Vegetable Oil-based Polymers Research Articles

Recent advances in vegetable oil based fine chemicals and polymers

Vegetable oil as a kind of renewable resource has been considered as promising raw material to replace petrochemical resources. This article focuses on several highly reactive sites of triglycerides, including carbon-carbon double bonds, allyl groups, and ester groups. The vegetable oil-based platform monomers/polymers with different structures and functions are obtained via chemical modification such as epoxidation, ozone decomposition, hydroformylation, transesterification and thiolene. Vegetable oil-based chemicals mainly include polyols, biodiesel fuels, lubricants and plasticizers, and vegetable oil-based polymers mainly include inks, coatings and polyurethane foams. This paper summarizes and analyzes the review of vegetable oil-based chemicals and polymers in various industries, and puts forward the prospect for their future applications.

Bio-based conductive polyurethane composites derived from renewable castor oil with enhanced self-healing ability for flexible supercapacitors

To alleviate the pressure on the petrochemical industry and address environmental concerns, the utilization of polyurethane (PU) derived from castor oil (CO) (as an ester polyol replacement of petrochemical-based materials) has garnered significant attention in recent decades. Extending the service life of materials requires imparting self-healing properties to vegetable oil-based polymers, an aspect that has received limited attention in current studies. However, low self-healing efficiency still poses a significant challenge, and non-conductivity also remains an obstacle in current research, crucial for their application in electronic devices. In this work, we present the first series of electrically self-healing biopolymer composites constructed by incorporating carbon nanotube (CNT) networks into crosslinked castor oil-based polyurethane (BPU) through a simple curing process. These materials address the challenges mentioned above and exhibit improved mechanical, electrical, and self-healing capabilities compared to other bio-based self-healing materials. The resulting BPU/CNT composite demonstrated exceptional repeated self-healing capacity, restoring both mechanical properties and electrical performance even after experiencing severe mechanical damage. Notably, this composite served as a conductive substrate in flexible solid-state supercapacitor (FSSC) devices. Consequently, the FSSC derived from the composite conductive substrate achieved an impressive 92.4 % self-healing efficiency even after undergoing 7 cutting/healing cycles. The device remained virtually unchanged even after being bent at a 180° angle with a bending radius of 1.6 mm, indicating excellent repeatability and durability. The exceptional self-healing ability, with ∼98 % electrical recovery at 100 °C for 70 s and 93 % at 80 °C after 6 min, of these composites was attributed to the synergistic interactions of the dynamic exchange reactions of disulfide bonds and dense hydrogen bonds within the BPU matrix, which provide a reversible dynamic polymer network. The healing efficiency of these dynamic bonds was evaluated by adjusting the composition ratio of the long linear chain of pTHF in hybrid polyols of the crosslinked polymer network. Overall, this work highlights a series of green, simple, and highly efficient self-healing polymer composites derived from renewable castor oil, and it establishes an essential framework for future sustainable polymer composite design.

Synthesis and application of sustainable vegetable oil-based polymers in 3D printing

Chemical modifications of vegetable oil and their 3D printing applications are discussed. Acrylate resin compatibility with 3D printing methods are presented. 3D printed products using vegetable oil-derived materials, providing insights into future opportunities are explored.

Thermo-Responsive Shape-Memory Dual-Cured Polymers Based on Vegetable Oils.

The development of thermo-responsive shape-memory polymers has attracted attention due to their ability to undergo reversible deformations based on temperature changes. Vegetable oils are confirmed to be an excellent biorenewable source of starting materials for the synthesis of polymers. Therefore, the objective of this research was to synthesize thermo-responsive shape-memory polymers based on vegetable oils by using the dual-curing technique and obtaining polymers with tailorable properties. Acrylated epoxidized soybean oil and two epoxidized vegetable oils, linseed oil and camelina oil, were chosen for dual curing with m-xylylenediamine. Rheological tests were used to analyze the curing kinetics of systems undergoing radical photopolymerization, thermal cationic polymerization, and dual-curing processes. The rheological, mechanical, and thermal characteristics of the polymers were enhanced by the second curing stage. Dual-cured vegetable oil-based polymers had shape-memory properties with a recovery ratio of 100%, making them suitable for a variety of applications, including electronics, biomedical devices, and robotics.

