Novel oil-based epoxy acrylate (EA)-like prepolymers were synthesized via the ring-opening reaction of epoxidized plant oils with a new unsaturated carboxyl acid precursor (MAAMA) synthesized by reacting maleic anhydride (MA) with methallyl alcohol (MAA). Since the employed epoxidized oils including epoxidized soybean oil (ESO), epoxidized rubber seed oil (ERSO), and epoxidized wilsoniana seed oil (EWSO) possessed epoxy values of 7.34–4.38%, the obtained epoxy acrylate (EA)-like prepolymers (MMESO, MMERSO, and MMEWSO) indicated a C=C functionality of 7.81–4.40 per triglyceride. Furthermore, effects of the C=C functionality and the addition of hydroxyethyl methacrylate (HEMA) diluent on the ultimate properties of the resulting UV-cured EA-like materials were investigated and compared with those of commercially available acrylated ESO (AESO) resins. As the C=C functionality increased, the storage modulus at 25 °C (E’25), glass transition temperature (Tg), 5% weight–loss temperature (T5), tensile strength and modulus (σ and E), and hardness of the coating for both the pure EA and EA/HEMA resins increased significantly as well. These properties indicated similar trends when comparing the EA materials with 30% of HEMA with those pure EA materials. Specially, although ERSO had a clearly lower epoxy value that ESO, both the UV-cured pure MMERSO and MMERSO/HEMA materials showed much better E’25, Tg, σ, and E than their AESO counterparts, indicating that the MAAMA modification of epoxidized plant oils was much more effective than the modification of acrylic acid to achieve high-performance oil-based epoxy acrylate resins.
Novel UV-curable polyurethane acrylate (PUA) resins were developed from rubber seed oil (RSO). Firstly, hydroxylated rubber seed oil (HRSO) was prepared via an alcoholysis reaction of RSO with glycerol, and then HRSO was reacted with isophorone diisocyanate (IPDI) and hydroxyethyl acrylate (HEA) to produce the RSO-based PUA (RSO-PUA) oligomer. FT-IR and 1H NMR spectra collectively revealed that the obtained RSO-PUA was successfully synthesized, and the calculated C=C functionality of oligomer was 2.27 per fatty acid. Subsequently, a series of UV-curable resins were prepared and their ultimate properties, as well as UV-curing kinetics, were investigated. Notably, the UV-cured materials with 40% trimethylolpropane triacrylate (TMPTA) displayed a tensile strength of 11.7 MPa, an adhesion of 2 grade, a pencil hardness of 3H, a flexibility of 2 mm, and a glass transition temperature up to 109.4 °C. Finally, the optimal resin was used for digital light processing (DLP) 3D printing. The critical exposure energy of RSO-PUA (15.20 mJ/cm2) was lower than a commercial resin. In general, this work offered a simple method to prepare woody plant oil-based high-performance PUA resins that could be applied in the 3D printing industry.
Plastic pollution endangers all natural ecosystems and living creatures on earth. Excessive reliance on plastic products and excessive production of plastic packaging are extremely dangerous for humans because plastic waste has polluted almost the entire world, whether it is in the sea or on the land. This review introduces the examination of pollution brought by non-degradable plastics, the classification and application of degradable materials, and the current situation and strategy to address plastic pollution and plastic degradation by insects, which mainly include Galleria mellonella, Zophobas atratus, Tenebrio molitor, and other insects. The efficiency of plastic degradation by insects, biodegradation mechanism of plastic waste, and the structure and composition of degradable products are reviewed. The development direction of degradable plastics in the future and plastic degradation by insects are prospected. This review provides effective ways to solve plastic pollution.
New tung oil (TO)-based, unsaturated, co-ester (Co-UE) macromonomers bearing steric hindrance were synthesized by modifying a TO-based maleate (TOPERMA) monomer with an anhydride structure with hydroxyethyl methacrylate (HEMA) and methallyl alcohol (MAA), respectively. The obtained Co-UE monomers (TOPERMA-HEMA and TOPERMA-MAA) were then characterized by 1H NMR and gel permeation chromatography (GPC). For comparison, hydroxyethyl acrylate (HEA)-modified TOPERMA (TOPERMA-HEA) was also synthesized and characterized. Subsequently, the obtained Co-UEs were thermally cured with styrene, and the ultimate properties of the resulting materials were studied. It was found that by introducing the structure of steric hindrance into the TO-based Co-UE monomer, the tensile strength and Young’s modulus of the resulting materials were improved. Furthermore, by reducing the length of the flexible chain in the Co-UE monomer, the tensile strength, Young’s modulus, and glass transition temperature (Tg) of the resultant materials were also improved. The TOPERMA-MAA resin gave the best performance in these TO-based Co-UE resins, which showed a tensile strength of 32.2 MPa, Young’s modulus of 2.38 GPa, and Tg of 130.3 °C. The developed ecofriendly materials show promise in structural plastic applications.
Vegetable oils have been widely used in food, surfactants, lubricants, biodiesel, coatings, and other fields due to their advantages such as renewable, abundant, suitable for further processing, and biodegradable. On the other hand, microwave technology has attracted extensive attention in organic and polymeric chemistry because the technology can greatly shorten the reaction time, improve the yield of products, reduce side reactions, etc. This paper summarized recent advances on the microwave-assisted modification of vegetable oils or their derivatives, such as esterification of free fatty acids, transesterification of triglycerides, epoxidation, and polymerization.
Lignin and cellulose derivatives have vast potential to be applied in polymer materials. The preparation of cellulose and lignin derivatives through esterification modification is an important method to endow cellulose and lignin with good reactivity, processability and functionality. In this study, ethyl cellulose and lignin are modified via esterification to prepare olefin−functionalized ethyl cellulose and lignin, which are further used to prepare cellulose and lignin cross−linker polymers via thiol–ene click chemistry. The results show that the olefin group concentration in olefin−functionalized ethyl cellulose and lignin reached 2.8096 mmol/g and 3.7000 mmol/g. The tensile stress at break of the cellulose cross−linked polymers reached 23.59 MPa. The gradual enhancement in mechanical properties is positively correlated with the olefin group concentration. The existence of ester groups in the cross−linked polymers and degradation products makes them more thermally stable. In addition, the microstructure and pyrolysis gas composition are also investigated in this paper. This research is of vast significance to the chemical modification and practical application of lignin and cellulose.