节点文献
新型苯并咪唑离子液体的合成和性质研究
Synthesis and Properties of New Ionic Liquids Comprising N, N’-Dialkylbenzimidazolium Salt
【作者】 王可飞；
【导师】 建方方；
【作者基本信息】 青岛科技大学 ， 应用化学， 2009， 博士
【摘要】 本论文合成了102种未见报道的苯并咪唑离子液体,采用元素分析、红外光谱对所合成的离子液体的结构进行了表征,得到了17个结构新颖的离子液体的单晶结构,研究了它们的熔点、电导率、磁性和液晶等性质并推断了结构和性质之间的关系。1.合成了一系列无机酸根二烷基苯并咪唑[(CnH2n+1)2-bim]X （bim为苯并咪唑） [n = 4,6,8,10,12,14;X = F-,Cl-,Br-,NO3-,BF4-,ClO4-,HSO4-,H2PO4-和SiF62-]离子液体,采用元素分析、红外光谱对所合成的离子液体进行了表征,并得到了7个离子液体单晶,如:[(C12H25)2-bim]2SiF6和[（C10H21）2-bim]BF4等。利用示差扫描热分析（DSC）和偏光显微镜（POM）研究了该系列化合物的液晶性质,部分化合物如[(C12H25)2-bim]HSO4和[(C12H25)2-bim]H2PO4显示好的液晶性质。并测试了该系列离子液体的电导率。2.合成了一系列含铜二烷基苯并咪唑[(CnH2n+1)2-bim]2[CuCl4] （n = 4,6,8,10,12,14）离子液体,采用元素分析、红外光谱对所合成的离子液体进行了表征,并得到了[(C8H17)2-bim]2[CuCl4]、[（C10H21）2-bim]2[CuCl4]和[(C12H25)2-bim]2[CuCl4]的单晶结构。并对该系列化合物进行了DSC、热重分析（TG/DTG）和电导率研究。3.合成了一系列含钴的二烷基苯并咪唑[（CnH2n+1）-bim]2[CoCl2]和[(CnH2n+1)2-bim]2[Co（SCN）4] （n = 4,6,8,10,12,14）金属液晶,采用元素分析、红外光谱对所合成的离子液体进行了表征,并得到了部分离子液体单晶,如:[(C8H17)-bim]2[CoCl2]和[(C12H25)2-bim]2[Co（SCN）4]。用DSC、TG/DTG和POM研究了该系列化合物的热稳定性和液晶性质,部分化合物如[(C8H17)-bim]2[CoCl2]和[(C12H25)2-bim]2[Co（SCN）4]显示好的液晶性质。研究[(C12H25)2-bim]2[Co（SCN）4]在不同溶剂中的电导率及[（C12H25）-bim]2[CoCl2]和[(C12H25)2-bim]2[Co（SCN）4]的磁性。4.合成了新型含铁锰锌的二烷基苯并咪唑[(CnH2n+1)2-bim]MClm （n = 4,6,8,10,12,14,M为铁、锰、锌,m = 3或4）系列离子液体,采用元素分析、红外光谱对所合成的离子液体进行了表征,并得到了[（C4H9）2-bim]FeCl4的单晶。研究了[（C4H9）2-bim]FeCl4热稳定性和电导率,利用这个新的金属离子液体制作了一个本体修饰碳糊电极,对其电化学和电催化进行考察。该修饰电极对过氧化氢氧化为氧气和还原为水起到双重催化作用,而且催化溴酸根在电极上的还原。5.合成了一系列新型含镉的二烷基苯并咪唑[(CnH2n+1)2-bim]2[Cd2Cl6] （n = 4,6,8,10,12,14）系列离子液体。采用元素分析、红外光谱对所合成的离子液体进行了表征,得到了[（C10H21）2-bim]2[Cd2Cl6]的单晶并通过X-射线晶体衍射表征结构。研究了[（C10H21）2-bim]2[Cd2Cl6]热稳定性和电导率,利用这个新的金属离子液体制作了一个本体修饰碳糊电极,对其电化学和电催化进行考察。该修饰电极对过氧化氢、亚硝酸根、溴酸根和三氯乙酸还原起到很好的催化作用。6.合成了新型含稀土的二烷基苯并咪唑[(CnH2n+1)2-bim]3[Ln（NO3）6] （n = 4,6,8,10,12,14,Ln=La和Y）系列离子液体。采用元素分析、红外光谱对所合成的离子液体进行了表征,得到了[（C4H9）2-bim]3[La（NO3）6]的单晶并通过X-射线晶体衍射表征结构。研究了[（C4H9）2-bim]3[La（NO3）6]热稳定性和电导率,并用这个新的金属离子液体制作了一个本体修饰碳糊电极,对其电化学和电催化进行考察。该修饰电极对过氧化氢、亚硝酸根、溴酸根和三氯乙酸还原起到很好的催化作用。7.利用合成的离子液体[(C12H25)2-bim]Br做催化剂,催化由芳醛合成偶酰的反应,催化效果较好,反应条件温和,产率较高。
【Abstract】 102 kinds of new benzimidazolium ionic liquids were synthesized and the structures were characterized by IR spectroscopy and elemental analysis, and 17 single crystals of the ionic liquids were obtained and characterized by single crystal X-ray diffraction. The melting points, conductivities, liquid crystals and magnetic properties were studied and the relationships of the structures and properties were infered.1. A series of ionic liquids of N,N’-dialkylbenzimidazolium salts of [(CnH2n+1)2-bim]X （bim= benzimidazole） [n=4, 6, 8, 10, 12, 14; X = F-, Cl-, Br-, NO3-, BF4-, ClO4-, HSO4-, H2PO4- and SiF62-] were synthesized and the structures were characterized by IR spectroscopy and elemental analysis. Seven crystal structures such as [（C10H21）2-bim]BF4 and [(C12H25)2-bim]2SiF6 were characterized by single crystal X-ray diffraction. The liquid crystalline behaviors of those compounds were examined by differential scanning calorimetry （DSC） and polarized optical microscopy （POM）. Particularly, the ionic liquids [(C12H25)2-bim]HSO4 and [(C12H25)2-bim]H2PO4 displayed liquid crystal smectic A phase （SmA）.2. A series of copper-containing ionic liquids of N,N’-dialkylbenzimidazolium salts of [(CnH2n+1)2-bim]2[CuCl4] （n = 4, 6, 8, 10, 12, 14） were synthesized and the structures were characterized by IR spectroscopy and elemental