High-performance castor oil-based polyurethane thermosets: Facile synthesis and properties

With the growing concern on the shortage of fossil resources and the environmental problems associated with their use, vegetable oils as renewable resources are important alternatives to fossil resources. Here, we used castor oil to synthesize 1-thioglycerol modified castor oil polyol with ultra-high hydroxyl value up to 463 mg KOH g−1 via a solvent-free thiol-olefin click reaction. The cross-linked polyurethanes were prepared from this polyol in a solvent-free and catalyst-free manner, and exhibited high tensile strength of ∼83 MPa and Tg of ∼124 °C, much higher than other reported vegetable oil-based polyurethanes. Besides, the obtained polyurethanes exhibited excellent coating and optical properties, much better than the polyurethane from the unmodified castor oil. This work provides a green and high-efficient method of synthesizing vegetable oil-based polyol with ultra-high hydroxyl value to construct high-performance polyurethanes, which will expand the application of vegetable oil-based polymers.

One-pot and solvent-free synthesis of castor oil-based polyurethane acrylate oligomers for UV-curable coatings applications

Due to the complex chemical modification, harsh synthesis conditions and imperative post-treatment, the industrial products of vegetable oil-based polymers are very rare. In this study, castor oil-based polyurethane acrylic resin (COPUA) was synthesizled by one-pot method from castor oil (CO), isophorone diisocyanate (IPDI), hydroxyethyl acrylate (HEA) and isobbornyl acrylate (IBOA). 1H NMR and FT-IR measurements were employed to verify the successful preparation of COPUA. Various UV curable films were prepared by mixing non-treated COPUA, photoinitiator (PI-1173), mono-functional active diluent hydroxyethyl methacrylate (HEMA) or bifunctional active diluent tripropylene glycol diacrylate (TPGDA). The mechanical performances of the cured films were studied. Besides, DMA and TGA analyses were used to determine the dynamic thermodynamic performances and the thermal stability of the cured films. As a result, the pure COPUA cured film exhibited excellent thermal stability, storage modulus (421 MPa at 25 °C), tensile strength (9.87 MPa) and high glass transition temperature (60.3 °C). The cross-linking density of films improved with increasing the content of active diluent, resulting in excellent overall performances. In addition, all films possessed excellent hardness, adhesion, solvent resistance and flexibility. In this study, it provides a green and environmentally friendly strategy for the synthesis of vegetable oil-based polymers, reducing our chemical dependence on petrochemical energy.

Bio-Based Composites with Enhanced Matrix-Reinforcement Interactions from the Polymerization of α-Eleostearic Acid

Vegetable oil-based composites have been proposed as interesting bio-based materials in the recent past. The carbon–carbon double bonds in unsaturated vegetable oils are ideal reactive sites for free radical polymerization. Without the presence of a reinforcement, typical vegetable oil-based polymers cannot achieve competitive thermo-mechanical properties. Compatibilizers have been utilized to enhance the adhesion between resin and reinforcement. This work discusses the antagonist implications of polarity and crosslink density of an unprecedented polar α-eleostearic acid-based resin reinforced with α-cellulose, eliminating the need of a compatibilizer. It is shown that the polar regions of α-eleostearic acid can interact directly with the polar reinforcement. The successful isolation of α-eleostearic acid from tung oil was verified via GC-MS, 1H NMR, Raman, and FT-IR spectroscopies. The optimal cure schedule for the resin was determined by DSC and DEA. The composites’ thermo-mechanical properties were assessed by TGA, DSC, and DMA.

(Epoxidized castor oil – citric acid) copolyester as a candidate polymer for biomedical applications

Vegetable oil-based polymers are attractive regarding environmental concerns to produce polymers through an environmentally friendly process to noble applications, as the biomedical ones. Epoxidized vegetable oils can be used as a comonomer; however, its polymerization processes commonly use toxic raw materials which do not enable its use for biomedical application. In this paper is presented the synthesis procedure for a copolyester derived from epoxidized castor oil and citric acid, using a green route approach, with non-toxic solvents and reagents, without the use of catalysts or initiators, and no production of hazardous residues. Fourier transform infrared spectroscopy presented the infrared absorption bands of the copolyester. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) revealed good thermal stability (190 °C) and an elastomeric behavior (Tg < 5 °C). Absorption capacity and gel fraction analysis indirectly showed the influence of the citric acid in the degree of reticulation. The cell colonization viability of the copolyester surface was evaluated by scanning electron microscopy (SEM), and the direct toxicity assessment investigated its non-toxic response. These results suggest the potential for biomedical application of the (epoxidized castor oil - citric acid) copolyester.

