Computational Screening of Lewis Acid Catalysts for the Ene Reaction between Maleic Anhydride and Polyisobutylene
Computational Screening of Lewis Acid Catalysts for the Ene Reaction between Maleic Anhydride and Polyisobutylene
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DOI：
10.1021/acs.iecr.0c04860
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发表时间：
2021-01-13
影响因子：
4.2
通讯作者：
Mpourmpakis, Giannis
中科院分区：
文献类型：
--
作者：
Morales-Rivera, Cristian A.;Proust, Nico;Mpourmpakis, Giannis
聚异丁烯基琥珀酸酐 (PIBSA) 及其琥珀酰亚胺衍生物是润滑剂和燃料配方中最重要的添加剂之一。这些添加剂通常是通过马来酸酐（MAA）和聚异丁烯（PIB）之间的烯反应合成的。尽管该反应在热力学上是可行的，但它需要升高温度来克服动力学限制。在这方面，路易斯酸通过使亲烯体更加缺电子而被证明是烯反应的重要催化剂。尽管 PIBSA 在汽车工业中具有重要的工业重要性，但尚未建立一种计算方法来筛选用于 MAA 和 PIB 之间烯反应的潜在路易斯催化剂。在此，我们基于第一性原理计算报告了路易斯酸催化烯反应的详细机理。我们证明了 MAA 和 PIB 之间烯反应的最有利途径是通过协同反应机制。通过筛选不同的路易斯酸催化剂，我们开发了活化能与催化剂物质的吸附/解吸能之间的活性关系。周转频率计算表明，在研究的路易斯酰氯基催化剂中，AlCl3 表现出最高的催化活性。总的来说，我们的工作介绍了催化活性关系，可以加速发现用于具有工业重要性的烯反应的路易斯酸催化剂。
Polyisobutenyl succinic anhydrides (PIBSAs) and their succinimide derivatives are one of the most important additives in lubricant and fuel formulations. These additives are commonly synthesized through the ene reaction between maleic anhydride (MAA) and polyisobutene (PIB). Although this reaction is thermodynamically feasible, it requires elevated temperatures to overcome kinetic limitations. In this regard, Lewis acids are shown to be prominent catalysts for the ene reaction by making the enophile more electron-deficient. Despite the industrial importance of PIBSA in the automotive industry, a computational methodology to screen potential Lewis catalysts for the ene reaction between MAA and PIB has not been established. Herein, we report the detailed mechanism of the Lewis acid-catalyzed ene reaction based on first principles calculations. We demonstrated that the most favorable pathway for the ene reaction between MAA and PIB is through a concerted reaction mechanism. By screening different Lewis acid catalysts, we developed activity relationships relating the activation energy with the adsorption/desorption energies of the species from the catalyst. Turnover frequency calculations revealed that, among the Lewis acid chloride-based catalysts studied, AlCl3 exhibits the highest catalytic activity. Overall, our work introduced catalytic activity relationships that can accelerate the discovery of Lewis acid catalysts for ene reactions of industrial importance.