TEMPO功能化共轭微孔聚合物催化氧化醇性能  

TEMPO Radical Functionalized Conjugated Microporous Polymer for Selective Oxidation of Alcohols

作　　者：王晨 毛会玲 薛云 晏秘 申妍铭 庄金亮 WANG Chen;MAO Hui-ling;XUE Yun;YAN Mi;SHEN Yan-ming;ZHUANG Jin-liang(Key Laboratory of Functional Materials and Chemistry of Guizhou Province,School of Chemistry and Materials Science,Guizhou Normal University,Guiyang 550001,Guizhou,China)

机构地区：[1]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

出　　处：《精细化工》2019年第12期2447-2451,2475,共6页Fine Chemicals

基　　金：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)

摘　　要：将2,2,6,6-四甲基哌啶氧自由基(TEMPO)嫁接到2,5-二溴苯甲酸侧链,并与1,3,5-三乙炔苯(Ⅰ)通过Sonogashira偶联反应,合成出TEMPO自由基功能化共轭微孔聚合物CMP-3-TEMPO。利用SEM、XRD、FTIR和EPR等测试了CMP-3-TEMPO的形貌和结构组成。催化性能测试结果表明:CMP-3-TEMPO在氧气氛围、较温和条件下(80℃,常压),可将各种一级醇、二级醇以及杂原子醇氧化成相应的醛或酮化合物,转化率为70%~100%。CMP-3-TEMPO经过3次循环利用后,催化性能有所降低,可能的原因是反应过程中CMP-3-TEMPO存在局部解体,导致催化活性位点降低。2,2,6,6-Tetramethylpiperidineoxyl(TEMPO) radical was grafted to 2,5-dibromobenoic acid, and further reacted with 1,3,5-triethynylbenzene(Ⅰ) through Sononashira coupling reaction to obtain a TEMPO radical decorated conjugated microporous polymer(CMP), named CMP-3-TEMPO. The chemical composition and structural information of CMP-3-TEMPO were characterized by SEM, XRD, FTIR, and EPR spectra. The results showed that CMP-3-TEMPO could oxidize a broad range of primary and secondary aromatic alcohols, and heteroatom aromatic alcohols into corresponding aldehydes and ketones with conversions in the range from 70% to 100% under mild aerobic conditions(80 ℃, normal atmospheres). The catalytic activity of CMP-3-TEMPO significantly decreased after three catalytic cycles, which was caused due to the partial decomposition of CMP-3-TEMPO during the reaction process.

关 键 词：共轭微孔聚合物 醇氧化 TEMPO自由基 异相催化 SONOGASHIRA偶联反应 

分 类 号：TQ244[化学工程—有机化工]