This paper provides an overview of the recent progress in research and development dealing with polymers derived from plant oils. It highlights the widening interest in novel approaches to the synthesis, characterization, and properties of these materials from renewable resources and emphasizes their growing impact on sustainable macromolecular science and technology. The monomers used include unmodified triglycerides, their fatty acids or the corresponding esters, and chemically modified triglycerides and fatty acid esters. Comonomers include styrene, divinylbenzene, acrylics, furan derivatives, epoxides, etc. The synthetic pathways adopted for the preparation of these materials are very varied, going from traditional free radical and cationic polymerizations to polycondensation reactions, as well as metatheses and Diels–Alder syntheses. In addition to this general appraisal, the specific topic of the use of tung oil as a source of original polymers, copolymers, and (nano)composites is discussed in greater detail in terms of mechanisms, structures, properties, and possible applications.
Unsaturated vegetable oils with conjugated carbon–carbon double bonds, such as tung oil, can undergo free-radical polymerization, originating alternatives to petroleum-based materials. The introduction of fillers to vegetable oil-based polymer matrices results in composites with improved mechanical properties. In this work, thermosets were synthesized by the free-radical polymerization of a mixture of tung oil, divinylbenzene, and n-butyl methacrylate, and reinforced with bio-based fillers, namely Miscanthus, Pinus taeda (also known as southern pine), and algae (Microspora and Oedogonium) biomass. The effect of filler particle size on the composites’ properties was evaluated. Additionally, to develop a better interaction between the hydrophobic resin and the hydrophilic reinforcements, and improve the mechanical properties of the composites prepared, itaconic anhydride, a bio-based molecule derived from itaconic acid, was added to the resin. Thermogravimetric analysis (TGA) showed that the presence of itaconic anhydride improved the overall thermal stability of the composites. The storage modulus of the composites at room temperature, assessed by dynamic mechanical analysis (DMA), was increased by approximately 32% and 68%, for Miscanthus and southern pine composites, respectively, when itaconic acid was added to the resin. It was also observed that the glass transition temperatures were not significantly affected by the presence of itaconic acid. Scanning electron microscope (SEM) images indicated better matrix-reinforcement adhesion in the presence of itaconic anhydride.
Natural polymers, such as starch, and polymers derived from renewable resources, such as vegetable oils, have been considered as alternatives to petroleum-based plastics during recent decades, due to environmental concerns. Indeed, these materials can offer a variety of advantages, such as low cost, wide availability, carbon neutrality, elevated thermal stability, and easily tunable mechanical properties. However, some of these polymers alone exhibit poor mechanical properties, making them not suitable for some applications. Hence, the reinforcement of these bio-based polymers with other materials is often considered to overcome this challenge. In this work, thermosetting composites based on tung and linseed oil resins were prepared using starch as reinforcement. Analyses from Soxhlet extractions showed that the higher the concentration of tung oil in comparison to linseed oil in the resins, the lower the mass of unreacted material, leading to an optimum resin entirely based on tung oil. Dielectric analysis (DEA), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) indicated that the polymerization was completed in 3 h 20 min, at 140 °C, and that the composites were thermally stable until 270 °C. Finally, dynamic mechanical analysis (DMA) confirmed that the addition of starch to the resins increased the room temperature storage modulus (E’25) from 94 MPa to 893 MPa. Composites prepared with a resin formulation that did not contain a compatibilizer exhibited E’25 of 441 MPa. The composites investigated in this work are promising candidates for applications that require improved mechanical properties.
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