Epoxidized Soybean Oil Research Articles

Study on the physicochemical properties of human hair fiber‐reinforced modified epoxidized soybean oil‐based composites

This paper investigates the effect of fiber surface treatment on various properties of hair fiber reinforced composites. Human hair fiber reinforced modified epoxidized soybean oil based composites were prepared by compression molding technique. Acid treatment of hair fibers was carried out by using three different concentrations of HCl solution (0.25%, 0.75%, and 1%, respectively) in order to achieve improvement in adhesion between the fiber and the matrix. Epoxidized soybean oil was modified using methacrylic acid and methacrylic anhydride to form methacrylic anhydride modified epoxidized soybean oil. Rosin acid derivative (a rigid comonomer) was prepared and used as a crosslinker. Fourier‐transform infrared spectroscopy was carried out to study the interaction among the components of the composites. Various properties, namely, mechanical, thermal, flame resistance, and chemical resistance were checked. Scanning electron microscopy of the fractured surface of the composites was carried out to examine the morphologies. Hair fibers treated with 0.75% of HCl showed maximum improvement in all the properties and could be employed as reinforcement in various composites to be used for structural applications.

Sustainable Packaging with Waterborne Acrylated Epoxidized Soybean Oil

Sustainable Packaging with Waterborne Acrylated Epoxidized Soybean Oil

Biobased and biodegradable imine vitrimers from epoxidized soybean oil as packaging

AbstractA flexible and stretchable vitrimer was synthesized using exclusively biobased building blocks and following green chemistry principles. Epoxidized soybean oil (ESO), vanillin, the biobased diamine, Priamine®, and oleic acid were used to create a material that can replace fossil‐derived, non‐biodegradable packaging. Vanillin and Priamine® were used to develop a crosslinker that could react with the epoxide groups of ESO without the need for solvents, with a catalyst‐free synthesis that does not generate any waste or byproducts. Oleic acid was incorporated, to tune the properties of the final material, since it can react with ESO and control the crosslink density. The vitrimers produced in this work showed excellent reprocessability and recyclability. They possess the ability to be molded, and they can also strongly adhere on surfaces. Moreover, they exhibited oxygen and water vapor barrier comparable to low density polyethylene, while showing very low migration into food simulant, which position them as a promising material for flexible food and general packaging market. The vitrimers showed also the capability of biodegradation in seawater, providing a safe end of life in case of mismanagement.

In vitro evaluation of bone cell response to novel 3D-printable nanocomposite biomaterials for bone reconstruction.

Critically-sized segmental bone defects represent significant challenges requiring grafts for reconstruction. 3D-printed synthetic bone grafts are viable alternatives to structural allografts if engineered to provide appropriate mechanical performance and osteoblast/osteoclast cell responses. Novel 3D-printable nanocomposites containing acrylated epoxidized soybean oil (AESO) or methacrylated AESO (mAESO), polyethylene glycol diacrylate, and nanohydroxyapatite (nHA) were produced using masked stereolithography. The effects of volume fraction of nHA and methacrylation of AESO on interactions of differentiated MC3T3-E1 osteoblast (dMC3T3-OB) and differentiated RAW264.7 osteoclast cells with 3D-printed nanocomposites were evaluated in vitro and compared with a control biomaterial, hydroxyapatite (HA). Higher nHA content and methacrylation significantly improved the mechanical properties. All nanocomposites supported dMC3T3-OB cells' adhesion and proliferation. Higher amounts of nHA enhanced cell adhesion and proliferation. mAESO in the nanocomposites resulted in greater adhesion, proliferation, and activity at day 7 compared with AESO nanocomposites. Excellent osteoclast-like cells survival, defined actin rings, and large multinucleated cells were only observed on the high nHA fraction (30%) mAESO nanocomposite and the HA control. Thus, mAESO-based nanocomposites containing higher amounts of nHA have better interactions with osteoblast-like and osteoclast-like cells, comparable with HA controls, making them a potential future alternative graft material for bone defect repair.

