化学学报 ›› 2011, Vol. 69 ›› Issue (11): 1337-1346. 上一篇    下一篇

研究论文

在醛基化交联聚苯乙烯微球表面同步合成与固载卟啉及固载化金属卟啉的高效催化氧化性能

陈英军,高保娇*,田鹏,马云霞   

  1. (中北大学化学工程系 太原 030051)
  • 收稿日期:2010-10-08 修回日期:2010-12-01 出版日期:2011-06-14 发布日期:2011-01-21
  • 通讯作者: 高保娇 E-mail:gaobaojiao@126.com
  • 基金资助:

    山西省自然科学基金资助项目

Studies on Synchronously Synthsizing and Immobilizing Porphyrins on Crosslinked Polystyrene Microspheres and High Efficient Catalytic Performance of Immobilized Metalloporphyrins in Oxidation

CHEN Ying-Jun, GAO Bao-Jiao, TIAN Peng, MA Yun-Xia   

  1. (Department of Chemical Engineering, North University of China, Taiyuan 030051)
  • Received:2010-10-08 Revised:2010-12-01 Online:2011-06-14 Published:2011-01-21
  • Contact: Bao-jiao GAO E-mail:gaobaojiao@126.com

采用Kornblum氧化反应, 先将氯甲基交联聚苯乙烯(CMCPS)的氯甲基氧化为醛基, 制得醛基(AL)化改性微球ALCPS, 然后使改性微球ALCPS与溶液中的苯甲醛(或取代的苯甲醛)、吡咯之间发生固-液相之间的Adler反应, 成功地实现了卟啉在交联聚苯乙烯微球表面的同步合成与固载, 制得了固载有苯基卟啉(PP) 、对氯苯基卟啉(CPP)、对硝基苯基卟啉(NPP)的功能微球, 最后使功能微球与钴盐发生配合反应, 制备了固载有三种钴卟啉的固体催化剂. 研究重点有两方面: (1)考察主要因素对卟啉同步合成与固载过程的影响|(2)考察固载化钴卟啉在催化分子氧氧化环己烷羟基化过程中的催化特性. 实验结果表明, 以醛基化改性微球ALCPS与溶液中的吡咯及小分子苯甲醛(或取代的苯甲醛)为共反应物, 通过固-液之间的Adler反应, 可以顺利地实现卟啉在微球ALCPS表面的同步合成与固载, 这是制备固载化卟啉的新途径|苯甲醛的取代基结构、催化剂的酸性与溶剂的性质对卟啉的同步合成与固载都有较大的影响|所制备的固体催化剂对分子氧氧化环己烷羟基化的反应, 具有很高的催化活性(环己烷最高转化率约为40%)与选择性(环己醇的选择性在90%以上), 这是由固体催化剂特殊的化学结构所决定的.

关键词: 交联聚苯乙烯, 苯基卟啉, 合成, 固载, 环己烷羟基化

By adopting Kornblum reaction, the chloromethyl groups of chloromethylated crosslinked polystyrene (CMCPS) microspheres were first oxidated as aldehyde groups, resulting in aldehyde group (AL)-modified microspheres ALCPS. Subsequently, synchronistic synthesis and immobilization of porphyrins on CPS microspheres were realized successfully by using benzaldehyde (or substituted benzaldehyde), pyrrole and the microspheres ALCPS as the co-reactants and via the Adler reaction between solid and liquid phases, obtaining three kinds of functional microspheres, on which phenyl porphyrin (PP), p-chlophenyl porphyrin (CPP) and p-nitrophenyl porphyrin (NPP) were immobilized, respectively. Finally, three immobilized cobalt porphyrins were prepared through the complex reaction between these functional microspheres and cobalt salt. This study focused on two aspects: (1) the effects of the main factors on the synchronistic synthesis and immobilization process of porphyrins were examined|(2) the catalytic characters of the immobilized metalloporphyrins in the cyclohexane hydroxylation with molecular oxygen were investigated. The experimental results show that the synchronistic synthesis and immobilization of porphyrin on CPS microspheres can be carried out smoothly by using ALCPS microspheres, benzaldehyde (or substituted benzaldehyde) and pyrrole in solution as co-reactants via the Adler reaction between solid and liquid phases. The substituent structure of benzaldehyde derivatives, the acidity of the catalysts and the properties of the solvents affect the synchronistic synthesis and immobilization of porphyrin greatly. The prepared immobilized metalloporphyrins have very high catalytic activity (a maximum cyclohexane conversion of about 40%) and excellent selectivity (selectivity of more than 90% for cyclohexanol), and this is attributed to their special chemical structure.

Key words: crosslinked polystyrene, phenyl porphyrin, synthesis, immobilization, cyclohexane hydroxylation

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