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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

董婷婷 ,  毕丛丛 ,  高保娇

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引用本文: 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. doi: 10.11944/j.issn.1000-0518.2016.09.150452 shu
Citation:  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. doi: 10.11944/j.issn.1000-0518.2016.09.150452 shu

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

  • 1.

    中北大学化学工程系 太原 030051

    • 通讯作者: 高保娇,教授;Tel:0351-6273347;Fax:0351-3922118;E-mail:gaobaojiao@126.com;研究方向:功能高分子材料的化学与物理
  • 基金项目:

    山西省青年科学基金资助项目（2014021015-1） 

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%。

English

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  • 收稿日期:  2015-12-17
  • 网络出版日期:  2016-03-28
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