The influence of palm oil-derived plasticizers and lubricants on the rheological and mechanical properties of styrene butadiene rubber

Researchers have recently focused on green processing aids made from plants and vegetables to avoid the high concentration of polycyclic aromatic hydrocarbons (PAHs) from petroleum-based processing oils, which is hazardous to human health. This paper focuses on the effect of lubricants and plasticisers produced from palm oil on the rheological, mechanical and thermal aging properties of styrene-butadiene rubber (SBR). These lubricants and plasticisers are known as glycerol trioleate (GTO), n-butyl stearate (NBS), ethylene bis-steramide (EBS), ethylene bis-oleamide (EBO), pentaerythritol tetrastearate (PETS) and stearyl stearate. The abrasion performance, visual inspection appearance, and cure characteristics of the lubricants and plasticisers on SBR were examined and compared to processing oil-treated distillate aromatic extract (TDAE), paraffin wax, microcrystalline wax, polyethylene (PE) wax, epoxidised soybean oil (ESBO), and stearic acid. It discovered that rubber compounds based on GTO, stearic acid, and EBS exhibited better abrasion resistance and cure properties than rubber compounds based on processing oil. These samples were selected and subjected to mechanical properties, thermal aging effects analysis and comparison with processing oil. Tensile strength shows that SBR with EBS (22.49 MPa) and EBS with GTO (EBS/GTO; 21.25 MPa) are closely similar to SBR compounds with processing oil (21.02 MPa). The findings imply that EBS and EBS/GTO, green plasticisers and lubricants, are viable alternatives to petroleum-based processing oils while being cost-effective for tire production.

Outstanding performance of flower-like NiO nanostructures in epoxied soybean oil-based polyurethane nanocomposite coatings: Investigation of anticorrosion and antibacterial properties

Nowadays, nanocomposite coatings have gained much attention from both academic and industrial aspects mainly because of the outstanding properties which they can offer simultaneously. Specifically, anti-corrosion properties can make them one of the best choices to solve destructive corrosion problems. Nickel oxide (NiO) nanoparticles have been synthesized to create these outstanding properties in vegetable oil-based polyurethane coatings. To this end, epoxidized soyabean oil was utilized to synthesize polyol and produce polyurethane coatings, and NiO nanoparticles were incorporated into the obtained coatings. The obtained coatings were evaluated through the FTIR, H NMR, and FESEM techniques and their performance in terms of water uptake, anticorrosion and antibacterial properties were investigated. The obtained results clearly showed that the presence of NiO nanoparticles has had an undeniable effect on the performance of the coating in protecting mild steel substrate against corrosion. Moreover, using these nanoparticles has created remarkable antibacterial properties in the coating besides improved mechanical performance compared to pure polyurethane coating.

Improving the 3D Printability and Mechanical Performance of Biorenewable Soybean Oil-Based Photocurable Resins.

The general requirement of replacing petroleum-derived plastics with renewable resources is particularly challenging for new technologies such as the additive manufacturing of photocurable resins. In this work, the influence of mono- and bifunctional reactive diluents on the printability and performance of resins based on acrylated epoxidized soybean oil (AESO) was explored. Polyethylene glycol di(meth)acrylates of different molecular weights were selected as diluents based on the viscosity and mechanical properties of their binary mixtures with AESO. Ternary mixtures containing 60% AESO, polyethylene glycol diacrylate (PEGDA) and polyethyleneglycol dimethacrylate (PEG200DMA) further improved the mechanical properties, water resistance and printability of the resin. Specifically, the terpolymer AESO/PEG575/PEG200DMA 60/20/20 (wt.%) improved the modulus (16% increase), tensile strength (63% increase) and %deformation at the break (21% increase), with respect to pure AESO. The enhancement of the printability provided by the reactive diluents was proven by Jacobs working curves and the improved accuracy of printed patterns. The proposed formulation, with a biorenewable carbon content of 67%, can be used as the matrix of innovative resins with unrestricted applicability in the electronics and biomedical fields. However, much effort must be done to increase the array of bio-based raw materials.

Photopolymerization of Limonene Dioxide and Vegetable Oils as Biobased 3D-Printing Stereolithographic Formulation.

Epoxidized vegetable oils and limonene dioxide, a bis-epoxide derived from the terpene limonene, are photo-copolymerized to yield highly crosslinked networks with high conversion of all epoxide groups at ambient temperature. However, the slow polymerization of such biobased formulation polymerizes is not compatible for a use in a commercial SLA 3D printer. Adding an acrylated epoxidized vegetable oil to the bis-epoxide leads to a decrease of curing time and an increase in LDO conversion to polymer. For example, in a 60:40 wt:wt mixture of LDO and epoxidized soybean oil, the conversions of both exocyclic and endocyclic epoxide groups of LDO are ≥95%. These formulations were successfully used in SLA 3D printers, leading to generation of hard and dry complex objects using biobased formulations.

