生物基增塑剂的高效两步法生产：柠檬酸脱水加氢，然后进行 Fischer 酯化,Green Chemistry

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生物基增塑剂的高效两步法生产：柠檬酸脱水加氢，然后进行 Fischer 酯化
Green Chemistry ( IF 9.3 ) Pub Date : 2023-03-21 , DOI: 10.1039/d2gc04678d
Anthony De Bruyne ₁ , Wouter Stuyck ₁ , Willem Deleu ₂ , Jarne Leinders ₁ , Carlos Marquez ₁ , Kwinten Janssens ₁ , Dimitrios Sakellariou ₁ , Ruben Ghillebert ₂ , Dirk E. De Vos ₁

Affiliation

我们报告了从柠檬酸 (CA) 开始生产生物基增塑剂的过程，该过程包括 CA 的脱水-氢化，然后是 Fischer 酯化。基于柠檬酸的增塑剂的使用在PVC中是众所周知的。然而，随着时间的推移，柠檬酸酯往往会从 PVC 材料中浸出。这个问题目前通过复杂和环境污染的过程乙酰化 CA 的叔羟基来解决。我们的替代策略包括去除叔羟基，从而产生丙烷-1,2,3-三羧酸 (PTA)。首先，使用 Al ₂ (SO ₄ )在相对温和的反应条件（150 °C 和 20 bar H ₂）下进行大量 CA (20 mmol) 的脱水反应₃作为均相催化剂，水作为绿色溶剂。催化系统被证明在时间上和在其他有机官能团（例如具有不同官能团的氨基酸、二酸）存在下是稳健的在第二步中，将反应混合物转移到 Dean-Stark 装置中，以便与正丁醇进行 Fischer 酯化反应，在此期间可以回收_{之前使用的 Al 2} (SO₄ )_{3 。}这导致总产率为 90% 丙烷-1,2,3-三羧酸三丁酯 (TBPTC)，可用作 PVC 中的增塑剂。

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Efficient two-step production of biobased plasticizers: dehydration-hydrogenation of citric acid followed by Fischer esterification

We report the production of biobased plasticizers starting from citric acid (CA) by a two-step process comprising dehydration-hydrogenation of CA followed by a Fischer esterification. The use of citric acid based plasticizers is well-known in PVC. However, citrate esters tend to leach out of the PVC material over time. This problem is currently tackled by acetylating the tertiary hydroxyl group of CA via complex and environment polluting processes. Our alternative strategy consists in the removal of the tertiary hydroxyl group, resulting in propane-1,2,3-tricarboxylic acid (PTA). First, dehydration reactions of a large amount of CA (20 mmol) were performed at relatively mild reaction conditions (150 °C and 20 bar H₂) using Al₂(SO₄)₃ as a homogeneous catalyst and water as a green solvent. The catalytic system was proven to be robust in time and in the presence of other organic functionalities (e.g. amino acids with different functional groups, diacids). In a second step, the reaction mixture was transferred to a Dean–Stark setup in order to perform a Fischer esterification with n-butanol, during which the previously used Al₂(SO₄)₃ could be recuperated. This resulted in an overall yield of 90% tributyl propane-1,2,3-tricarboxylate (TBPTC), which can be used as a plasticizer in PVC.

更新日期：2023-03-24

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