以水滑石为前驱体的新溴源体系的研究

发布时间：2018-07-25 08:42

【摘要】：以溴酸根插层的锌铝水滑石(Zn/Al-BrO3--LDHs)为载体,与Br-等还原剂构建形成新型的溴源体系。用不同方法制备了Zn/Al-BrO3--LDHs,利用XRD、TG、FTIR手段对水滑石样品进行了表征分析。为实现溴源体系在实际应用中的有效控溴,对Zn/Al-BrO3--LDHs中BrO3-的释放行为进行了研究,并考察了合成方法、温度、交换离子类型、p H值等因素对BrO3-释放行为的影响,结果表明用共沉淀法合成的水滑石的可控性能较好,温度升高会加速BrO3-的释放,交换离子的交换性越强,Br O3-释放得越快,在pH为9.0的磷酸盐缓冲溶液中的释放速率要比pH为4.0的磷酸盐缓冲溶液中的快。进一步采用四种动力学模型进行动力学拟合,拟合结果表明LDHs-BrO3-中BrO3-的释放行为符合Bhaskar方程。将溴酸根插层的水滑石作为存放溴酸根离子的容器与还原剂溴离子构建形成新型的溴源体系,应用于3,5-邻氨基苯甲酸甲酯的合成,考察投料比、溶剂、反应温度及反应时间等因素对产物收率的影响。结果表明:用该体系合成3,5-邻氨基苯甲酸甲酯反应条件比较温和,腐蚀小,污染较少。在n(BrO3-):n(邻氨基苯甲酸甲酯)=2.5:3,二氯甲烷:水(10 ml:5 ml)作混合溶剂的30°C条件下反应6 h,得3,5-二溴邻氨基苯甲酸甲酯的收率为91.43%。在优化条件下,对芳胺溴代底物进行了扩展研究。研究结果表明,该反应是一个温和,环保的新型溴代方式。
[Abstract]:A new bromine source system was constructed by using zinc-aluminum hydrotalcite (Zn/Al-BrO3--LDHs) intercalated with bromate as carrier and with Br- and other reducing agents. Zn- / Al-BrO3-LDHs were prepared by different methods. The samples of hydrotalcite were characterized by XRD- TG- FTIR. In order to control bromine effectively in practical application, the release behavior of BrO3- in Zn/Al-BrO3--LDHs was studied, and the effects of synthesis method, temperature, pH value of exchange ion type on BrO3- release behavior were investigated. The results show that the hydrotalcite synthesized by coprecipitation has better controllable performance, and the higher the temperature, the faster the release of BrO3-, the stronger the exchangeability of ion is, the faster the release of BrO3- is. The release rate in phosphate buffer solution with pH 9.0 is faster than that in phosphate buffer solution with pH 4.0. Furthermore, four kinds of kinetic models were used to simulate the kinetics. The results show that the release behavior of BrO3- in LDHs-BrO3- conforms to the Bhaskar equation. A new bromine source system was constructed by using bromate intercalated hydrotalcite as a container for storing bromate ion and reducing bromine ion. The bromine source system was applied to the synthesis of methyl 3,5-aminobenzoate. The effect of reaction temperature and reaction time on the yield of the product. The results showed that the reaction conditions were mild, corrosion was small and pollution was less. Under the conditions of n (BrO3-): n (methyl o-aminobenzoate) 2.5: 3, dichloromethane: water (10 ml:5 ml) as the mixed solvent for 6 h, the yield of 3-dibromo-o-aminobenzoate was 91.43. Under the optimized conditions, the expansion of arylamine brominated substrates was studied. The results show that the reaction is a mild, environmental-friendly new bromination method.
【学位授予单位】：浙江工业大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB34

【相似文献】