In English

Natural fibre reinforced polymer composites nowadays are considered to be attractive cheap, safe and eco-friendly materials. The main problem of such composites related to the hydrophilicity of plant fibres may be successfully solved by chemical modification of their surface. However, some characteristics of the materials may be suppressed after this procedure. Therefore, the aim of the research is to find out the impact of chemical modification of filler on thermooxidative stability, tensile and flexural strength, as well as on biodegradability of polymer composites. The novelty of this work is in the examining new materials on the basis of Si-containing epoxyurethanes and chemically treated hemp woody core (HWC). Woody core that is the side product of hemp industry requiring its apropriate utilization was exposed to mercerization with sodium hydroxide solution and to further functionalization with epoxidized soybean oil (ESO) or 3-aminopropyltriethoxysilane (APS). Raw and surface treated HWC was used as reinforcement for two types of organic-inorganic epoxyurethane matrices made from sodium silicate, polyurethane prepolymer based on polyisocyanate and castor oil, and either diglycidyl ether of bisphenol-A (DGEBA) or ESO as epoxy component. Functionalization of HWC led to better mechanical properties of composites. Compared to the corresponding materials including untreated filler, maximum increase in flexural strength (26 %) was observed for the samples with ESO-containing epoxyurethane and silanized HWC, while maximum increase in tensile strength (53 %) was revealed for the ones with DGEBA-containing epoxyurethane and oil treated HWC. Thermooxidative stability was also higher for composites reinforced with functionalized HWC. The specimens with APS-treated HWC performed the best at thermal decomposition. The values of their T50% were up to 68 °C more than those for composites with unmodified filler. At the same time, the samples based on APS- or ESO-treated HWC were the most resistant to biodegradation, which may be concluded from their smallest weight loss during soil burial test.

Biobased antibacterial underwater adhesive based on in situ siliconization crosslinking

Underwater adhesives have gained significant attention because of their bright application prospects in industry and biomedical fields. However, exploiting a facial strategy to prepare an antibacterial biobased adhesive with admirable underwater adhesion remains a challenge. In this study, a novel biobased antibacterial underwater adhesive was developed based on the biomimetic siliconization strategy. Epoxidized soybean oil (ESO) was decorated with (3-aminopropyl) triethoxysilane through reactions between the amino and epoxy groups to prepare silanized soybean oil (ESO-Si). Under hydrolysis, tannic acid (TA) served as crosslinking cores to induce Si–O–C bonding with ESO-Si to improve the cohesion of ESO-Si. The TA cross-linked silicification system endowed ESO-Si/TA with admirable underwater adhesion on various substrate surfaces. Benefiting from the antibacterial effect of TA, the prepared ESO-Si/TA underwater adhesive also exhibited a good antibacterial property. A novel method of utilizing water-induced bio-siliconization system to develop high-performance underwater adhesive was proposed, offering a new idea for the preparation of new biobased underwater adhesives.

Synthesis and Performance of Biobased Polyurethane Adhesives from Epoxidized Soybean Oil and Isosorbide

Synthesis and Performance of Biobased Polyurethane Adhesives from Epoxidized Soybean Oil and Isosorbide

Biomass carboxylic acid modified hydrotalcites for improving the mechanical strength and recyclability of 100 % biobased carbon content epoxy soybean oil based vitrimers

To realize the demand of sustainable development in materials industry, vitrimers deriving from epoxidized soybean oil (ESO) have received considerable attention because of their environmentally friendly and renewable. However, they suffer from poor mechanical strength and non-reprocessability, which confine their application. Herein, a facile design of 100 % bio-based carbon contents vitrimers incorporating ESO and citric acid modified layered double hydroxides (CA-LDHs) was proposed, which showing good mechanical properties and accelerated stress relaxation. Optimal performances of vitrimers with best tensile strength, curing and repairing efficiency were obtained at 20 wt% CA-LDHs loading. The tensile strength of 20EC-CLE increased by 233 % compared with pure EC-E due to the reinforcing effect of CA-LDHs and the increased cross-linking density. Benefit from the abundant Al3+ catalytic sites and large contact areas of the CA-LDHs lamella, the vitrimers showed an excellent curing and 82 % reprocessing efficiency. Interestingly, the precursor of the vitrimers was used as an adhesive layer for polyvinyl chloride (PVC) leather and provided 3.4 ± 0.4 N/cm peel strength and bonding reproducibility.

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.

