Page 126 - 《精细化工》2020年第5期

第 37 卷第 5 期 精 细 化 工 Vol.37, No.5
202 0 年 5 月 FINE CHEMICALS May 2020

催化与分离提纯技术
TEMPO 功能化共轭微孔聚合物作为

高效醇催化氧化剂

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毛会玲，王 晨，晏 秘，薛 云，申妍铭，庄金亮
（贵州师范大学 化学与材料科学学院，贵州省功能材料化学重点实验室，贵州 贵阳 550001）

摘要：2,5-二溴对苯二甲酸通过酰化反应得到了 2,5-二溴对苯二甲酰氯（Ⅱ）。接着，中间体Ⅱ与 4-氨基-2,2,6,6-
四甲基哌啶-1-氧自由基（4-NH 2 -TEMPO）反应获得了侧链嫁接双 2,2,6,6-四甲基哌啶氧自由基（TEMPO）的有
机单体。然后，该有机单体与四（4-乙炔基苯）甲烷通过 Sonogashira 偶联反应，合成了高密度 TEMPO 自由基
功能化的 CMP-4-(TEMPO) 2 共轭微孔聚合物。利用核磁共振谱（NMR）、扫描电子显微镜（SEM）、X 射线衍射
（XRD）、红外吸收光谱（FTIR）和电子顺磁共振谱（EPR）对所合成单体及 CMP-4-(TEMPO) 2 进行了表征。
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结果表明，CMP-4-(TEMPO) 2 由微球和中空纳米管组成，具有较高的比表面积（486 m /g），含有微孔、介孔以
及大孔复合孔，孔道含有丰富的 TEMPO 自由基官能团，可将各种芳香醇和杂原子醇高效、高选择性地氧化成
相应的醛和酮。
关键词：共轭微孔聚合物；多孔材料；异相催化；醇氧化；4-氨基-TEMPO；催化技术
中图分类号：TQ244 文献标识码：A 文章编号：1003-5214 (2020) 05-0976-06

TEMPO radical functionalized conjugated microporous
polymer as an efficient catalyst for alcohol oxidation

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MAO Huiling, WANG Chen, YAN Mi, XUE Yun, SHEN Yanming, ZHUANG Jinliang
（Key Laboratory of Functional Materials and Chemistry of Guizhou Province, School of Chemistry and Materials
Science, Guizhou Normal University, Guiyang 550001, Guizhou, China）

Abstract: 2,5-Dibromoterephthaloyl dichloride (Ⅱ) was prepared from 2,5-dibromoterephthalic acid by
acylation reaction. Then, the intermediateⅡreacted with 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl
(4-NH 2-TEMPO) to obtain an organic monomer with side chain grafted double TEMPO (2,2,6,6-
tetramethylpiperidine-1-oxyl, TEMPO) radicals. The Sonogashira coupling reaction between the organic
monomer and tetrakis (4-ethynylphenyl)methane led to a high density TEMPO radical functionalized
conjugated microporous polymer, named CMP-4-(TEMPO) 2. The organic monomer and functionalized
conjugated microporous polymer were characterized by NMR, SEM, XRD, FTIR, and EPR techniques. The
results showed that CMP-4-(TEMPO) 2 was composed of microspheres and nanotubes, had high BET
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surface area of 486 m /g, containing micropores, mesopores and macroporous composite pores. The
channels of CMP-4-(TEMPO) 2 were rich in TEMPO radicals, which could effectively oxide a broad range
of alcohols, such as aromatic alcohols and heteroatomic alcohols, into their aldehydes and ketones with
excellent selectivity.
Key words: conjugated microporous polymers; porous material; heterogeneous catalysis; alcohol oxidation;
4-amino-TEMPO; catalysis technology

收稿日期：2019-10-27; 定用日期：2020-01-16; DOI: 10.13550/j.jxhg.20191016
基金项目：国家自然科学基金（21861013）；贵州省科技厅重点基金项目（黔科合基础[2016]1413）；贵州省科技计划项目（黔科合平
台人才[2018]5769 号）
作者简介：毛会玲（1993—），女，硕士生，E-mail：maomao917@foxmail.com。联系人：庄金亮（1983—），男，副教授，E-mail：
jizhuang@xmu.edu.cn。