Lotos Elena-Daniela, Dinu Roxana, Mihai Marcela, Simionescu Bogdan C, Mija Alice
Petru Poni Institute of Macromolecular Chemistry, 41A Grigore Ghica Voda Alley, Iasi, Romania.
Côte d'Azur University, ICN, Nice, France.
Chemistry. 2025 May 14;31(27):e202500624. doi: 10.1002/chem.202500624. Epub 2025 Apr 16.
Herein, bisphenol A-free, biobased, and sustainable thermosets were obtained for the first time by using two naturally derived compounds. Zein, a renewable biopolymer extracted from maize, exhibited excellent reactivity and versatility, while the diglycidyl ether of vanillyl alcohol (DGEVA), a biobased epoxy monomer derived from vanillin, served as a sustainable alternative to petrochemical epoxides. By chemically integrating Zein into DGEVA thermosetting networks, environmentally friendly resins with excellent thermomechanical properties were developed. A comprehensive analysis of seven formulations, incorporating up to 30 wt.% Zein, provided critical insights into the relationship between protein content and resin properties. Differential scanning calorimetry (DSC) analysis highlighted a strong interaction between Zein and DGEVA's epoxy groups, resulting in significantly higher polymerization enthalpies compared to neat DGEVA homopolymerization. This indicates the formation of robust crosslinked networks driven by Zein's multifunctional groups. Dynamic mechanical analysis (DMA) demonstrated substantial improvements in the thermosets' glass transition (T), with values increasing from 52°C in neat DGEVA to 73°C in DGEVA/30% Zein systems, indicating enhanced stiffness and thermal performance. Furthermore, thermogravimetric analysis (TGA) confirmed good thermal stability of the bioresins, with degradation temperatures exceeding 300°C. Beyond these technical achievements, this study underscores the broader significance of incorporating Zein, a byproduct of corn agriculture, into biobased thermosets.
在此，首次通过使用两种天然衍生化合物获得了不含双酚A、生物基且可持续的热固性材料。玉米醇溶蛋白是一种从玉米中提取的可再生生物聚合物，具有出色的反应活性和多功能性，而香兰醇二缩水甘油醚（DGEVA）是一种源自香草醛的生物基环氧单体，可作为石化环氧树脂的可持续替代品。通过将玉米醇溶蛋白化学整合到DGEVA热固性网络中，开发出了具有优异热机械性能的环保型树脂。对七种配方（玉米醇溶蛋白含量高达30 wt.%）进行的全面分析，为蛋白质含量与树脂性能之间的关系提供了关键见解。差示扫描量热法（DSC）分析突出了玉米醇溶蛋白与DGEVA环氧基团之间的强相互作用，与纯DGEVA均聚相比，聚合焓显著更高。这表明由玉米醇溶蛋白的多官能团驱动形成了坚固的交联网络。动态力学分析（DMA）表明热固性材料的玻璃化转变温度（T）有显著提高，其值从纯DGEVA中的52°C增加到DGEVA/30%玉米醇溶蛋白体系中的73°C，表明刚度和热性能增强。此外，热重分析（TGA）证实了生物树脂具有良好的热稳定性，降解温度超过300°C。除了这些技术成果外，本研究还强调了将玉米农业副产品玉米醇溶蛋白纳入生物基热固性材料的更广泛意义。
