【作者】 佘江波；

【导师】 张国防；

【作者基本信息】 陕西师范大学 ， 无机化学， 2007， 硕士

【摘要】 随着我国航天事业发展和国防科技对高、精、尖武器的要求不断提高，高性能的推进剂成为研究的热点问题。燃速催化剂是调节固体推进剂燃烧性能不可缺少的组分之一，是固体推进剂配方中非常关键的功能材料。寻找性能优良的燃速催化剂成为在现有推进剂主要成分不变的情况下提高推进剂性能的主要方向。论文第一部分对燃速催化剂的成分、作用、种类及其在各种推进剂中的应用进行了归纳，对3，5—二硝基羟基吡啶含能催化剂的研究进展进行了综述。本论文第二部分合成了三种3，5—二硝基羟基吡啶配体，通过元素分析、红外光谱等表征手段，对这些配体组成和结构进行了表征，并用X—射线单晶衍射分析法研究了2—羟基—3，5—二硝基吡啶（1）和4—羟基—3，5—二硝基吡啶氮氧化物（3）的单晶结构，将获得的2—羟基—3，5—二硝基吡啶粉末X射线图样和单晶数据模拟X射线图样对比，证明了合成的配体为纯相物质。论文第三部分用三种3，5—二硝基羟基吡啶配体和碱金属、碱土金属的氢氧化物、重稀碱金属的碳酸盐反应合成了18种含能钝感配合物，通过元素分析、红外光谱以及热重分析等表征手段，对这些配合物的组成和结构进行了表征。并且得到11个配合物的单晶结构，用X射线单晶衍射仪对这11个配合物进行了晶体结构表征。4—羟基—3，5—二硝基吡啶钠盐（14）的晶体中有两分子的结晶水，钠离子和配体通过羰基氧原子和吡啶氮原子连接为一维链。三个配体和重稀碱金属（铷、铯）的含能配合物的单晶结构表明：2—羟基—3，5—二硝基吡啶铷盐（7）和2—羟基—3，5—二硝基吡啶铯盐（8）的单晶结构显示它们的金属离子都表现为8配位环境，其中化合物（8）的晶体中有一分子的结晶水；4—羟基—3，5—二硝基吡啶铷盐（16）和4—羟基—3，5—二硝基吡啶铯盐（17）结构相似，由两个金属离子和两个桥氧原子组成的近似平行四边形结构单元M₂O₂沿着c轴无限延伸；4—羟基—3，5—二硝基吡啶氮氧化铷盐（21）中存在中性配体、配体阴离子和金属离子配位，4—羟基—3，5—二硝基吡啶氮氧化铯盐（22）在晶体的自组装过程中，氧桥键表现了非常重要的作用，沿着b轴，两组氧桥键和四组氧桥键交替连接铯离子形成了一个波浪型的长链，并且存在吡啶环之间的π—π堆积作用。2—羟基—3，5—二硝基吡啶镁盐（9）和4—羟基—3，5—二硝基吡啶镁盐（18）都是以静电引力将配体阴离子和金属离子结合在一起的，金属离子仅仅和水之间配位。2—羟基—3，5—二硝基吡啶钡盐（12）和4—羟基—3，5—二硝基吡啶钡盐（19）都表现为桥氧双核二聚体。部分配合物的热分析图表现了优良的钝感特性，分解温度都在200℃以后，配合物7、9、16、17的粉末XRD证明所得化合物为纯相物质。论文第四部分利用3，5—二硝基羟基吡啶配体的酸性和过渡金属的碳酸盐作用，合成了10种含能配合物，通过元素分析、红外光谱以及热重分析等表征手段，对这些配合物的组成和结构进行了表征。并且得到2个配合物的单晶，用X射线单晶衍射仪对它们进行了晶体结构表征。2—羟基—3，5—二硝基吡啶铅（27）存在非常明显的相对于配位配体的反式空隙的半直接的配位方式，孤对电子填充在配位空隙处。4—羟基—3，5—二硝基吡啶氮氧化铜盐（31）中由于配位水和氮氢氧体系的存在表现出非常丰富的氢键。本论文合成了一系列3，5—二硝基羟基吡啶含能配合物，通过对其物理化学性质表征，为寻找性能更优良的含能催化剂提供了数据，并且确定了大部分物质的晶体结构，为从微观方面解释催化作用机理提供了依据。更多还原

