有机化学 ›› 2004, Vol. 24 ›› Issue (10): 1262-1266. 上一篇    下一篇

研究简报

固体超强酸催化剂SO2-4/TiO2-WO3的制备及其催化性能研究

杨水金*,a,b, 白爱民a, 余协卿a, 孙聚堂b   

  1. a湖北师范学院化学与环境工程系 黄石 435002;
    b武汉大学化学与分子科学学院 武汉 430072
  • 收稿日期:2003-11-10 修回日期:2004-03-25 接受日期:2004-04-19 发布日期:2022-09-20
  • 基金资助:
    国家自然科学基金(No. 29971024)和湖北省教育厅重点科研基金(Nos. 2002A00008; 2004D007)资助项目.

Preparation and Catalytic Activity of SO2-4/TiO2-WO3

YANG Shui-Jin*,a,b, BAI Ai-Mina, YU Xie-Qinga, SUN Ju-Tangb   

  1. aDepartment of Chemistry and Environmental Engineering, Hubei Normal University, Huangshi 435002;
    bCollege of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072
  • Received:2003-11-10 Revised:2004-03-25 Accepted:2004-04-19 Published:2022-09-20
  • Contact: * E-mail: yangshuijin@163.com; Tel.: 0714-3620366.

制备了固体超强酸催化剂SO2-4/TiO2-WO3,并以丁酸丁酯的合成作为探针反应,系统考察了WO3的含量、硫酸浸渍浓度、焙烧温度等制备条件对SO2-4/TiO2-WO3催化活性的影响.实验表明:制备催化剂的适宜条件为m(H2WO4)=12.5%,硫酸浸渍浓度为1.0 mol·L-1,焙烧温度为580 ℃,活化时间3 h.利用优化条件下制备的催化剂SO2-4/TiO2-WO3催化合成缩醛(酮),在醛/酮与二元醇(乙二醇,1,2-丙二醇)的投料摩尔比为1∶1.5,催化剂的用量占反应物总投料质量的0.5%,反应时间为1 h条件下,2-甲基-2-乙氧羰甲基-1,3-二氧环戊烷的收率为78.7%, 2,4-二甲基-2-乙氧羰甲基-1,3-二氧环戊烷的收率为83.0%,环己酮-乙二醇缩酮的收率为85.9%,环己酮-1,2-丙二醇缩酮的收率为84.6%,丁酮-乙二醇缩酮的收率为70.7%,丁酮-1,2-丙二醇缩酮的收率为88.3%, 2-丙基-1,3-二氧环戊烷的收率为80.6%, 4-甲基-2-丙基-1,3-二氧环戊烷的收率为79.6%, 2-异丙基-1,3-二氧环戊烷的收率为64.2%, 4-甲基-2-异丙基-1,3-二氧环戊烷的收率为83.3%, 2-苯基-1,3-二氧环戊烷的收率为75.3%, 4-甲基-2-苯基-1,3-二氧环戊烷的收率为95.1%.

关键词: SO2-4/TiO2-WO3, 固体超强酸, 催化, 丁酸丁酯, 缩醛, 缩酮

A novel solid superacid catalyst, SO2-4/TiO2-WO3, was prepared. Its catalytic activity for twelve important ketals andacetals was measured with esterification of n-butanoic acid with n-butyl alcohol as probing reaction. The preparation conditions of SO2-4/TiO2-WO3 have also been investigated, that is, the mass ratio of the H2WO4 used in the compound is 12.5%, the calcining temperature is 580 ℃, the calcining time is 3 h, and the soaked consistency of H2SO4 is 1.0 mol·L-1. Experimental results showed that SO2-4/TiO2-WO3 is an excellent catalyst for the synthesis of twelve important ketals and acetals. The optimumreaction conditions are that the molar ratio of aldehyde/ketone to glycol is 1∶1.5, the mass ratio of the catalyst used in the reactants is 0.5%, and the reaction time is 1.0 h. Under these conditions, the yield of 2-methyl-2-ethoxycarbonylmethyl-1,3-dioxolane is 78.7%, 2,4-dimethyl-2-ethoxycarbonylmethyl-1,3-dioxolane 83.0%, cyclohexanone ethylene ketal 85.9%, cyclohexanone 1,2-propanediol ketal 84.6%, butanone ethylene ketal 70.7%, butanone1,2-propanediol ketal 88.3%, 2-propyl-1,3-dioxolane 80.6%, 4-methyl-2-propyl-1,3-dioxolane 79.6%, 2-isopropyl-1,3-dioxolane 64.2%, 4-methyl-2-isopropyl-1,3-dioxolane 83.3%, 2-phenyl-1,3-dioxolane 75.3%, 4-methyl-2-phenyl-1,3-dioxolane 95.1%, respectively.

Key words: SO2-4/TiO2-WO3, solid superacid, catalysis, butyric butyl, acetal, ketal