Bio-based Raw Materials Research Articles

Synthesis and properties of chlorine and phosphorus containing rubber seed oil as a second plasticizer for flame retardant polyvinyl chloride materials

Abstract The synthesis of multifunctional plasticizer using rubber seed oil can increase its added value and expand the application field of plasticized products. Recent studies on bio-based plasticizers focus on bio-based raw materials but products lack functionality. In this study, flame retardant phosphate and chlorine were introduced into the chemical structure of rubber seed oil to synthesis a nitrogen and phosphorus synergistic flame retardant plasticizer based on rubber seed oil(NPFP) and apply it to plasticize polyvinyl chloride (PVC). Thermal stability, limiting oxygen index, plasticizing property, solvent extraction resistance, and microstructure of plasticized PVC materials were characterized. The results showed that NPFP with excellent solvent extraction resistance can significantly enhance the limiting oxygen index and thermal stability of plasticized PVC materials, and can partially replace dioctyl phthalate(DOP) as multifunctional auxiliary plasticizer.

Development of a strong and conductive soy protein adhesive by building a hybrid structure based on multifunctional wood composite materials

In this study, a strong and multifunctional soy protein adhesive was designed and developed. It was then combined with wood units to prepare a clean and electromagnetic shielding wood-based panel via simple hot press. Specifically, bio-based raw material was prepared by grafting pyrrole (PY) and dopamine hydrochloride (DOPA) in sequence on to soy protein isolate (SPI), and then combined with AgNO3 and a self-synthesized bio cross-linker epoxidized quercetin (EQC), to develop a strong and conductive soy protein-based adhesive with mildew-proof and flame-retardant properties. A covalent cross-linked structure and noncovalent bond (hydrogen bonds and ionic bonds) were formed among SPI, EQC, DOPA, and Ag+. As well, a hybrid structure was formed via in situ polymerization of Ag NPs, resulting in an adhesive with improved water resistance. Thus, the dry and wet shear strengths of plywood bonded with resultant adhesive increased by 78% and 52.4%, respectively, relative to those of the SPI adhesive. The modified adhesive exhibited good mildew resistance (shelf life ＞ 15 d) due to the natural antibacterial properties of quercetin, and the dynamic equilibrium of Ag NPs and Ag+ in the presence of DOPA. Meanwhile, the LOI of the modified adhesive was 41.3%, which is higher than that of SPI, improving flame retardancy of the resultant plywood. Notably, the obtained adhesive exhibited conductivity owing to the presence of polypyrrole (up to 7.09 S/cm), which can be used to develop reflection-based particle board with electromagnetic shielding ability. This study provides a high-potential and feasible strategy for developing multifunctional biomass composites to replace metal and polymer materials, which is an important and practical approach to promote sustainable development of materials and reduce carbon emissions.

LyondellBasell delivers renewable-based polymers for the medical device industry

On April 24, 2023, LyondellBasell announced that CirculenRenew polymers will be used in the housing of a female urinary catheter, called “LoFric Elle”, which is marketed by Wellspect HealthCare, a Swedish MedTech business. In an industry that is heavily reliant on fossil based raw materials for its plastic, this project is reportedly one of the first of its kind for medical devices. The LyondellBasell grade is ISCC PLUS certified and offers a mass balance certificate to allocate the bio-based raw materials to the product.

Green Fabrication of Sustainable Porous Chitosan/Kaolin Composite Membranes Using Polyethylene Glycol as a Porogen: Membrane Morphology and Properties.

One of the major challenges in membrane manufacturing today is to reduce the environmental footprint by promoting biobased raw materials and limiting the use of toxic solvents. In this context, environmentally friendly chitosan/kaolin composite membranes, prepared using phase separation in water induced by a pH gradient, have been developed. Polyethylene glycol (PEG) with a molar mass ranging from 400 to 10,000 g·mol-1 was used as a pore forming agent. The addition of PEG to the dope solution strongly modified the morphology and properties of the formed membranes. These results indicated that PEG migration induced the formation of a network of channels promoting the penetration of the non-solvent during the phase separation process, resulting in an increase in porosity and the formation of a finger-like structure surmounted by a denser structure of interconnected pores of 50-70 nm in diameter. The hydrophilicity of the membrane surface increased likely related to PEG trapping in the composite matrix. Both phenomena were more marked as the PEG polymer chain was longer, resulting in a threefold improvement in filtration properties.