Preparation and characterization of polymeric dispersants based on vegetable oils for printing ink application

In this work, a novel vegetable oil-based polymers were prepared by epoxidation of soybean oil (SBO) and castor oil (CO) followed by ring opening reaction of epoxidized oil with polyether amine and poly propylene glycol. The prepared polymers were characterized by FTIR and GPC. The properties of vegetable oils and epoxidized vegetable oil (EVO) were studied. The prepared polymers were employed as novel polymeric dispersants for pigment dispersion in solvent based printing ink application. The mechanical and optical properties of prepared ink were studied. The net technical properties of the new ink formulations are relatively comparable to the prepared printing ink from standard polymeric dispersant. The polymeric dispersant 2 (PD2) and polymeric dispersant 4 (PD4) gave the best optical and mechanical properties among the prepared polymers.

A Review of Vegetable Oil-Based Polymers: Synthesis and Applications

The reviewed work addressed the shift in focus from conventional polymers to bio-based and renewable polymers. The environmental attributes of the renewable polymers make them preferred choice of matrix. The properties of the matrices from renewable origin could compete in high end applications. The composition of the fatty acids in plant seed oil was discussed and the determination of the level of unsaturation used the iodine value. This review also extensively discussed the values of various fatty acid components present in the oils. Areas of application of the thermosetting polymers obtained from plant seed oils were also discussed.

Evaluation of Castor Oil Polyurethane Reinforced with Lignin and Cellulose from Sugarcane Straw

The search for materials from renewable sources such as vegetable oil-based polymers, polyurethane based on castor oil represents a promising alternative in researches. Using castor oil polyurethane as matrix for composites reinforced with lignin and cellulose from sugarcane straw is in tune with economical and environmental interests. The objective of this work was the evaluation of the changes on the structure and thermal behavior of castor oil polyurethane composites reinforced with lignin and cellulose from sugarcane straw. The cellulose and lignin were extracted from the straw by acid hydrolysis and then they were milled. For the production of the polyurethane, the mass reason between polyol (castor oil) and diisocyanate was 1.5:1.0. Reinforcement of the matrix was done changing the concentration of cellulose and lignin. SEM micrographs of fractured surfaces of the obtained composites and thermal analysis (TGA) were done. No lignin could be seen in SEM micrographs, what suggests a blend material behavior. The addition of cellulose fibers (30%) and lignin (40%) to the polyurethane matrix has caused an increase of the stiffness in the resulting composite when compared with the pure matrix. Above these rates, stiffness decreases. The presence of lignin or cellulose fibers in polyurethane matrix seems to increase mechanical properties of the composite, and also introduce better thermal stability than the pure matrix. Its presence might also bring other significant synergetic properties to the final composite, what has currently been studied. At the same time, the blend behavior of Polyurethane-Lignin composites has been investigated.

Vegetable oil-based polymeric materials: synthesis, properties, and applications

The use of vegetable oils as renewable raw materials for the synthesis of various monomers and polymeric materials is reviewed. Vegetable oils are generally considered to be the most important class of renewable resources, because of their ready availability and numerous applications. Recently, a variety of vegetable oil-based polymers have been prepared by free radical, cationic, olefin metathesis, and condensation polymerization. The polymers obtained display a wide range of thermophysical and mechanical properties from soft and flexible rubbers to hard and rigid plastics, which show promise as alternatives to petroleum-based plastics.

Vegetable Oil Based-Polymers Reinforced with Wood Flour

Liquid polymer precursors were synthesized from vegetable oils to be utilized in the preparation of oil based-resins to be later reinforced with a filler also obtained from natural sources. In this work, an unsaturated oil, tung oil, produced in the region was selected as raw material. The vegetable oil was chemically functionalized to obtain a polyol to be further used in polyurethane formulations. Different analysis techniques were used to investigate the hydroxyl content in the modified oil. Oil based composites containing pine wood flour as filler were prepared and mechanically tested.

Biodegradation Behavior of Some Vegetable Oil-Based Polymers

The potential biodegradability of several vegetable oil-based polymers was assessed by respirometry in soil for 60-100 days at temperatures of 30-58°C. Films of soybean oil and linseed oil which were oxidatively polymerized (Co catalyst) on a kraft paper support were 90%-100% mineralized to CO2 after 70 days at 30°C. Mineralization of polymerized tung oil to CO2 was much slower than soy or linseed oils. Mineralization of epoxy resins made from epoxidized soybean oil (ESO) and aliphatic dicarboxylic acids was rapid while mineralization of similar resins made with a triacid (citric) was slower. There was no significant degradation of polyamine/ESO resins after 100 days at 58°C. Mineralization of the available carbon in vegetable oil polyurethanes and cationically polymerized ESO was less than 7.5% after 70 days at 30°C and 25 days at 55°C compared to 100% for soybean oil. From these results, it appears that triglycerides highly cross-linked with non-degradable linkages are not biodegradable to a significant extent while triglycerides cross-linked with hydrolysable bonds such as esters remain biodegradable.