高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

四聚型季胺类多金属氧酸盐相转移催化氧化甲苯合成苯甲醛

钱  澍1, 于凤丽1, 顾  雪1, 袁  冰1, 解从霞1, 于世涛2   

  1. 1.青岛科技大学化学与分子工程学院, 生态化工国家重点实验室培育基地, 青岛266042; 
    2.青岛科技大学化工学院, 青岛266042
  • 收稿日期:2024-03-12 修回日期:2024-04-10 网络首发:2024-04-12 发布日期:2024-04-12
  • 通讯作者: 于凤丽 E-mail:yufilqust@163.com
  • 基金资助:
    国家自然科学基金（批准号：21878116）资助；山东省自然科学基金（批准号：ZR2020MB131）资助.

Phase transfer catalyzed toluene of oxidation to benzaldehyde using tetrameric quaternary ammonium polyoxometalates

QIAN Shu1, YU Fengli1, GU Xue1, YUAN Bing1, XIE Congxia1, YU Shitao2   

  1. 1. State Key Laboratory Base of Eco-chemical Engineering, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China; 
    2. College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
  • Received:2024-03-12 Revised:2024-04-10 Online First:2024-04-12 Published:2024-04-12
  • Contact: YU Fengli E-mail:yufilqust@163.com
  • Supported by:
    Supported by the National Natural Science Foundation of China (No.21878116); Natural Science Foundation of Shandong Province (No.ZR2020MB131).

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摘要： 甲苯氧化制备苯甲醛在工业应用中通常涉及有毒试剂或产生多种难以分离的副产物. 本文中采用乙二胺, 环氧氯丙烷, N, N—二甲基丁基叔胺等作为初始原料, 首先合成了四聚型季铵盐氯化物，然后与Keggin型钨钒磷杂多酸发生阴离子交换反应，制备了一系列四聚型季胺类多金属氧酸盐, 并通过在乙腈中使用H2O2 (30 wt.%)将甲苯氧化为苯甲醛的反应来评价这些新型的多金属氧酸盐催化剂. 四核阳离子的引入不仅可以调节杂多阴离子的氧化还原性质，而且可以使催化剂具有密集的协同催化活性位点. 另外，优选出的催化剂具有良好的两亲性相转移催化能力, 不仅显著提高了反应速率，而且实现了催化剂的简便回收重复使用. 在经过7次重复使用后催化剂的性能几乎没有下降, 并且实现了可接受的甲苯转化率(40%)和苯甲醛选择性(75%). 因此, 本研究开发了一条与工业相关的碳氢化合物催化氧化的环境友好型工艺, 为实际工业应用奠定了一定的理论研究基础.

关键词: 甲苯氧化, 苯甲醛, 季铵盐, 两亲性, 相转移催化

Abstract: The oxidation of toluene to benzaldehyde in industrial applications typically involves toxic reagents or the generation of various difficult-to-separate byproducts. In this study, starting materials such as ethylenediamine, epichlorohydrin, and N,N-dimethyldodecylamine were used to synthesize tetrameric quaternary ammonium chloride. Subsequently, an anion exchange reaction with Keggin-type tungstovanadophosphoric heteropolyacid was conducted to prepare tetrameric quaternary ammonium polyoxometalates. These polyoxometalate catalysts were then evaluated via the oxidation of toluene to benzaldehyde using H2O2 (30 wt.%) in acetonitrile. The introduction of four nucleated cations not only modulated the redox properties of the heteropolyanions but also provided the catalyst with densely packed cooperative catalytic active sites. Additionally, the resulting catalyst exhibited excellent amphiphilic phase-transfer catalytic capabilities, significantly enhancing the reaction rate and enabling easy catalyst recovery for repeated use. After seven repeated uses, the catalyst's performance showed minimal decline, maintaining acceptable toluene conversion (40%) and benzaldehyde selectivity (75%). Therefore, this study has developed an environmentally friendly process for the catalytic oxidation of hydrocarbons relevant to industry, laying a theoretical foundation for practical industrial applications.

Key words: Toluene oxidation, Benzaldehyde, Quaternary ammonium salt, Amphipathy, PTC(Phase transfer catalyst)

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