analysis. Crystal [(C8H17)2-bim]2[CuCl4], [（C10H21）2-bim]2[CuCl4] and [(C12H25)2-bim]2[CuCl4] were characterized by single crystal X-ray diffraction. Thermal analysis and conductivity of the series of ionic liquids were studies.3. A series of cobalt-containing liquid crystals of N,N’-dialkylbenzimidazolium salts of [（CnH2n+1）-bim]2[CoCl2] and [(CnH2n+1)2-bim]2[Co（SCN）4] （n = 4, 6, 8, 10, 12, 14） were synthesized and the structures were characterized by IR spectroscopy and elemental analysis. Four crystal structures such as [(C8H17)-bim]2[CoCl2] and [(C12H25)2-bim]2[Co（SCN）4] were characterized by single crystal X-ray diffraction. The liquid crystalline behaviors and thermal stability of those complex were examined by DSC, TG/DTG and POM. Particularly, some ionic liquids such as [[(C8H17)-bim]2[CoCl2] and [(C12H25)2-bim]2[Co（SCN）4] displayed liquid crystal smectic A phase （SmA）. The electrical conductivity of [(C12H25)2-bim]2[Co（SCN）4] in different solvents and the magnetic properties of [（C12H25）-bim]2[CoCl2] and [(C12H25)2-bim]2[Co（SCN）4] were studied.4. A series of iron-, manganese- and zinc-containing ionic liquids of N,N’-dialkylbenzimidazolium salts of [(CnH2n+1)2-bim]MCl4 （n = 4, 6, 8, 10, 12, 14, M for iron, manganese, zinc） were synthesized and the structures were characterized by IR spectroscopy and elemental analysis. Crystal [（C4H9）2-bim]FeCl4 was characterized by single crystal X-ray diffraction, and thermal stability and conductivity of the complex were examined. The electrochemical properties of [（C4H9）2-bim]FeCl4 bulk-modified carbon paste electrode had been studied, and the results indicated that it had good electrocatalytic activities toward the hydrogen peroxide and bromate.5. A series of cadmium-containing ionic liquids of N,N’-dialkylbenzimidazolium salts of [(CnH2n+1)2-bim]2[Cd2Cl6] （n = 4, 6, 8, 10, 12, 14） were synthesized and the structures were characterized by IR spectrum and elemental analysis. Crystal [（C10H21）2-bim]2[Cd2Cl6] was characterized by single crystal X-ray diffraction, and thermal stability and conductivity of the complex were examined. The electrochemical properties of [（C10H21）2-bim]2[Cd2Cl6] bulk-modified carbon paste electrode had been studied, and the results indicated that it had good electrocatalytic activities toward the reduction of the hydrogen peroxide, nitrite, bromate and trichloroacetic acid.6. A series of Ln-containing ionic liquids of N,N’-dialkylbenzimidazolium salts of [(CnH2n+1)2-bim]3[Ln（NO3）6] （n = 4, 6, 8, 10, 12, 14, Ln for La and Y） were synthesized and the structures were characterized by IR spectroscopy and elemental analysis. Crystal [（C4H9）2-bim]3[La（NO3）6] were characterized by single crystal X-ray diffraction, and thermal stability and conductivity of the complex were examined. The electrochemical properties of [（C4H9）2-bim]3[La（NO3）6] bulk-modified carbon paste electrode had been studied, and the results indicated that it had good electrocatalytic activities toward the reduction of the hydrogen peroxide, nitrite, bromate and trichloroacetic acid.7. The ionic liquid [(C12H25)2-bim]Br was used as catalyst in the reaction of synthesizing the derivatives of benzil from aromatic aldehydes, which showed better catalytic effect, mild reaction conditions and higher yield.
【Key words】 Benzimidazole； Ionic liquids； Liquid crystal； Electrocatalysis； Conductivity；