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Dawso结构磷钨酸催化合成对羟基苯甲酸正丁酯
  • ISSN号:1004-1656
  • 期刊名称:化学研究与应用
  • 时间:2015.9.20
  • 页码:1247-1252
  • 分类:O625.523[理学—有机化学;理学—化学]
  • 作者机构:[1]九江学院化学与环境工程学院,江西九江332005
  • 相关基金:国家自然科学基金项目(21161009)资助; 江西省自然科学基金项目(20132BAB203004,20122BAB213001)资助; 江西省教育厅科技项目(GJJ12616,GJJ14731)资助; 九江学院科技项目(2013KJ005)资助
  • 相关项目:负载Dawson型磷钨酸盐催化剂的设计合成、催化性能及负载机制研究
作者: 曹小华|
中文摘要:

以对羟基苯甲酸和正丁醇为原料、Dawson结构磷钨酸(H6P2W18O62·13H2O)为催化剂,催化对合成对羟基苯甲酸正丁酯,并对催化剂进行Py-IR、NH3-TPD表征。通过正交实验考察了各因素对酯收率的影响,探索了反应机理。Py-IR结果显示催化剂同时具有Brnsted酸中心和Lewis酸中心,NH3-TPD证实催化剂表面存在弱酸、中强酸和强酸位,其中中强酸位所占比例最大。实验结果表明:酯化催化反应同时发生在Brnsted酸中心和Lewis酸中心上,H6P2W18O62·13H2O具有较好的催化活性。当反应温度为125℃,反应时间为3.0h,催化剂用量为4.9%(基于反应物总质量),醇酸摩尔比为2∶1时,产物分离收率达91.3%。催化剂重复使用5次,产物收率仍可达70.3%。H6P2W18O62·n H2O替代硫酸作催化剂,既提高了产物的收率和纯度,又简化了工艺流程,减少了环境污染,催化剂经简单处理即可重复使用。

英文摘要:

Preparation of n-butyl p-hydroxybenzoate by the esterification of p-hydroxy benzoic acid and n-butanol using dawson structure phosphotungstic acid as catalyst was reported. The catalyst was characterized by Py-IR and NH3-TPD. The main influential factors of reaction were investigated by orthogonal experiments and the possible reaction mechanism was discussed. Py-IR results showed that both Bronsted(B)acid sites and Lewis(L)acid sites co-exist on the surface of the catalyst. The results of NH3-TPD suggested that the catalyst possessed weak,medium and strong acid sites,among which the medium acid sites accounted for the lar-gest proportion. The results obtained indicated that the esterification reaction was a Br? nsted acid-Lewis acid cooperativity catalytic reaction. Dawson structure phosphotungstic acid possessed a fairly high catalytic activity for the esterification reaction. The optimal condition could be listed as follows:the best reaction temperature was 125℃,the reaction time was 3. 0 h,the mass ratio of the cata-lyst to total reactants was 4. 9%,and the molar ratio of n-butyl alcohol to p-hydroxyl benzoic acid was 2∶1. Under these conditions, the yield of butyl p-hydroxyl benzoate could reach 91. 3%, and it was still over 70. 3%when the catalyst was reused for five times. The primary advantage of replacement of sulphuric acid to dawson structure phosphotungstic acid might be not only as the im-provement of yield and selectivity,but also the simplification of the process and the reduction of environmental pollution. The cata-lyst could be used repeatedly after being treated simply.

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期刊信息
  • 《化学研究与应用》
  • 中国科技核心期刊
  • 主管单位:四川省科学技术协会
  • 主办单位:四川省化学化工学会 四川大学
  • 主编:胡常伟
  • 地址:成都市武候区望江路29号四川大学化学学院内
  • 邮编:610064
  • 邮箱:chemra@scu.edu.cn
  • 电话:028-85418495
  • 国际标准刊号:ISSN:1004-1656
  • 国内统一刊号:ISSN:51-1378/O6
  • 邮发代号:62-180
  • 获奖情况:
  • 化学类中文核心期刊,美国化学文摘(CA)收录期刊,中国科学引文数据库来源期刊
  • 国内外数据库收录:
  • 美国化学文摘(网络版),日本日本科学技术振兴机构数据库,中国中国科技核心期刊,中国北大核心期刊(2004版),中国北大核心期刊(2008版),中国北大核心期刊(2011版),中国北大核心期刊(2014版),英国英国皇家化学学会文摘,中国北大核心期刊(2000版)
  • 被引量:16918