionalities are facilitated by the inherent structures of bio-based feedstock. Perspectives on issues regarding further advances in this field are proposed at the end.

Fast-curing bio-based thermoset foams produced via the Michael 1,4-addition using fatty acid-based acetoacetate and acrylate

This study introduces an approach for creating bio-based polymer foams exploiting the Michael reaction that could be utilized as thermal insulation. The thermoset foams were developed using a second-generation bio-based feedstock – tall oil. Tall oil is a by-product of wood pulping in paper manufacturing and mainly comprises unsaturated fatty acids like oleic and linoleic acid. The study explores the use of tall oil-based acetoacetates (Michael donor) combined with various acrylates (Michael acceptor), petrochemical-based (bisphenol-A ethoxylate diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate), and bio-based (epoxidized soybean oil acrylate, epoxidized tall oil free fatty acids-based acrylate), to develop polymer foams that meet today's sustainability requirements. The developed polymer foams underwent extensive characterization. Matrix curing parameters were assessed by measuring changes in dielectric polarization during curing. Foaming parameters, including start and rise times, were precisely measured. The chemical composition of the foams was analysed using Fourier-transform infrared spectroscopy. Their thermal, thermo-mechanical, and mechanical properties were evaluated through thermal gravimetric analysis, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and compression tests. Additionally, the content of closed-cell and the coefficient of thermal conductivity were determined, further characterizing the foams as potential thermal insulation materials. Foams from bio-based donors with petrochemical-based acceptors exhibited a range of enhanced properties. They not only achieved high glass transition temperatures (up to 85 °C by DSC and up to 108 °C by DMA) but also displayed a spectrum of mechanical strengths (compression strength ranging from moderate to as high as ∼ 0.40 MPa) and good thermal isolation properties (thermal conductivity coefficient ∼ 31mW/(m·K)). Bio-based foams, derived from renewable resources, were characterized by properties fitting for flexible foam applications, such as low glass transition temperatures (down to −9.7 °C by DSC and down to 9.8 °C by DMA), reduced compression strength (approximately 0.011 MPa), and increased thermal conductivity (up to 46.7mW/(m·K)), indicating their potential utility in applications where flexibility is a key requirement.

Bio-based, closed-loop chemical recyclable aromatic polyamide from 2,5-furandicarboxylic acid: Synthesis, high performances, and degradation mechanism

The resource and environmental challenges posed by the extensive use and disposal of plastics have increased the urgency of research into plastic recycling and the hunt for bio-based alternative feedstocks. As one of the five general engineering polymers, polyamide has not yet been systematically explored in terms of its recycling performance or mechanism, especially aromatic polyamides. In addition, research on novel structured bio-based aromatic polyamides has not received sufficient attention due to the harsh polymerization conditions. In this work, bio-based fully aromatic polyamides based on 2,5-furandicarboxylic acid (FDCA) was successfully synthesized through the acyl chloride method, exhibiting thermal, mechanical, and barrier properties comparable to or superior to those of fossil derived isophthalic acid based polyamides. Moreover, both synthesized polyamides could be hydrolyzed in alkaline environments through the cleavage of amide bonds, as demonstrated by molecular dynamics simulations. The presence of furan rings lowered the energy barrier of hydrolysis as compared to benzene rings. Furthermore, a simple and efficient acidification followed by filtration approach with high recovery yields was developed to recover initial monomers from degradation solutions, thus achieving closed-loop chemical recovery of two polyamides. This work will further expand the application of bio-based feedstock, FDCA, and open new avenues for polyamide recycling research.