The effect of triglycerol diacrylate on the printability and properties of UV curable, bio-based nanohydroxyapatite composites

3D printable biopolymer nanocomposites composed of hydroxyapatite nanoparticles and functionalized plant-based monomers demonstrate potential as sustainable and structural biomaterials. To increase this potential, their printability and performance must be improved. For extrusion-based 3D printing, such as Direct Ink Writing (DIW), printability is important for print fidelity. In this work, triglycerol diacrylate (TGDA) was added to an acrylated epoxidized soybean oil:polyethylene glycol diacrylate resin to increase hydrogen bonding. Greater hydrogen bonding was hypothesized to improve printability by increasing the ink's shear yield strength, and therefore shape holding after deposition. The effects of this additive on material and mechanical properties were quantified. Increased hydrogen bonding due to TGDA content increased the ink's shear yield stress and viscosity by 916% and 27.6%, respectively. This resulted in improved printability, with best performance at 3 vol% TGDA. This composition achieved an ultimate tensile strength (UTS) of 32.4 ± 2.1 MPa and elastic modulus of 1.15 ± 0.21 GPa. These were increased from the 0 vol% TGDA composite, which had an UTS of 24.8 ± 1.8 MPa and a modulus of 0.88 ± 0.06 GPa. This study demonstrates the development of bio-based additive manufacturing feedstocks for potential uses in sustainable manufacturing, rapid prototyping, and biomaterial applications.

Curing and degradation kinetics of crosslinked epoxidized soybean oil with isosorbide-based curing agent

This work explores the synthesis of the isosorbide-based curing agent with methyltetrahydrophthalic anhydride (MTHPA). Synthesized for the first time, the isosorbide methylphthalate acid (IMPA) and its effects on the crosslinking of epoxidized soybean oil (ESO) are investigated. The curing and degradation kinetics of the synthesized compounds were investigated for molar ratios 1:1, 1:0.50 and 1:0.25 for ESO/IMPA and 1:1 ESO/MTHPA. ESO/IMPA 1:0.50 had the lowest cure activation energies during the highest cure conversion range, between 10% and 55%, and the highest degradation activation energies during the 30 and 60% conversion. The Friedman and Vyazovkin isoconversional models provided R2 > 0.99 for cure, except for the ESO/MTHPA composition, presenting a lower R2. In degradation kinetics, the Kissinger-Akahira-Sunose (KAS) and Ozawa-Flynn-Wall (OFW) kinetic models presented R2 > 0.99, while the degradation mechanisms were adequately adjusted with Avrami-Erofeev (An) and autocatalytic (n,m)th order (Cnm) during the first and second degradation step. Microstructural analyzes and deeper investigations into the degradation mechanisms in the solid state indicated that in the ESO/IMPA and ESO/MTHPA compounds the processes are controlled by diffusion.

Soybean-Based Bio-Adhesives: Role of Diamine on the Adhesive Properties.

One possible approach to achieving sustainable development in the materials sector is to produce polymers from plant oils (POs), which are renewable and environmentally beneficial. Polymers with a high concentration of functional groups can be used as cross-linking agents to enhance the properties of epoxidized POs (epoxidation of plant oil)-based polymers. In this work, a unique resin with novel properties and potential uses was produced by cross-linking epoxidized soybean oil (ESO) with branched and flexible polyamines by ring-opening and amidation polymerizations. This approach is straightforward and ecologically benign. After curing, melamine pentane diamine (MPD) polymer maintained its position as the strongest structural adhesive among the synthesized resins, with a bonding strength of almost 2000 kPa for stainless steel; irrespective of the temperature, stainless steel consistently outperforms melamine ethylene diamine-ESO resin in strength comparisons. At 100 °C, stainless steel has a lap shear strength of about 300 kPa, which is far higher than copper and aluminum; at 180 °C, this value increases by another 750 kPa. While MPD-ESO resin has a shear strength of 1996 kPa at 180 °C, melamine butane diamine-ESO resin has a shear strength of only 1220 kPa.

