【作者】 高丰琴；

【导师】 王博；

【作者基本信息】 陕西师范大学 ， 应用化学， 2006， 硕士

【摘要】 在环保和节能的推动下,必须有更经济高效的无铅化汽油抗爆剂来满足人们对高辛烷值汽油的需求。论文的第一部分对汽油抗爆剂尤其是无铅汽油抗爆剂的发展及种类进行了综述。在树枝状高分子和过渡金属配合物研究的基础上提出本课题的研究内容。 论文的第二部分合成出了一系列不同的树枝状高分子过渡金属配合物和嘧啶过渡金属配合物并对它们进行了表征。树枝状高分子是以乙二胺为核,马来酸酐为支化结构单元合成的,其配体是用水杨醛对该树枝状高分子的外部官能团进行修饰而得。合成的配体进一步与小分子过渡金属盐作用即得到树枝状高分子过渡金属配合物。本课题合成的树枝状高分子金属配合物分别为:Cu（Ⅱ）、Mn（Ⅱ）、Ni（Ⅱ）、Cu（Ⅰ）/（Ⅱ）、Fe（Ⅱ）/（Ⅲ）、羰基铁及混合金属（Fe（Ⅲ）/Cu（Ⅱ）/Mn（Ⅱ）/Ni（Ⅱ））配合物。嘧啶配体是硫脲与乙酰丙酮反应而得,与过渡金属盐反应后得到对应的嘧啶铜、钴、镍配合物（Cu（HL）₂（H₂O）₂Cl₂,[Co（HL）₃（H₂O）₂Cl]Cl·2H₂O,[Ni（HL）₃（H₂O）₂Cl]Cl·2H₂O）。采用凝胶渗透色谱、红外光谱、紫外光谱、X-射线光电子能谱（XPS）、热分析（TG-DTG）等方法对所合成的化合物进行了结构表征,其中应用X-射线光电子能谱,得出了更为精确的关于配体及其配合物的内层电子的变化情况,对化合物结构的推测提供了强有力的理论基础。结果表明,合成的树枝状高分子配体和嘧啶配体与过渡金属离子之间以配位键结合方式存在。 论文第三部分对合成的过渡金属配合物用作汽油抗爆剂进行了研究。将合成的几种过渡金属配合物在不同溶剂中寻找合适的助溶剂,并分别通过助溶剂配制成一定浓度的溶液,按比例加入汽油中,对汽油的稳定性和对汽油抗爆性能的改善效果进行了研究。实验结果表明,添加高分子类和嘧啶类过渡金属配合物后,汽油的稳定性良好;嘧啶类化合物对汽油抗爆效果无明显改善,而高分子配体及其配合物对汽油的辛烷值都有不同程度的影响。其中高分子锰配合物和混合金属配合物对汽油的抗爆效果产生负影响,而高分子配体及其它金属配合物对汽油的辛烷值有一定程度的提高。高分子羰基铁配合物和变价铁配合物在100ml汽油中含量仅为0.08g时即可将汽油辛烷值提高2-3个单位,高分子镍配合物和铜配合物提高幅度不是很大,但在加量相对较少的情况下也不失为一种优良的汽油抗爆剂。另外,通过对抗爆剂加和效应的研究发现,抗爆剂的加量与其抗爆效果之间不存在简单的线性关系,对于不同的抗爆剂,应该存在最佳、最经济的添加量。 论文的第四部分对汽油抗爆剂的抗爆机理作了简单综述,在此基础上对高分更多还原

【Abstract】 Today it is urgent to search and produce more economical and effective antiknock additives for automobile engines to use unleaded clean fuels, which can satisfy the increasing demand for environmental protection and energy conservation. In the first part of the dissertation, the basic knowledge of development and species of the gasoline antiknock （especially nonleaded） is introduced and reviewed. The content of this subject study is presented on the basis of studies on dendritic macromolecule and transition metal complex.The second part of this dissertation shows the synthesis and characterization of some different kinds of transition metal complexes of a new dendritic macromolecule and pyrimidine. The dendritic macromolecule was prepared using ethylenediamine as core and maleic anhydride as branched units. Its ligand of the dendritic macromolecule was obtained by salicylaldehyde’s modifying the peripheral functional group of the dendritic macromolecule. From the reaction of the ligand with transition metal salts, a series of transition metal complexes were synthesized successfully: Cu（II）, Mn（II）, Ni（II）, Cu（I） /（II）, Fe（II） /（III）, carbonyl iron and mixed metals （Fe（III）, Cu（II）, Mn（II）, Ni（II）） complexes. The ligand of pyrimidine was synthesized by thiourea and 2,4-pentandione diacetylmethane and its complexes as follows: Cu（HL）₂（H₂O）₂Cl₂, [Co（HL）₃（H₂O）₂Cl]Cl·2H₂O and [Ni（HL）₃（H₂O）₂Cl]Cl·2H₂O. These complexes were characterized by gel permeation chromatography, infrared spectrum, ultraviolet spectra, X-ray photoelectron spectra （XPS） and thermal analysis （TG-DTG）. Some more detailed data on the changes of the ligand and their complexes, which can provide the changes of internal electronic state about the suggested structures of the complexes, was obtained from XPS spectrometry. From these results it can be concluded that the ligand of the dendritic macromolecule and pyrimidine have been synthesized and integrated with the transition metal ions by coordinated bond.In the third part of this dissertation, the transition metal complexes prepared used as gasoline antiknock have been studied. The stability and the improvement effect on the gasoline were also studied. The results showed that transition metal complexes derived from the dendritic macromolecule and pyrimidine had a good stability on thegasoline and less effective improvements has been shown with the complexes of the pyrimidine as additives, while different impacts with the complexes of the dendritic macromolecule as additives has been observed: Mn（II） and mixed metals （Fe（III）, Cu（II）, Mn（II）, Ni（II）） complex of the dendritic macromolecule had negative effect on antiknock property, while the addition of the ligand and the other complexes can improve the antiknock number of the same gasoline. When 0.08 g of the antiknock additives were added into 100 ml gasoline, the Fe（II） /（III） and carbonyl iron complexes of the dendritic macromolecule can increase 2-3 units of octane number of the gasoline, whereas the Cu（II） and Ni（II） complexes did not exhibit an obvious improvement, they might be a fine antiknock additive because of less mass comparatively. In addition, the results revealed that there exited no single linear relations between the addition and the effect of the antiknock. There lies a better and more economical addition to different antiknock.In the forth part of this dissertation, a brief summarization on mechanics of the antiknock was made and the possible mechanics of the transition metal complexes of the macromolecule was proposed: the reaction occurred between the high-valent metal oxide and hydrocarbon peroxide free radical, which can effectively restrain the reaction velocity and obtain a better antiknock effect.In this dissertation, a series of transition metal complexes were synthesized and characterized, especially by XPS analysis, which enriched its species and physicochemical data. Moreover, there is no report in consulted literature about the transition metal complexes of the macromolecule using as an antiknock additive of gasoline. The synthesis process of the complexes conducted in our research is brief and the raw materials are abundant and relatively cheap. With less addition, the carbonyl iron, Fe（II） /（III）, Ni（II） and Cu（II） complexes of the dendritic macromolecule may have good prospects of development and application as the gasoline antiknock.更多还原