以自制的负载氯化锂强酸性离子交换树脂为催化剂,采用间歇法研究了硼酸和甲醇酯化可逆反应的动力学。对可逆反应动力学方程进行线性化处理,确定了积分法拟合可逆反应动力学参数的方法,并以幂函数形式表达了指前因子与催化剂浓度的关系。测定了不同反应温度和催化剂用量下硼酸三甲酯得率随时间的变化,对动力学数据采用线性拟合,得到硼酸三甲酯非均相催化合成反应动力学方程式为:rA=4994C038cat exp(-〖SX(〗31 920〖〗RT〖SX)〗)CACB-3977C008cat exp(-〖SX(〗29 780〖〗RT〖SX)〗)CRCS。
Abstract
The kinetics of the reversible reaction between boronic acid and methanol was investigated by using the selfmade strong acid cation exchange resin loaded with lithium chloride as the catalyst. A method was established for fitting parameters of reversible reaction kinetic model derived from the integration method, and the relationship between preexponential constants and concentration of catalyst was expressed by power function. According to the variation of trimethyl borate yield with time, temperature and the amount of catalyst, the kinetic model was fitted by linear method. The equation of synthesis kinetics of trimethyl borate by inhomogeneous catalysis was showed as:rA=4994C038cat exp(-〖SX(〗31 920〖〗RT〖SX)〗)CACB-3977C008cat exp(-〖SX(〗29 780〖〗RT〖SX)〗)CRCS
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参考文献
[1]郑学家. 硼及硼酸盐产品开发和应用前景[J]. 无机盐工业, 2005,37(4): 1-3.
[2]张兴, 唐洪, 杨增家. 二氟甲氧基苯酚酯类液晶的合成[J]. 液晶与显示,2008,23(4):409-411.
[3]任元龙. 2-氯-5-三氟甲基苯基硼酸合成[J]. 宁波大学学报:理工版,2007,20(1):83-85.
[4]蒋欢妹,邓燕,张永强,等.对叔丁基苯硼酸的合成及表征[J]. 精细化工中间体,2007,37(1):34-36.
[5]肖海波,冷冰,田禾. 三苯胺-螺硅芴共聚物的合成[J].应用化学,2006,23(2):140-143.
[6]Chiras S J, Falls N. Process of preparing trimethyl borate[P]. US: 2947776, 1960-08-02.
[7]James B. Process for manufacture of trimethyl borate[P]. CA: 640596, 1961-01-05.
[8]Scheehte W H. Production of trimethyl borate[P]. US: 2689259, 1954-09-14.
[9]Mason R G. Method for the preparation of trimethyl borate[P].UK:818.62,1955-11-08.
[10]李小保,朱亮,苑光光,等. 氯化锂催化下硼酸和甲醇酯化反应动力学研究[J].无机盐工业,2009,41(12):25-26.
[11]王英,李程鹏,杨琨,等. 大孔磺酸树脂负载FeCl3固体超强酸催化剂的制备[J]. 天津师范大学学报:自然科学版,2003,23(1):22-24.
[12]金海玲,胡恭任,张卫江,等. 用三氟化硼乙醚络合物合成硼酸三甲酯[J]. 化学工业与工程,2006,23(3):243-246.
[13]段雪,苗敏,王作新,等. 二甘醇单丁醚硼酸酯合成动力学研究[J].北京化工学院学报:自然科学版,1992,19(3):57-62.
[14]段雪,苗敏,王作新,等. 非等温硼酸酯化反应动力学研究[J].化学学报,1992,50(11):1051-1055.
[15]廖安平,张雷,蓝丽红,等. 强酸性离子交换树脂催化合成乙酸乙酯动力学[J].化学反应工程与工艺,2008,24(4):363-367.
基金
收稿日期:2011-06-12修回日期:2011-10-08基金项目:江苏省高校优势学科建设工程资助项目第一作者:李小保,讲师,博士生。Email: njfulxb@126.com。