Low-Shrinkage and Degradable UV Imprint Lithography Based on Biomass-Derived Epoxidized Soybean Oil and Cardanol

Low-Shrinkage and Degradable UV Imprint Lithography Based on Biomass-Derived Epoxidized Soybean Oil and Cardanol

Effects of synthesis temperature on structures and properties of epoxidized soybean oil oligomers and starch‐based bioplastics

AbstractThe work investigated the synthesis of the oligomers with citric acid (CA) and epoxidized soybean oils (ESO) at various temperatures and the effects of the oligomers on the structures and properties of starch‐based bioplastics. CA was bonded effectively onto ESO via ring‐opening polymerization at 90°C as confirmed by the results of Fourier‐transform infrared spectroscopy, thermogravimetric analysis, and carboxylic group contents of CA‐ESO oligomers (CESO). The oligomers exhibited higher thermal stability than ESO. Regarding starch‐based bioplastics, CESO disrupted the hydrogen bonding interaction within starch molecules and formed the esterification reaction with starch. The bioplastics containing CESO exhibited remarkably higher structural homogeneity and opacity as the synthesis temperatures of CESO increased. However, the thermal properties of the bioplastics with various CESO reduced, which might be due to the decomposition of starch by CESO. The films containing CESO also exhibited lower tensile strength than the film with ESO, which might be related to the decomposition, crosslinking, and plasticization effects of CESO on starch. The bioplastics with CESO exhibited lower degradation due to a more intense interaction of CESO and starch. The study demonstrated the potential of CA as an interfacial linker of starch/ESO‐based bioplastics by adjusting the synthetic temperatures of CESO.

Thermo-responsive properties of self-healable thermosets based on epoxidized soybean oil

In this work, epoxidized soybean oil (ESO) based thermosetting materials cured with citric acid (CA) and modified with low molecular weight 4′-(hexyloxy)-4-biphenyl-carbonitrile (HOBC) nematic liquid crystal were synthesised and characterized. In order to find adequate curing conditions, the non-isothermal differential scanning calorimetry (DSC) was performed and the formation of thermosetting systems was confirmed by Fourier transform infrared spectroscopy (FTIR). As expected, the addition of HOBC nematic liquid crystal affected strongly the curing reaction of ESO/CA mixture. Thus, HOBC liquid crystal phase was partially miscible with ESO for low HOBC content, while its phase separation from ESO/CA matrix was detected for more than 20 wt% HOBC content. Thermal behaviour and thermal stability depend strongly on HOBC content leading, for high HOBC content, to thermosetting systems with nematic-isotropic transition characteristic for HOBC liquid crystal. Optical properties of HOBC-ESO/CA thermosetting systems confirmed the capability of HOBC liquid crystal phase to switch reversibly photoluminescence properties applying temperature. Moreover, an improvement of the thermo-responsive behaviour (shorter switching time and sharper switching temperature range) can be obtained modifying developed system with a small amount of poly(ε-caprolactone-b-lactide) (CLLA) block copolymer. Designed HOBC-ESO/CA thermosetting systems maintained self-healing properties attributed to ESO/CA thermosetting system. Thus, HOBC-ESO/CA thermosetting system modified with CLLA block copolymer was able to reach an interface width reduction of 98% after 2 h of self-healing process at 160 °C. This research work allowed to develop thermosetting systems, which combine self-healing properties of ESO/CA matrix with thermo-responsive properties of HOBC liquid crystal phase. Designed thermosetting materials can broad potential applications of ESO/CA thermosetting system.

High-performance pervious concrete using cost-effective modified vinyl ester as binder

Pervious concrete has a unique open-skeleton structure and high permeability, which effectively control water runoff, mitigate urban heat island effects, and reduce traffic noise in urban constructions. However, low strength, easy granulation, and poor durability often limit its application in pavement engineering. As a polymer binder, vinyl ester (VE) resin has high strength, wear resistance, durability, and corrosion resistance, which can remedy the shortage of pervious concrete. In this work, by optimizing the aggregate gradation and curing temperature, high-performance pervious concrete using VE resin as binder was fabricated. To further improve the performance of VE binder, renewable acrylated epoxidized soybean oil (AESO) and diphenylmethane diisocyanate (MDI) were used to increase the crosslinking degree of the resin and the durability of pervious concrete. When using 15% AESO and 10% MDI based on the weight of VE, the pervious concrete achieved an enhanced flexural strength of up to 7.72 MPa. A significant improvement was achieved by incorporating 50 wt% solid wastes copper slag into the pervious concrete, the compressive strength and flexural strength reached 37.72 MPa and 7.53 MPa, respectively. The permeability coefficient of the permeable concrete was 2.64 mm/s, and the connected porosity was 11.33%, which are higher than the requirements of China national standard. The satisfactory durability of pervious concrete was also verified through freeze-thaw, abrasion, and aging tests. This work offers a viable strategy for cost-efficient and sustainable high-performance pervious concrete, providing insights into the utilization of renewable feedstocks and solid wastes in civil materials.