【Abstract】 With the development of our country’s spaceflight and the promotingneeds of high-technology arms in national defense area, the research for high-propertypropellants are hot-spot currently. Buming-rate catalysts are the indispensablecomponent for solid propellants in order to adjust and improve their trajectoryproperties, and also the very important energetic material in the propellant. Researchfor good burning-rate catalysts is the main direction to improving properties withoutchanging the major components of the propellants. In the first part of this dissertation,the ingredients, functions, species and their applications of burning-rate catalysts arebriefly summarized and energetic catalysts derived from 3,5-dinitropyridone arereviewed concisely.In the second part of this dissertation, three 3,5-dinitropyridone ligands weresynthesized and were characterized by Elemental Analysis, FT-IR and thermoanalysis.Single crystals of the compounds 2-hydroxy-3,5-dinitropyridine（1） and 4-hydroxy-3,5-dinitropyridine-N-oxide（3）, suitable for X-ray diffraction analysis, were grown andtheir structures were determined. The powder XRD profile of 1 indicated that thevalues of diffraction peaks of the polycrystalline sample are in good agreement withthe results simulated on the basis of single-crystal structure, which proves the phasepurity of the powder product.In the third part, eighteen energetic complexes were synthesized with the threeligands and alkali metals and alkaline earth metal compounds. These resultingcomplexes were also undergone Elemental analysis, FT-IR and TG-DSC analysis. Thecrystal structures of eleven complexes were determined by single-crystal X-raydiffraction analysis. The structures revealed that sodium 3,5-dinitropyrid-4-onate（14）molecule contains two water molecules and that the anions link the Na⁺ ions, each ofwhich is coordinated by four water molecules, into a linear chain that runs along the caxis of the unit cell. The crystal structures of the heavy alkali-metal complexesrevealed that the cation atom is eight-coordinate in both rubidium3,5-dinitropyrid-2-onate（7） and cesium 3,5-dinitropyrid-2-onate（8）, with a crystalwater in 8; rubidium 3,5-dinitropyrid-4-onate（16） and cesium 3,5-dinitropyrid-2-onate（17） are very similar in structure and the parallelogram M₂O₂ units, consisting of two metal atoms and two bridging oxygen atoms, extend along the c axis. Neutralligands and anion ligands coordinate with cations in rubidium 3,5-dinitro-4-pyridone-N-hydroxylate（21）. In the self-assembly of the cesium 3,5-dinitro-4-pyridone-N-hydroxylate（22） configuration, the versatile oxygen bridges act important roles, alongthe b axis; the two oxygen-bridges and the four oxygen-bridges appear alternativelybetween the adjacent cesium cations which results in a corrugated chain, aromaticπ-π-stacking was also found in this compound. In the magnesium3,5-dinitropyrid-2-onate（9） and magnesium 3,5-dinitropyrid-4-onate（18）, the cationsand anions are linked by static interactions with each cation being coordinated with sixwater molecules. Both barium 3,5-dinitropyrid-2-onate（12） and barium3,5-dinitropyrid-4-onate（19） are consisting of oxygen-bridged dimeric units. Thethermoanalysis results clearly indicated that they are blunt compounds as thedecomposition tempreture are higher than 200℃. The powder XRD analyses ofcompounds 7, 9, 16 and 17 revealed that the four powder products are of high purity.In the fourth part, ten energetic complexes were synthesized utlizing the acidproperty of ligands to react with a few transition-metal carbonates. These compoundswere also undergone Elemental analysis and FT-IR charactgerization. The crystalstructures of two complexes were determined by X-ray diffraction analysis. Incompound lead 3,5-dinitropyrid-2-onate（27）, the arrangement of the ligands suggests agap or hole in the coordination geometry around the metal ion and the coordinationsphere around the lead atoms is hemidirected with a significant gap trans to thechelating ligands. Beacause of the existence of water molecules and the N-H…O systemin compound copper 3,5-dinitro-4-pyridone-N-hydroxylate（31）, abundant hydrogenbonds are found in it.In this paper, a series of 3,5-dinitro-hydroxy-pyridine energetic complexes weresynthesized and characterized by physicochemical methods, which enriched data forseeking better energetic catalysts. Also, the molecular structures of most part of thecompounds are determined which will provide support based on the viewpoint ofmolecular level for the catalytic machanisms of these type of compounds.更多还原