Vat Photopolymerization of Nanocellulose-Reinforced Vegetable Oil-Based Resins: Synergy in Morphology and Functionalization

With the advancement of additive manufacturing (AM) and the mass adoption of 3D printing technology, it is essential to shift focus to environmentally and economically sustainable materials. As the utilization of renewable feedstocks is quite limited in this context, the utilization of more bio-based raw materials in the ongoing development of AM represents an essential means of achieving this shift. In this work, vat photopolymerization 3D printing has been used to process vegetable oil-based (VO) resins with an ultralow concentration of 0.07 vol % nanocellulose fibrils (NFC) and crystals (NCC). The developed nanocellulose containing bio-based vat photopolymerization resin shows excellent shelf stability, enabling high-resolution printing. Compatibilization of the nanocellulose with the polymer matrix was achieved through the introduction of isocyanate or acrylate groups via reactions of acryloyl chloride (AC) and hexamethylene diisocyanate (HMDI) with cellulose surface hydroxyls. Surface functionalization results in ∼20–30% increases in interfacial adhesion and stress transfer, yielding significant improvements in mechanical performance (4× higher toughness, 2.4× higher tensile strength, and 2× higher tensile strain) in 3D-printed specimens. Fourier-transformation infrared (FTIR) spectroscopy complemented by solid-state nuclear magnetic resonance (NMR) techniques enabled a more detailed study of the chemical structure of these materials as well. Tensile performance comparison with literature data on VO-based natural fiber-reinforced resins showed that this work brought bio-based resins one step closer to competing with petroleum-based resins. The prepared VO/nanocellulose resins are promising candidates for high-performance bio-based resins derived from completely renewable feedstocks.

Investigation of the Characteristics of Bio-based Raw Materials: Technical Hemp Fibers

The relevance of the topic is indicated. Examples of the use of technical hemp fibers for the manufacture of various products are given. The research methods used to obtain qualitative indicators of the characteristics of technical hemp fibers are described. A description of the samples is compiled. The data obtained as a result of measuring the parameters of technical hemp fibers are presented. A comparative analysis of samples of technical hemp fibers from various regions of the spring harvest is carried out. The disadvantages of the obtained raw materials are revealed. A proposal is introduced to unify requirements in order to improve the quality of raw materials and products.

Damage detection in bio-polyamide 11/woven basalt fibres composite laminates subjected to dynamic events

The complexity of the damage behavior of composite materials due to the simultaneous evolution of different mechanisms involving matrixes, reinforcements and interfaces is a topic which, despite decades of knowledge, still requires specific insights and is the subject of a multitude of researches. Recently, with the attention increasingly directed towards biobased raw materials, these aspects have shown a renewed interest, prompting the need for further contributions. In this context, this experimental research work aims to investigate the damage behavior of laminate structures based on a commercial polyamide obtained from castor oil, reinforced with woven basalt fibers. The focus was on samples obtained by hot compaction using two different pressure profiles and subjected to low velocity impacts with different impact energies. Damage analysis was performed on impacted specimens using ultrasonic phased array inspections and pulsed thermography. The non-destructive analysis supported low velocity impact test results, confirming the different contribution of the damage mechanisms involved, as expected from the different level of compaction of the materials, in turn due to diverse manufacturing conditions. This research has emphasized the complementarity and effectiveness of these two non-destructive characterization techniques, providing potentially useable results for the optimal design and manufacturing of biocomposite systems.

Application of Vegetable Oil-Based Monomers in the Synthesis of Acrylic Latexes via Emulsion Polymerization

In this work, two bio-based raw materials, rapeseed oil and technical-grade oleic acid, were modified to yield acrylated monomers. Polymeric latexes designed for coating applications were synthesized using emulsion polymerization. Methyl methacrylate and butyl acrylate were copolymerized with various ratios of the acrylated bio-based monomers (0–20 wt.% in the monomer mixture). The polymerization with high monomer conversion and low coagulum content was successfully performed up to the content of 15 wt.% of the bio-based monomers, leading to long-term stable latexes. The asymmetric flow field flow fractionation coupled with a multi-angle light scattering detector was used to describe the molar mass distribution of the synthesized copolymers. Ultra-high molar mass fractions were detected in copolymers comprising the bio-based monomers due to the presence of multi-acrylated bio-based ingredients originating from linoleic and linolenic fatty acids. This phenomenon became more pronounced for the rapeseed oil-originated monomer. The prepared latexes comprising copolymerized bio-based monomers showed comparable or even better coating performance in terms of gloss and water resistance in comparison with the reference acrylic coating, which makes the acrylated vegetable oil-based monomers attractive for the manufacturing of sustainable water-borne materials in the coating industry.

Synthesis of cyclic carbonates from CO2 cycloaddition to bio-based epoxides and glycerol: an overview of recent development.

