【作者】 王琼；

【导师】 张正波；

【作者基本信息】 华中科技大学 ， 有机化学， 2013， 硕士

【摘要】 六氯环三磷腈是合成磷腈类化合物的重要原料，六氯环三磷腈由氮磷单双键交替连接而成，由于磷氯键的活泼性，可在其骨架中接入不同的官能团实现不同功能化作用，应用于膜技术、阻燃材料、特种橡胶及弹性体、光学材料、生物化学与药物医用材料等。我国磷资源丰富，因此对磷腈化合物的研究有实用前景。被认为是“绿色”溶剂的离子液体，由于具有独特的离子性质、结构及组成，而具有优良的催化及助催化等性质，作为溶剂时兼有催化剂的特殊效果。在此基础上，本文探索以离子液体为溶剂合成六氯环三磷腈以及聚磷腈。本文以五氯化磷，氯化铵为原料，以含氯阴离子离子液体为溶剂，催化合成六氯环三磷腈。首先在1-甲基-3-丁基咪唑氯和氯化锌组成的离子液体中，探索了离子液体组成、离子液体用量、反应温度等条件对六氯环三磷腈合成的影响。当1-甲基-3-丁基咪唑氯与ZnCl₂物质的量比为6:1，离子液体与反应物五氯化磷质量比为5:1，反应温度为130℃，反应时间5h时，六氯环三磷腈产率为71.9%。作为反应溶剂的离子液体不需提纯，可以重复使用7次，其催化活性基本保持不变。与传统合成方法相比，后处理很简单，离子液体可循环利用，极大地减少了有机溶剂的使用。在此基础上，考察了不同离子液体对合成六氯环三磷腈的影响，首先改变阳离子结构，发现咪唑型离子液体要优于季铵型离子液体；咪唑型离子液体中，咪唑环上侧链碳原子的增加对产率的影响不大；其次考察了金属氯化物的种类对合成六氯环三磷腈的影响，发现1-甲基-3-丁基咪唑氯分别与ZnCl₂、FeCl₃、CuCl₂、NiCl₂、CrCl₃、AlCl₃、CuCl、MgCl₂等金属氯化物混合形成的离子液体中，ZnCl₂与1-甲基-3-丁基咪唑氯组成的离子液体，合成效果最好。最后，以ZnCl₂与1-甲基-3-丁基咪唑氯组成的离子液体为溶剂和催化剂，探索以氨基甲酸铵或乙酸铵取代氯化铵，与五氯化磷在均相体系中反应合成六氯环三磷腈，效果不很理想。也尝试研究了在离子液体中六氯环三磷腈的聚合反应。更多还原

【Abstract】 Hexachlorocyclotriphosphazene, with a backbone of alternating phosphorus and nitrogenatoms, is an important feedstock to prepare phosphazene compounds, Because the chlorideatoms on hexachlorocyclotriphosphazene show high reacticity, it can be substituted bymany useful groups which can be used in many fileds, such as membrane technology, fireretardancy, special rubber, elastomers, optical and biomedical materials etc. There isrealistic value for us to study the phosphazene compounds because phosphorus resources isrich in China. Which is considered a environmentally friendly solvents, Ionic liquids isdiffer from molecular solvents by their unique ionic character and their “structure andorganization” which can lead to specific effects. On this basis,hexachlorocyclotriphosphazene and polyphosphazene were prepared by reaction in ionicliquids.Hexachlorocyclotriphosphazene was prepared by the reaction of ammonium chloridewith phosphorus pentachloride in the ionic liquids with chlorine anion. First, The reactioneffects of hexachlorocyclotriphosphazene in1-butyl-3-methylimidazolium chloride/znicchloride ionic liquids was compared with each other. The effect of1-butyl-3-methylimidazolium chloride/znic chloride ratio, reaction temperature, theamount of the ionic liquids used in this reaction were investigated. The experimental resultsshowed that the highest yield was achieved in71.9%at the temperature of130℃after5husing1-butyl-3-methylimidazolium chloride and ZnCl₂（mole ration is6:1） as thepromoting media, and this catalyst could be used7times almost without losing its catalyticactivity. Compared with conventional synthetic methods, that the ionic liquids were used asan alternative for the traditional organic solvent, the after-treatment is very simple, the ionicliquid can be recycled, and greatly reducing the use of organic solvents.Second, the reaction effects of hexachlorocyclotriphosphazene in different ionic liquidswas compared with each other, changing the cation structure, We found that theimidazolium ionic liquids is superior to the quaternary ammonium ionic liquids andimidazolium salts of different alkyl groups has little effect on the yield. Different metallicsalts （ZnCl₂, FeCl₃, CuCl₂, NiCl₂, CrCl₃, AlCl₃, CuCl, MgCl₂） with 1-butyl-3-methylimidazolium chloride were tested for this reaction and found that thereaction effect in this1-butyl-3-methylimidazolium chloride/znic chloride ionic liquid isexcellent.At last, hexachlorocyclotriphosphazene was also synthesized in ionic liquid ammoniumcarbamate or ammonium acetate as the nitrogen source, but the effect of that reaction is notideal. The ploymerization of hexachlorocyclotriphosphazene was also experimented inthese ionic liquids.更多还原