交联聚苯乙烯微球固载2,2,6,6-四甲基哌啶氮氧自由基的催化氧化性能与机理

doi:10.11944/j.issn.1000-0518.2016.09.150452

摘要/Abstract

摘要：

将交联聚苯乙烯(CPS)微球表面固载有2,2,6,6-四甲基哌啶氮氧自由基(TEMPO)的非均相催化剂微球(TEMPO/CPS)与过渡金属盐相结合,构成复合催化剂体系,用于分子氧对肉桂醇的氧化过程的研究。分别采用高价金属离子氧化性比硝酸根NO3-更弱和更强的两类过渡金属盐为助催化剂,与微球TEMPO/CPS构成组合催化剂,深入探索研究了其催化性能与催化机理。研究结果表明,几种过渡金属盐(如Fe、Cu、Mn、Co盐)与微球TEMPO/CPS形成的复合催化剂,可有效地催化分子氧对肉桂醇的氧化过程,将其转化为唯一的产物肉桂醛。以过渡金属硝酸盐为助催化剂,当硝酸盐结构中对应的高价态(氧化态)金属离子的氧化性比NO3-离子弱时(如Fe(NO₃)₃与Cu(NO₃)₂),正负离子共同发挥助催化作用;当硝酸盐结构中对应的高价态(氧化态)金属离子的氧化性比NO3-离子强时,比如Co(NO₃)₂与Mn(NO₃)₂对应的Co(Ⅲ)与Mn(Ⅲ)离子,金属离子单独发挥助催化作用,NO3-离子不起作用。实验结果表明,对于肉桂醇的分子氧催化氧化,在几种过渡金属盐中,Fe(NO₃)₃作为最适宜的助催化剂,温和条件下(55 ℃、常压O₂),可高效地将肉桂醇转化为肉桂醛,转化率为92%。

关键词: 四甲基哌啶氮氧自由基, 非均相催化剂, 肉桂醇, 分子氧氧化, 催化氧化

Abstract:

2,2,6,6-Tetramethylpiperidine-1-oxyl(TEMPO) was immobilized on crosslinked polystyrene(CPS) microspheres to give a heterogeneous microspheres TEMPO/CPS catalyst. A combined catalysts of TEMPO/CPS microspheres and metal salts were used in the oxidation of cinnamyl alcohol with molecular oxygen as the oxidant. The catalytic properties and catalytic mechanisms of these combinational catalysts were investigated. Some combined catalysts can effectively catalyze the oxidation reaction of cinnamyl alcohol to cinnamyl aldehyde as sole product. For nitrate co-catalysts, if the corresponding metal ion has weaker oxidizing ability than NO3- ion, for example, Fe(NO₃)₃ and Cu(NO₃)₂, the cations and anions will work together in the catalytic process. If the oxidizability of metal ion is stronger than NO3- ion, for example, Co(NO₃)₂ and Mn(NO₃)₂, the metal ion will alone play a role in the oxidation. Among several transition metal salts, Fe(NO₃)₃ is the best co-catalyst, and leads to the oxidation of cinnamyl alcohol to cinnamyl aldehyde in 92% conversion under mild conditions(at 55 ℃ and with O₂ at ordinary pressure).

Key words: tetramethylpiperidine-1-oxyl, heterogeneous catalyst, cinnamyl alcohol, molecular oxygen, catalytic oxidation

董婷婷, 毕丛丛, 高保娇. 交联聚苯乙烯微球固载2,2,6,6-四甲基哌啶氮氧自由基的催化氧化性能与机理[J]. 应用化学, 2016, 33(9): 1017-1025.

DONG Tingting, BI Congcong, GAO Baojiao. Catalytic Oxidation Property and Mechanism of 2,2,6,6-Tetramethylpiperidine-1-oxyl Immobilized on Crosslinked Polystyrene Microspheres[J]. Chinese Journal of Applied Chemistry, 2016, 33(9): 1017-1025.

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