Anthropogenic carbon dioxide (CO2) emissions contribute significantly to global warming and deplete fossil carbon resources, prompting a shift to bio-based raw materials. The two main technologies for reducing CO2 emissions are capturing and either storing or utilizing it. However, while capture and storage have high reduction potential, they lack economic feasibility. Conversely, by utilizing the CO2 captured from streams and air to produce valuable products, it can become an asset and curb greenhouse gas effects. CO2 is a challenging C1-building block due to its high kinetic inertness and thermodynamic stability, requiring high temperature and pressure conditions and a reactive catalytic system. Nonetheless, cyclic carbonate production by reacting epoxides and CO2 is a promising green and sustainable chemistry reaction, with enormous potential applications as an electrolyte in lithium-ion batteries, a green solvent, and a monomer in polycarbonate production. This review focuses on the most recent developments in the synthesis of cyclic carbonates from glycerol and bio-based epoxides, as well as efficient methods for chemically transforming CO2 using flow chemistry and novel reactor designs.

Xanthan Gum—Bio-Based Raw Material for Wood Adhesive

Xanthan Gum—Bio-Based Raw Material for Wood Adhesive

Sustainable Sources for Cosmetic Ingredients – Evaluation of the Biomass of Crete as a Model Region

Sustainable sourcing of cosmetic ingredients nowadays includes the use of bio-based raw materials. In order to avoid waste and to use by-products of agriculture in the best possible way, a Material and Energy Management (MEM) system of the bioeconomy has to be established. As a new approach towards sources for cosmetic basics and actives, an evaluation of local biomass was carried out in this study, using the Greek island of Crete – which has a rich endemic flora – as a model region.

Recent progress in biobased synthetic textile fibers

The use of synthetic fibers in our daily life is growing continuously; however, the excessive dependence of these chemical fibers on petroleum-based chemicals will lead to large consumption of non-renewable resources. The scarcity of oil resources, economic and environmental problems, reliance on a few oil-rich countries, and predicted depletion of these resources. Therefore, research and development of biobased materials to reduce the use of fossil fuels have become increasingly important. Biobased synthetic fiber has a low carbon footprint in the synthesis process because its raw materials are derived from biomass. In addition, most biobased synthetic fibers have excellent biodegradability, which can be composted and degraded in natural environments or by microorganisms with or without specific conditions. However, all biobased fibers cannot be proven to be biodegradable, so the development of biodegradability is an important driving force for the progress of research on biobased fibers. In the past, biobased fiber was obtained, extracted, or synthesized from food crops, which was soon replaced by non-food crops. With environmental protection, sustainability, and resource conservation, it has become necessary to make non-food crops and food residues biobased raw materials to obtain biobased textile fibers and even to develop ideal biobased raw materials that are carbon negatives, such as moss and CO2. Besides, there is huge potential for these biobased textile fibers to be used for sustainable clothing and medical textiles due to their non-toxicity, skin friendliness, and antibacterial properties. This review paper introduces biobased synthetic textile fibers, summarizes the recent development, and clarifies key concepts in this domain.

Transition of bioeconomy as a key concept for the agriculture and agribusiness development: An extensive review on ASEAN countries

Transition of bioeconomy plays an important role in the development of any economy. Therefore, the purpose of the current paper is to review the key concept of transition of the bioeconomy in the ASEAN economies that is considered to be an innovative collective method for observing the operation of national economies' numerous sectors that produce and process biological wealth. Based on current literature, it has been reviewed that the transition of bioeconomy is being presented with respect to the theoretical concept, and their essence and bioeconomy size, and the challenges and risks which are related to the bioeconomy transition. The various ways and the area of action along with present strategies which are supporting the development of bio economies and their relationship with the circular economies model had been presented. It was seen in the literature that ASEAN agricultures sectors had been contributing their major part in the development of value-added products and employment, except for Malaysia, Thailand, and Laos. Moreover, the analysis results had also shown that the transition of bioeconomy is considered to be an important concept in the growth of agriculture, forestry, agribusiness, and various sectors that produce and use bio-based raw materials. It was further found that for real bio-economy opportunities, it is essential that there should be a proper national and regional strategy for the bioeconomy development in place and for the development of a proper design and proper management coordination at every level of sectors, enterprises, and provincial systems.

