CeO_2-CuO/ZnO/Al_2O_3催化合成二乙基甲苯二胺及性质
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摘要
采用柠檬酸为络合剂,溶胶-凝胶法制备系列CeO_2-CuO/ZnO/Al_2O_3,在3.0 MPa压力和220~230℃反应条件下,甲苯二胺(TDA)和乙烯催化合成二乙基甲苯二胺(DETDA)为探针反应,考察其催化性能,其中CeO_2掺杂量为3%,催化活性最高。通过X射线衍射(XRD)、傅里叶红外光谱(FT-IR)、差热重量分析法(DTG-DTA)、核磁氢谱1 H NMR对CeO_2-CuO/ZnO/Al_2O_3、DETDA、TDA进行检测和表征,揭示了它们的微观结构和内在规律性。XRD检测发现CeO_2掺杂量增多,CeO_2-CuO/ZnO/Al_2O_3衍射峰强度增强,提高了晶化程度,金属原子存在协同效应,增多了活性中心。FT-IR揭示了DETDA内部化学键键型,拥有甲基、亚甲基的多取代芳胺。DTG-DTA检测出的质量变化与热效应两种信息,DETDA的DTG-DTA曲线在66.0、271.0℃存在二个吸热峰,分别为氨基脱离苯环、DETDA的分解产生。通过1 H NMR对DETDA、TDA检测,得到DETDA、TDA的氢原子的数目分别为18和10,分子中各个氢核对应所归属的吸收峰,分别和它们分子式中的氢原子数目吻合。CeO_2-CuO/ZnO/Al_2O_3催化合成DETDA,反应条件温和,工艺流程简单,容易实现高效率和连续化工业生产,因此具有广阔的发展前景。
A series of CeO_2-CuO/ZnO/Al_2O_3 were prepared by sol-gel method with citric acid as complex agent. The properties of CeO_2-CuO/ZnO/Al_2O_3 were investigated with the synthesis of diethyltoluenediamine(DETDA)catalyzed by toluenediamine(TDA)and ethylene catalytic as the probe reaction under 3.0 MPa pressure at 220~230 ℃.As the doping amount of CeO_2 is up to 3%,CeO_2-CuO/ZnO/Al_2O_3 shows the highest catalytic activity. CeO_2-CuO/ZnO/Al_2O_3, DETDA and TDA were characterized by X-ray diffraction, Fourier transform infrared spectroscopy(FT-IR), derivativethermogravimetric analysis and differential thermal analysis and 1 H NMR so as to reveal the microstructure and intrinsic regularity.Intensity of CeO_2-CuO/ZnO/Al_2O_3 diffraction peaks was strengthened,meanwhile the crystallization degree was improved with the increasing of CeO_2 doping content.There are more active centers as the metal atoms show synergistic effect.The chemical bond types in DETDA and TDA were revealed by FT-IR.DETDA is a multi-substituted aromatic amine with methyl and ethyl.Quality change and thermal effect were detected by differential thermal analysis(DTG-DTA).There were two peaks at 66.0 and 271.0℃respectively,as amino was broken away from benzene ring and DETDA decomposed.There are 18 and 10 hydrogen atoms in DETDA and TDA molecules,respectively,consistent with their formulas detected by1 H NMR.There is a wide development prospect in catalytic synthesis of DETDA over CeO_2-CuO/ZnO/Al_2O_3 due to its mild reaction conditions,simple technological process,high efficiency and easily implemented industrial production.
A series of CeO_2-CuO/ZnO/Al_2O_3 were prepared by sol-gel method with citric acid as complex agent. The properties of CeO_2-CuO/ZnO/Al_2O_3 were investigated with the synthesis of diethyltoluenediamine(DETDA)catalyzed by toluenediamine(TDA)and ethylene catalytic as the probe reaction under 3.0 MPa pressure at 220~230 ℃.As the doping amount of CeO_2 is up to 3%,CeO_2-CuO/ZnO/Al_2O_3 shows the highest catalytic activity. CeO_2-CuO/ZnO/Al_2O_3, DETDA and TDA were characterized by X-ray diffraction, Fourier transform infrared spectroscopy(FT-IR), derivativethermogravimetric analysis and differential thermal analysis and 1 H NMR so as to reveal the microstructure and intrinsic regularity.Intensity of CeO_2-CuO/ZnO/Al_2O_3 diffraction peaks was strengthened,meanwhile the crystallization degree was improved with the increasing of CeO_2 doping content.There are more active centers as the metal atoms show synergistic effect.The chemical bond types in DETDA and TDA were revealed by FT-IR.DETDA is a multi-substituted aromatic amine with methyl and ethyl.Quality change and thermal effect were detected by differential thermal analysis(DTG-DTA).There were two peaks at 66.0 and 271.0℃respectively,as amino was broken away from benzene ring and DETDA decomposed.There are 18 and 10 hydrogen atoms in DETDA and TDA molecules,respectively,consistent with their formulas detected by1 H NMR.There is a wide development prospect in catalytic synthesis of DETDA over CeO_2-CuO/ZnO/Al_2O_3 due to its mild reaction conditions,simple technological process,high efficiency and easily implemented industrial production.
引文
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[19]ZHANG S Y,HU Q,FAN G L.The Relationship Between the Structure and Catalytic Performance Cu/ZnO/ZrO2Catalysts for Hydrogenation of Dimethyl1,4-Cyclohexane Dicarboxylate[J].Catal Commun,2013,39(5):96-101.
