| 黄建龙,杨晓林,高保娇.化学通报,2015,78(5):427-432. |
| 聚合物微球固载的N-羟基邻苯二甲酰亚胺在分子氧氧化甲苯过程中的催化性能 |
| Catalytic Property of N-hydroxyphthalimide Immobilized on Polymer Microspheres in Oxidation of Toluene by Molecular Oxygen |
| 投稿时间：2014-10-31 修订日期：2014-11-25 |
| DOI： |
| 中文关键词: N-羟基邻苯二甲酰亚胺 固载化 交联聚苯乙烯微球 分子氧 催化氧化 |
| 英文关键词:N-hydroxyphthalimide Immobilization Crosslinking polystyrene Catalytic oxidation Toluene Molecular oxygen |
| 基金项目:山西省青年科学基金资助项目 |
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| 中文摘要: |
| 以交联聚苯乙烯微球(CPS) 为基质，经过几步大分子反应在聚合物微球表面合成与固载了N-羟基邻苯二甲酰亚胺(NHPI)，形成固载有NHPI的聚合物微球CPS-NHPI。本文主要将CPS-NHPI与过渡金属盐组成共催化体系，用于分子氧氧化甲苯的反应过程，深入考察该非均相催化剂的催化特性与催化氧化机理。研究结果表明，微球CPS-NHPI与Co(OAc)2所构成的共催化体系，在温和的条件下(80℃的温度和常压下的氧气)可有效地将甲苯深度氧化为苯甲酸，显现出高的催化活性(甲苯转化率达到57%)与优良的选择性(苯甲酸的选择性达到84%)。催化氧化反应遵循自由基链式反应的机理。几种过渡金属盐中，Co(OAc)2的助催化效果最好；主催化剂CPS-NHPI固载的NHPI与助催化剂Co(OAc)2适宜的摩尔比为14:1；主催化剂所含NHPI的摩尔量为底物的12mol%时，催化剂的用量比较适宜。固体催化剂CPS-NHPI具有良好的再循环使用性能。 |
| 英文摘要: |
| N-hydroxyphthalimide (NHPI) was synthesized and immobilized on polymer microspheres with crosslinked polystyrene microspheres via several steps of polymer reaction, resulting in the polymeric microspheres CPS-NHPI, on which NHPI was chemically immobilized. On this basis, in the present work, the solid catalyst CPS-NHPI was combined with some transition metal salts to form compositional catalysts. The compositional catalysts were used in the oxidation reaction of toluene, and their catalytic performance and the catalytic oxidation mechanism were investigated in depth. The experimental results show that the compositional catalyst constituted by CPS-NHPI and Co(OAc)2 can effectively catalyze the oxidation process of toluene by molecular oxygen under the mild conditions (at the temperature of 80℃ and using dioxygen under ordinary pressure), and make toluene to be deeply oxidized into benzoic acid, exhibiting high catalytic activity (the conversion of toluene is 57%) . Furthermore, the compositional catalyst has excellent catalytic selectivity, and the selectivity of benzoic acid reaches 84%. The catalytic oxidation reaction follows the mechanism of free radical chain reaction. Among several transition metal salts, the co-catalyst effect of Co(OAc)2 is the best. The suitable molar ratio of the immobilized NHPI on CPS-NHPI microspheres to Co(OAc)2 is 14:1, the appropriate used amount of the catalyst for the catalytic oxidation system is that the NHPI contained in the primary catalyst CPS-NHPI is 12 mol% of the substrate, and the appropriate reaction temperature is 80 ℃. The solid catalyst CPS-NHPI microspheres possess excellent reusing and cycling property. |
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