Bio-based vitrimeric elastomers enable completely sustainable triboelectric nanogenerator

Completely sustainable triboelectric nanogenerators (TENGs) with bio-based raw materials, green synthesis, resource-saving processing, durable mechanical and electrical performance, facile recycling, and degradation properties are highly desired for green energy harvesting and wearable electronics, but their preparation remains a challenge. This study develops bio-based vitrimers combining green synthesis, excellent elasticity, biodegradability, and recyclability to address this challenge. A salt-assisted three-dimensional (3D) printing strategy is developed to fabricate mechanically robust TENGs with hierarchical porous structures. The triboelectric contact between the surfaces and external triboelectric materials as well as that of the internal hierarchical pore’s wall contributes to the excellent electrical output performance. The resultant TENGs could be easily recycled into different forms by light-assisted fabrication to extend their lifetime. The main part of discarded TENGs shows facile degradation under benign conditions without negative influence on the environment, while the high-value conductive fillers can be readily recycled. Overall, this work presents a new paradigm for completely sustainable TENGs, which will inspire the development of sustainable electronic devices.

Effects of glutaric anhydride functionalization on filler-free benzoxazine/epoxy copolymers with shape memory and self-healing properties under near-infrared light actuation

We have developed new types of thermosets from bio-based benzoxazine/epoxy copolymers with shape memory and self-healing properties that could be triggered by using near-infrared (NIR) light, without using any filler. The copolymers were prepared from bio-based raw materials, including vanillin, furfurylamine, and epoxidized castor oil, along with functionalized with glutaric anhydride (GA), due to which self-healing properties of the copolymers were enabled through dynamic covalent bonds. Effects of GA content (0.00, 0.02, 0.04, 0.06, 0.08, and 0.10 mol) on molecular structure, mechanical properties, dynamic mechanical properties, and thermal stability of the copolymers were investigated. The results from infrared spectroscopy showed the formation of ester linkages and free carboxylic acids upon functionalization of copolymers with GA. The increased crosslinking density by GA was observed from increased tensile strength (from 11 to 16 MPa), glass transition temperature (72–150 °C), and degradation temperature at 5% weight loss (382–405 °C) of the copolymers. However, excess contents (0.08 and 0.10 mol) of GA might result in the existence of free components, hindering the formation of the copolymer network and diminishing the mechanical properties of the copolymers. Shape memory properties of GA-functionalized V-fa/ECO copolymers were investigated under NIR actuation; the results showed a 100% of shape recovery ratio within 20 s of actuation. Self-healing properties of GA-functionalized V-fa/ECO copolymers were investigated under NIR actuation; the results showed 94% of restored storage modulus after 20 min of actuation. Lastly, the self-healing mechanism under NIR actuation was proposed that NIR photothermal effects of the copolymers induced the crack closing due to their shape memory effects. Consequently, the copolymer chains could diffuse across the crack interface along with transesterification through GA functionalities, leading to crack healing. The findings of this study suggested a new way to produce NIR light-responsive self-healing polymer without using NIR photothermal filler. • Filler-free benzoxazine/epoxy copolymers with shape memory and self-healing effects triggered by NIR light were developed. • Copolymers were synthesized from bio-based raw materials and functionalized with glutaric anhydride (GA). • Copolymers showed 100% shape recovery within 20 s and 94% restored storage modulus after 20 min of NIR light actuation. • Self-healing mechanism involved shape memory effects and transesterification induced by NIR photothermal effects.

Fabrication of multi-functional bio-based vitrimer and conductive composites via ugi four-component polymerization

To alleviate the pressure of fossil fuels on the environment, a green and efficient idea is proposed to prepare a new class of bio-based vitrimers by introducing dynamic disulfide bonds into the cross-linked network with bio-based raw materials 1,8-methane diamine and 10-undecenal through Ugi four-component reaction and highly efficient UV curing method. Among these bio-based vitrimers, B-MDU16 displays excellent self-healing ability, reprocessability and shape memory ability. Furthermore, conductive vitrimer composites based on bio-based vitrimers were fabricated by doping 5 wt% of MWCNTs, which also exhibited good electrical conductivity, photo-thermal properties, reprocessability and degradability as well as promising applications in the field of skin sensing. This study proposes to use Ugi-4CR to prepare bio-based vitrimer and composites, revitalizing this “ancient” organic reaction in the smart composites field and sustainable development strategy.