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[2]AJORI S,ANSAR R.Vibrational Characteristics of Diethyltoluenediamines(DETDA)Functionalized Carbon Nanotubes Using Molecular Dynamics Simulations[J].Physica B,2015,459(2):58-61.
[3]SUN S,LIANG N,AN H L,et al.Kinetics for Dimethyl Toluene-2,4-dicarbamate Synthesis from 2,4-Diaminotoluene,Urea,and Methanol[J].Ind Eng Chem Res,2013,52(5):7 684-7 689.
[4]XIN H B,QI A.HTPB/PTMEG/DADMT Dynamic Properties of Polyurethane Elastomer[J].Polym Mater Sci Eng,2012,28(9):57-60(in Chinese).(辛浩波,齐安.HTPB/PTMEG/DADMT聚氨酯弹性体的动态性能[J].高分子材料科学与工程,2012,28(9):57-60.)
[5]LI Z F,LIANG Z L,TAN H,et al.Study on Chain Reaction Kinetic of a New Aromatic Two Amine Chain Extender DMTDA by in Situ Method[J].Polyurethane Ind,2004,19(3):18-20(in Chinese).(李再峰,梁自禄,田慧,等.新型芳香二胺扩链剂DMTDA的“原位”扩链反应动力学研究[J].聚氨酯工业,2004,19(3):18-20.)
[6]CHEN F,CHEN Z G,QIAN J C,et al.Study on Synthesis of Hierarchical Porous Cerium Oxide Materials and Their Catalytic Performance by the Maple Leaf as the Template[J].J Inorg Mater,2012,27(1):1-5(in Chinese).(陈丰,陈志刚,钱君超,等.以枫叶为模板合成分级多孔氧化铈材料及其催化性能研究[J].无机材料学报,2012,27(1):1-5.)
[7]REN S,YANG X,ZHAO X,et al.Synthesis,Characterization,and Polymerization of a Novel Benzoxazine Based on Diethyltoluenediamine[J].J Appl Polmy Sci,2015,132(17):41 920-41 925.
[8]REN S T,YANG X,ZHAO X J,et al.Kinetics and Properties of Diethyltoluenediamine Type Benzoxazine-cured Diglycidyl Ether of Bisphenol-A[J].Thermochim Acta,2015,616(9):33-41.
[9]JIANG J G,ZHONG W Q.A Preparation Method of Diethyltoluenediamine:CN 20071015624.4[P].2007(in Chinese).(蒋京岗,钟文清.一种二乙基甲苯二胺的合成方法[P].中国20071015624.4,2007.)
[10]ZUO Y,GUO X W,LIU M.A Synthesic Method of Diethyltoluenediamine:CN 201210067329.0[P].2012(in Chinese).(左轶,郭新闻,刘民.一种二乙基甲苯二胺的制备方法:中国201210067329.0[P].2012.)
[11]NOWAK A P,ZHOU C,SHARP R E.Low Temperature Segmented Copolymer Compositions and Methods:US 8957175[P].2015.
[12]JANG C,SHARIFI M,PALMESE G R,et al.Toughness Enhancement of Thermosetting Polymers Using a Novel Partially Reacted Substructure Curing Protocol:A Combined Molecular Simulation and Experimental Study[J].Polymer,2016,90(5):249-255.
[13]HANS-JOACHIM B,Leverkusen.Process for the Ortho-alkylation of Optionally Alkyl-substituted M-Phenylenediamines:US 4760185[P].1988.
[14]GUO-SHUH J L,MIDLAND,MICH,et al.Orthoalkylation of Aromatic Amines:PUS 5124483[P].1992.
[15]MENG X H,LIU Z C,ZHANG R.Catalytic Synthesis Diethyltoluenediamine by Catalytic Synthesis Alkyl Method of Toluenediamine in an Ionic Liquid:CN 102807493A[P].2012(in Chinese).(孟祥海,刘植昌,张睿.一种离子液体催化甲苯二胺烷基化合成二乙基甲苯二胺的方法:CN102807493A[P].2012.)
[16]GAO P,LI F,ZHAO N,et al.Influence of Modifier(Mn,La,Ce,Zr and Y)on the Performance of Cu/Zn/Al Catalysts via Hydrotalcite-like Precursors for CO2 Hydrogenation to Methanol[J].Appl Catal A:General,2013,468(5):442-452.
[17]BAN H Y,LI C M,ASAMI K J,et al.Influence of Rare-earth Elements(La,Ce,Nd and Pr)on the Performance of Cu/Zn/Zr Catalyst for CH3OH Synthesis from CO2[J].Catal Commun,2014,54(5):50-54.
[18]ZHU J Y,ZHU Z L,ZHANG H,et al.Enhanced Photocatalytic Activity of Ce-Doped Zn-Al Multi-metal Oxide Composites Derived from Layered Double Hydroxide Precursors[J].J Colloid Interface Sci,2016,481(1):144-157.
[19]ZHANG S Y,HU Q,FAN G L.The Relationship Between the Structure and Catalytic Performance Cu/ZnO/ZrO2Catalysts for Hydrogenation of Dimethyl1,4-Cyclohexane Dicarboxylate[J].Catal Commun,2013,39(5):96-101.
[20]NING C B.Organic Compounds,Structure Identification and Organic Spectroscopy[M].Beijing:Science Press,2000(in Chinese).(宁永成.有机化合物结构鉴定与有机波谱学[M].北京:科学出版社,2000.)