Epoxy fatty acids and waste vegetable oils can be strategically utilized as renewable feedstock for the synthesis of novel bio-based oligomers. Herein, we present an efficient synthetic methodology for producing a wide range of bio-oligomers from the ring-opening copolymerization (ROCOP) reaction of linoleic acid-derived epoxides (MLO, methyl linoleate oxide; ELO, ethyl linoleate oxide; ILO, isopropyl linoleate oxide) or epoxidized sunflower oil (ESO) with cyclic anhydrides (such as phthalic anhydride PA, and maleic anhydride MA). The reaction is catalyzed by a wide variety of commercially available amino acids (AAs) along with tetrabutylammonium iodide (TBAI) serving as a cocatalyst. Among the studied AAs as bio-organocatalysts, L-glutamic acid (L-Glu) exhibited the best performance for the preparation of poly(MLO-co-PA), poly(ELO-co-PA), poly(ILO-co-PA), poly(MLO-co-MA), poly(ELO-co-MA), and poly(ILO-co-MA) achieving a 100 % conversion at 80 °C in only 30 min. In contrast, the synthesis of poly(ESO-co-PA) and poly(ESO-co-MA) required 1 h to reach full conversion under the same conditions. The resulting oligomers were extensively characterized by using NMR, FT-IR, GPC, and TGA. Additionally, a set of computational simulations based on density functional theory (DFT) method was also carried out to support our experimental findings. Climbing-image nudged elastic band (CI-NEB) method was employed to find the minimum energy path (MEP) that describes the reaction mechanism associated with the first step of this chemical transformation. The calculated reaction path provides an energetic and atomistic picture of the studied reaction which aims to understand the role of both catalysts.

中文翻译：

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氨基酸作为 ROCOP 中的环保生物有机催化剂，用于从脂肪酸环氧化物和废弃葵花籽油制备生物基低聚物


环氧脂肪酸和废弃植物油可以战略性地用作合成新型生物基低聚物的可再生原料。在本文中，我们提出了一种有效的合成方法，用于从亚油酸衍生的环氧化物（MLO，亚油酸甲酯氧化物;ELO，亚油酸乙酯氧化物;ILO，亚油酸异丙酯氧化物）或含环状酐（如邻苯二甲酸酐 PA 和马来酸酐 MA）的环氧化葵花籽油 （ESO）。该反应由多种市售氨基酸 （AA） 和用作助催化剂的四丁基碘化铵 （TBAI） 催化。在作为生物有机催化剂的研究AAs中，L-谷氨酸（L-Glu）在制备聚（MLO-co-PA）、聚（ELO-co-PA）、聚（ILO-co-PA）、聚（MLO-co-MA）、聚（ELO-co-MA）和聚（ILO-co-MA）方面表现出最佳性能，在80 °C下仅需30 min即可实现100%的转化率。相比之下，在相同条件下，poly（ESO-co-PA） 和 poly（ESO-co-MA） 的合成需要 1 h 才能达到完全转化。通过使用 NMR、FT-IR、GPC 和 TGA 对所得低聚物进行了广泛表征。此外，还进行了一组基于密度泛函理论 （DFT） 方法的计算模拟来支持我们的实验结果。采用攀爬图像轻推松紧带 （CI-NEB） 方法找到描述与该化学转化第一步相关的反应机制的最小能量路径 （MEP）。 计算出的反应路径提供了所研究反应的能量和原子图，旨在了解两种催化剂的作用。