A Bio-based healable/renewable polyurethane elastomer derived from L-Tyrosine/Vanillin/Dimer acid

• A peculiar preparation method of bio-based self-healing/recyclable polyurethane: the raw materials come from cheap plant spices, dairy products and oils. The raw materials meet the requirements of sustainability. • A Combination of two different thermally reversible mechanism (deblocking/re-blocking of phenolic urethanes and imines metathesis) are introduced into the same system, thereby improving self-healing ability and recyclability. • The role of the non-toxic crosslinking agent triethanolamine (TEOA) was discussed. TEOA can promote bonding of phenolic urethanes. Even though HDI itself is low in activity, the lone pair of electrons provided by TEOA can guarantee the rapid reorganization of the cross-linked network. • Efficient self-healing/reprocessing reduces material waste. All the original properties of the material are preserved to the greatest extent. Bio-based, healable, and recyclable polyurethane materials conform to the sustainability of the polyurethane industry. By introducing dynamic covalent bonds, the cross-linked polyurethane can obtain the performance of network rearrangement, thereby realizing self-healing and reprocessing. In this work, a self-healing/renewable polyurethane based on bio-based vanillin and tyrosine was successfully synthesized solvent-freely and catalysts-freely. Due to two different thermal reversible mechanisms, metathesis of imines and deblocking/re-blocking of phenolic urethanes, the obtained PU has considerable self-healing efficiency and renewability. At 120 °C, the surface scratches almost completely disappear within 90 min, and the tensile strength can be restored to ∼ 95% within 2 h. After remolded for 5 times, the chemical structure, glass transition temperature, deblocking behavior, tensile strength, elongation at break and gel content didn’t change significantly. Both the environmental friendliness of bio-based raw materials and the renewability of the obtained polyurethane materials meet the requirements of sustainability.

Bio-based polyurethane/hindered phenol AO-80 composites for room temperature high damping properties

Elastomeric damping materials are essential in modern life. Apart from natural rubber, conventional elastomers are mostly based on petroleum-based sources. Moreover, elastomers exhibit excellent damping properties in the glass transition region, the glass transition temperature (Tg) of elastomers is lower than room temperature, resulting in poor damping properties at room temperature. However, because of limited and unsustainable petrochemical resources and environmental pollution, sustainable development and green environmental protection have become important principles in the design of damping materials, and most damping materials are used at room temperature. Therefore, designing bio-based materials with high damping properties at room temperature to replace conventional cross-linked rubber materials is crucial. Herein, we prepared bio-based millable polyurethane (bio-MPU)/hindered phenol 3,9-bis-{1,1-dimethyl-2[β-(3-tert-butyl-4-hydroxy-5-methylphenyl-)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro (Wang et al., 2016; Wang et al., 2016) [5,5]-undecane (AO-80) composites to overcome the challenge of sustainable development and high damping properties at room temperature. Bio-MPU samples with high Tg were synthesized from bio-based modified polylactic acid-based polyols, 4, 4′-diphenylmethane diisocyanate, and unsaturated chain extender 3-allyloxy-1, 2-propanediol. AO-80 was mixed with bio-MPU to further increase the Tgand enhance the damping properties of the bio-MPU/AO-80 composites. The properties of the bio-MPUs and bio-MPU/AO-80 composites were systematically evaluated. This study proposes a strategy to design high damping properties from bio-based raw materials and reduce our dependence on fossil resources.

Lanxess introduces Tepex thermoplastic composites from recycled/bio-based materials, halogen-free flame-retardant PBT compound, radar sensor materials, Modulast PUR modifier, large-scale EV-applications and sustainable colorants

On June 21, Lanxess reported that it is developing new Tepex thermoplastic composites that are being made starting from recycled or bio-based raw materials.

Techno-economic Assessment of Plastic Waste Management in Developing Countries: A Case Study for Sri Lanka

Worldwide, the plastic demand is increasing annually by 4%. Technologies can help save or reduce the material and energy consumption of the plastic material supply chain by applying proper waste management methods. However, comparative assessment is required to identify optimum material and energy recovery scenarios. Sri Lanka currently imports virgin plastic raw materials for different applications, which amounts to 300,000 tons per annum. Municipal solid waste generation of all solid waste is around 10,768 tons per day and collected by local authorities only 3,458 tons per day, in which over 50% of uncollected waste material, containing valuable plastics, goes to open dumps and the surrounding environment. At the end of life, plastic waste should not merely manage as energy recovery (such as waste to energy) however suitable technologies need to be applied to recycle the carbon for use as material feed stocks. Thermochemical and biochemical conversion technologies offer the option to utilize organic waste as chemical feedstock and subsequent polymers. The solution towards deriving synthetic materials allows a more closed cycle of materials and can help to reduce dependence on either fossil or bio-based raw materials. This study summarizes plastic waste management routes available and investigates how in the long-term they could be applied to enhance waste management in developing and emerging environments. Thus, the study aims to assess the technologies of plastic waste management in a Techno-economic framework in a typical developing country. Keywords: Plastic waste management, Material and energy recovery, Circular economy