Selective Synthesis of Monoesters of Itaconic Acid with Broad Substrate Scope: Biobased Alternatives to Acrylic Acid?
Selective Synthesis of Monoesters of Itaconic Acid with Broad Substrate Scope: Biobased Alternatives to Acrylic Acid?
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DOI：
10.1021/acssuschemeng.9b06330
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发表时间：
2020-01-27
影响因子：
8.4
通讯作者：
Robert, Tobias
中科院分区：
文献类型：
--
作者：
Arnaud, Sacha Perocheau;Andreou, Eleni;Robert, Tobias
在过去的几年里，人们越来越关注在紫外线固化材料中确定丙烯酸的生物基替代品。在这方面，由于其结构相似性，衣康酸引起了相当大的关注。然而，分子中的第二个酸基团限制了其在许多应用中的使用，因为可能发生不希望的副反应。一种解决方案是使用衣康酸的单酯来模拟丙烯酸的性质。然而，到目前为止，还没有普遍适用的和简单的合成方案已被报道。本文介绍了多种衣康酸单酯的合成。该方法耐受广泛的底物范围，是高效的，并且不遭受繁琐的纯化步骤;因此，它可以大规模应用。在下一步中，单酯与环氧化大豆油反应以产生生物基UV固化低聚物。研究了不同单酯对功能化植物油性质的影响，如粘度以及对紫外光诱导的自由基交联的反应性。此外，将这些结果与丙烯酸酯化大豆油的结果进行了比较。尽管基于衣康酸的低聚物的聚合速率较低，但在某些情况下双键转化率较高。此外，粘度被发现是较低的丙烯酸衍生的化合物相比，使这些新的单酯有前途的替代品的石油化工基丙烯酸。
Over the last few years, there has been an increasing interest to identify biobased alternatives to acrylic acid in UV-curing materials. In this respect, itaconic acid has drawn considerable attention, due to its structural similarity. However, the second acid group in the molecule limits its use in many applications, as undesired side reactions can occur. One solution is the use of monoesters of itaconic acid to mimic the properties of acrylic acid. However, to date, no general applicable and straightforward synthetic protocol has been reported. Herein, the synthesis of a variety of monoesters of itaconic acid is presented. The methodology tolerates a broad substrate scope, is highly efficient, and does not suffer from tedious purification steps; therefore it can be applied on large scale. In the next step, the monoesters were reacted with epoxidized soybean oil to produce biobased UV-curing oligomers. The influence of the different monoesters on the properties of the functionalized vegetable oils, such as viscosity as well as the reactivity toward UV-light induced radical cross-linking, was studied. In addition, these findings were compared with those of acrylated soybean oil. Despite the lower rate of polymerization of the itaconic acid-based oligomers, the double bond conversion was higher in some cases. In addition, the viscosity was found to be lower in comparison to that of the acrylic acid-derived compound, making these novel monoesters promising alternatives to the petrochemical-based acrylic acid.