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含苯氧基、联萘氧基、偶氮苯氧基均三嗪衍生物的制备与表征

Synthesis and Characterization of the S-triazine Derivatives with Phenoxy, Bi-naphthoxy and Azo-phenoxy

【作者】 陈剑伟

【导师】 翁家宝;

【作者基本信息】 福建师范大学 , 高分子化学与物理, 2010, 硕士

【摘要】 本文以三聚氯氰作为提供均三嗪环的主要原料,利用其结构中的三个氯原子参与反应时的不同反应活性,可以控制条件分步进行的特点,制备了一系列新型含均三嗪环化合物,采用元素分析、红外光谱、核磁共振等研究方法对它们的结构进行表征,并研究了其溶解性,热稳定性等性能。具体包括以下内容:1.以三聚氯氰和对硝基苯酚为原料,控制反应温度,采用丙酮水法制备了2,4,6-三(4-硝基苯氧基)-1,3,5-均三嗪。采用三种不同的还原方法对硝基进行还原,制得2,4,6-三(4-氨基苯氧基)-1,3,5-均三嗪。应用元素分析,1H-NMR, IR对所得的产品进行表征。其中2,4,6-三(4-硝基苯氧基)-1,3,5-均三嗪具有很好的热稳定性,初始分解温度为430℃。所选择的三种还原方法中以Pd/C水合肼催化体系的还原效果最好。2.以三聚氯氰和1,1’-联二萘酚为原料,NaOH为缚酸剂,十六烷基三甲基溴化铵为相转移催化剂,界面缩聚制备聚2-氯-4-1,1’-联萘氧基-1,3,5-均三嗪。采用紫外,荧光,IR, 1H-NMR, GPC等对聚合物进行表征;同时通过TG,DSC研究了该聚合物的热性能;通过原子力显微镜观察该聚合物薄膜微观形态。结果表明,此聚合物的二氯甲烷溶液能在玻璃片上成膜,且出现纳米级孔洞。3.以三聚氯氰和4,4-二羟基偶氮苯为原料,NaOH为缚酸剂,十六烷基三甲基溴化铵为相转移催化剂,界面缩聚制备聚2-氯-4,4,4’-偶氮苯氧基-1,3,5-均三嗪(PCCAB)。以NaOH为缚酸剂,在丙酮水溶液中将4,4’-二羟基偶氮苯和2-苯胺基-4,6-二氯-1,3,5-均三嗪反应制备了4,4’-二(间苯胺基一氯三嗪基)羟基偶氮苯(DIATOB)。通过红外、核磁、紫外对其结构进行表征。通过TG对产品进行热性能分析;通过紫外光谱测试了DIATOB的光响应性能;同时观察了两者的溶解性,通过比较结果表明,PCCAB即使在DMF中也不溶解,而DIATOB则可溶于多数常用溶剂。

【Abstract】 In this paper, cyanuric chloride which structure containing three chlorine atoms was used as the main raw material for the provision of s-triazine ring.With the different reactivities of the three chlorine atoms in cyanuric chloride, a series of new s-triazine ring compounds were received by the step-wise reaction through the controlling of the temperature.The structure of these compounds were characterized by Elemental analysis, IR,1H NMR and other research methods,also the solubility, thermal stability properties were studied. It can be summarized as follows.1. With cyanuric chloride and p-nitrophenol as the raw materials,2,4,6-3-p-nitrophenoxy-1,3,5-triazine was prepared by controlling of reaction temperature in acetone and water. Three different methods were used for nitro reduction to obtain 2,4,6--aminophenoxy-1,3,5-triazine. With elemental analysis,1H-NMR, IR,TG characterization the products obtained,2,4,6-3-p-nitrophenoxy-1,3,5-triazine shows good thermal stability which the initial decomposition temperature was at 430℃. Pd/C hydrazine catalyst system shows a good result in three kinds of reduction methods.2. With cyanuric chloride and 1,1’-BINOL as the raw materials, NaOH as base, cetyltrimethyl ammonium bromide as phase transfer catalyst, poly 2-chloro-4-1,1’-bi naphthyloxy-1,3,5-triazine were prepared through interfacial polymerization. Its structure was characterized using UV, IR,1H-NMR, RF, GPC. Also by atomic force microscope(AFM), the surface of the polymer film was observed.3. PCCAB was abtained by the reaction of cyanuric chloride and 4,4’-hydroxyazobenzene using interfacial polymerization. DIATOB was got by the reaction of 2-Anilino-4,6-dicholoride-1,3,5-traizine and 4,4’-hydroxyazobenzene at 40℃in the solvent of acetone and water. FTIR,1HNMR, TG, DSC, UV were used to characterize the structures. And the opticl response property of DIATOB was studied by UV-Vis. Also the solubility of the two products were studied, PCCAB won’t dissolve even in DMF, but DIATOB can be dissolved in most kinds of solvent.

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