Zhao Zicheng, Wu Hong, Liu Xudong, Kang Desheng, Xiao Zhihong, Lin Qiquan, Zhang Aihua
College of Mechanical Engineering and Mechanics, Xiangtan University Xiangtan 411105 China
State Key Laboratory of Utilization of Woody Oil Resource, Hunan Academy of Forestry Changsha 410000 China
RSC Adv. 2022 Aug 10;12(34):22119-22130. doi: 10.1039/d2ra03182e. eCollection 2022 Aug 4.
Using tung oil as the raw material, a new bio-based prepolymer was successfully synthesized by reacting with acrylic-modified rosin (β-acryloyl nutrient ethyl) ester (ARA)/acrylic-2-hydroxyethyl ester (HEA) followed by the use of the above composite material as the matrix and then reacting with the active diluent (2-HEMA, TPGDA) and the photoinitiator TPO and Irgacure1173 to successfully synthesize a new type of bio-based prepolymer-acrylate-epoxy tung oil polypolymer (AETP). The tung oil monomer before and after the epoxy formation was compared by proton NMR spectroscopy, and the chemical structure of AETP was analyzed by Fourier transform spectroscopy. Tung oil has an acid value of 1.5 mg KOH per g, an epoxy value of 5.38%, an iodine value of 11.28 g/100 g, and a refractive index of = 1.475. Composite-based 3D printing resins (like AETP) were cured using digital light treatment, while some samples were also post-treated ultraviolet (UV) light treatment. The AETP-based 3D printing resin has excellent thermal and mechanical properties, and the viscosity of its system is 313 mPa s; exposure time 4.5 s; the tensile strength, flexural strength and flexural modulus were 62 MPA, 63.84 MPa and 916.708 MPa, respectively; Shore hardness was 80 HD and shrinkage was 4.00%. The good performance of the AETP-based 3D printing resin is attributed to the rigidity of their tightly crosslinked structure. This study pioneered a method for producing photoactive acrylates (, tung oil-based acrylate oligomer resins) from renewable, low-cost biomass for light-curing 3D printing.
以桐油为原料，与丙烯酸改性松香（β-丙烯酰营养乙酯）酯（ARA）/丙烯酸-2-羟乙酯（HEA）反应，成功合成了一种新型生物基预聚物，然后以上述复合材料为基体，再与活性稀释剂（2-HEMA、TPGDA）和光引发剂TPO及Irgacure1173反应，成功合成了一种新型生物基预聚物——丙烯酸酯-环氧桐油多聚物（AETP）。通过质子核磁共振光谱对环氧形成前后的桐油单体进行了比较，并通过傅里叶变换光谱分析了AETP的化学结构。桐油的酸值为1.5mg KOH/g，环氧值为5.38%，碘值为11.28g/100g，折射率为 = 1.475。基于复合材料的3D打印树脂（如AETP）采用数字光处理进行固化，同时一些样品还进行了紫外线（UV）后处理。基于AETP的3D打印树脂具有优异的热性能和机械性能，其体系粘度为313mPa·s；曝光时间为4.5s；拉伸强度、弯曲强度和弯曲模量分别为62MPa、63.84MPa和916.708MPa；邵氏硬度为80HD，收缩率为4.00%。基于AETP的3D打印树脂的良好性能归因于其紧密交联结构的刚性。本研究开创了一种由可再生、低成本生物质生产用于光固化3D打印的光活性丙烯酸酯（即桐油基丙烯酸酯低聚物树脂）的方法。
