六氯环三磷腈及其衍生物的合成-高分子化学与物理专业论文.docxVIP

三峡大学硕士学位论文 三 峡 大 学 硕 士 学 位 论 文 万方数据 万方数据 摘 要 环三磷腈是一类骨架由磷、氮元素单双健交替排列形成的化合物，具有良好 的热稳定性和阻燃性，广泛用于阻燃、催化、医药、农业等领域。虽然六氯环三 磷腈及其衍生物的研究异常活跃，但是有关含酰腙基的六氯环三磷腈衍生物的研 究文献报道极少。具体研究内容如下： （1）本论文以三氯化磷、氯气和氯化铵为原料，氯苯为溶剂，以氧化锌和氯化 锌为催化剂合成六氯环三磷腈。通过对催化剂的种类和用量、物料比、反应溶剂、 反应时间，反应温度等影因素进行研究，探索出了最优合成工艺：n(PCl3): n(ZnO): n(ZnCl2) : n(NH4Cl) = 1: 0.042: 0.2: 1.3，三氯化磷的时间约 2.5h，同时向反应瓶 中通入氯气，时间约 2.75h，通氯气完毕，回流 7h， 最高环状粗品收率为 94.71%， 六氯环三磷腈纯品的收率为 75.77%。 （2）以六氯环三磷腈为原料，合成了 8 个新型的含酰腙基的六氯环三磷腈衍生 物，并对目标化合物进行了 IR、1H NMR、13C NMR、ESI-MS 和元素分析。这 些化合物是： III （3）用合成的含酰腙基的六氯环三磷腈类化合物（8a-8g）与 ABS 树脂制备了 阻燃 ABS 树脂，测试了其极限氧指数（LOI）和 UL 94 垂直燃烧性能。结果表 明，所合成的化合物（8a-8g）添加到 ABS 树脂中均可以显著改善 ABS 树脂的 阻燃性能，其中化合物 8e、8f 阻燃效果最好。 关键词：六氯环三磷腈；合成，六(4-酰腙基-2-甲氧基苯氧基)环三磷腈；阻燃 ABS 树脂；氧指数 III Abstract Because chlorocyclotriphosphazene contains high phosphorus and nitrogen portion, most derivatives containing hexachlorocyclotriphosphazene unit have excellent fire-retardant property and heat stability. Many of them have been developed for different purposed in the fire-retardant, catalysis, medicine and agriculture field. However, there is little report of a generally useful synthesis of hexakis- (4-acylhydrazone-2-aryl)cyclotriphosphazene. What the paper studied may be summarized as follows: Hexachlorocyclotriphosphazene was prepared by the reaction of ammonium chloride, chlorine gas, with phosphorous trichloride in chlorobenzene, using zinc oxide and zinc chloride as catalyst system. The optimal reaction condition was reached by choosing the kinds of catalyst and dosage of the catalyst, changing the proportion of the reactants, reaction solvent, reaction time, reaction temperature. The optimal reaction condition is as follows: the molar ration of n(PCl3): n(ZnO): n(ZnCl2) : n(NH4Cl) = 1: 0.042: 0.2: 1.3, PCl3 was added dropwise to the system with in 2.5h, Cl2 was added to he system with in 2.75h, then the reaction mixture was stirred for another 7h. The highest yield of crude hexachlorocyclotriphosphazene is 94.71% and the pure hexachlorocyclotripho