固体超强酸SO₄^2-/TiO₂/La³⁺催化合成TDCPP、TBC的研究

【作者】 于春红；

【导师】 杨锦飞；

【作者基本信息】 南京师范大学 ， 物理化学， 2008， 硕士

【摘要】 以三氯氧磷和环氧氯丙烷合成磷酸三（1，3-二氯-2-丙基）酯（TDCPP），以柠檬酸、正丁醇合成柠檬酸三丁酯（TBC）。考察了TDCPP和TBC的酯化合成体系。研究了固体超强酸SO₄^2-／TiO₂／La³⁺在合成TDCPP和TBC中的催化性能。并通过催化剂的活性评价和物化性能表征来研究催化剂的结构与性能的关系，为固体超强酸催化合成TDCPP和TBC的工业化提供了有益的依据。首先通过正交实验，考察了硫酸浓度、浸渍时间、焙烧温度、焙烧时间对固体超强酸催化剂SO₄^2-／TiO₂／La³⁺的催化活性的影响，并通过IR、XRD、热分析、SEM等方法对催化剂进行了表征。对TDCPP的酯化反应进行了考察，分别在TiCl₄、AlCl₃和自制固体超强酸催化剂SO₄^2-／TiO₂／La³⁺催化下研究了TDCPP的产率和酸值。研究了催化剂在TDCPP的合成反应中的催化性能和稳定性。结果表明硫酸浓度为0．8mol／L，焙烧温度为550℃，La³⁺的用量为5 mol％，浸渍时间为24 h，焙烧时间为3h，此时所制得催化剂具有较高的催化活性，TDCPP的产率高达98．5％。并通过IR，热分析等对TDCPP的结构进行了表征。对柠檬酸三丁酯（TBC）的酯化反应进行了考察，分别在无催化剂、浓硫酸、自制固体超强酸催化剂SO₄^2-／TiO₂／La³⁺催化下，研究了柠檬酸三丁酯（TBC）酯化合成反应中酸转化率、出水量与反应时间的关系，并在固体超强酸催化剂催化下通过单因素实验对酸醇比、催化剂用量等酯化反应条件进行了优化。当催化剂用量为总质量的3．5％，酸醇摩尔比为1：4．5，酯化温度控制在145℃左右时产率高达96．4％。通过IR、热分析对TBC、ATBC的结构进行了表征。更多还原

【Abstract】 To phosphorus oxychloride and epichlorohydrin Synthesis of （1,3-dichloro-2-propyl） ester （TDCPP）, citric acid, n-butyl alcohol synthesis of Tributyl Citrate （TBC）. The catalytic properties of the catalyst SO₄^2-/TiO₂/La³⁺ in esterification of citric acid with n-butanoland phosphorus oxychloride with epichlorohydrin were studied. The correlation between its structure and properties was also investigated. And through evaluation of the activity of catalysts and physico-chemical characterization of the catalysts to study the relationship between structure and properties of the catalytic synthesis of solid superacid TDCPP、TBC industrialization and provide a useful basis.By orthogonal experiment, inspected the concentration of sulfuric acid, soaking time, the calcination temperature and baking time on the solid superacid catalyst SO₄^2-/TiO₂/La³⁺ the impact of the catalytic activity, and through IR and XRD, thermal analysis and SEM methods of catalyst were characterized.This paper reported the Acid Value and esterification synthesis of Tris （1, 3-dichloro-2-propyl） ester under TiCl₄、AlCl₃ or solid super acid SO₄^2-/TiO₂/La³⁺. The catalytic properties and stability of SO₄^2-TiO₂/La³⁺ was surveyed. The suitable synthesis condition are defined as follows: Sulfuric acid concentration is 0.8mol/L, roasting temperature550℃, the mass of La³⁺5mol%, impregnation time 24h, roasting time 3h. The yield of TDCPP was about 98. 5%. The structure of the product was defined by IR and TG.This paper reported the esterification synthesis of TBC under no catalyst, H₂S0₄, or solid super acid S0₄^2-/Ti0₂/La³⁺ The correlation between reaction conversion, water yieldand reaction time was surveyed. The effects of initial molar ratio and catalyst quantity were investigated and the optimum synthesis conditions were found. The suitable synthesis condition are defined as follows: the mass of catalyst 3.5%, n （citric acid）: （n-butyl alcohol） =1: 4.5, esterification of temperaturel45℃. The yield of TBC was about 96. 5%. The structure of the products was defined by IR and TG.更多还原