含钴介孔分子筛Co-MCM-41耦合溴化四丁基铵协同催化苯乙烯直接氧化碳酰化制备苯乙烯环状碳酸酯

应用化学, 2014, 31(3): 268-273. doi: 10.3724/SP.J.1095.2014.30263

含钴介孔分子筛Co-MCM-41耦合溴化四丁基铵协同催化苯乙烯直接氧化碳酰化制备苯乙烯环状碳酸酯

王芳霄 ^1, , 朱前程 ^2, , 向丹 ^3, , 梁林 ^4, , 孙建敏 ^5,

1.哈尔滨工业大学基础与交叉科学研究院哈尔滨150080

2.哈尔滨工业大学基础与交叉科学研究院哈尔滨150080

3.西安交通大学理学院西安710049

4.哈尔滨工业大学生命科学与技术学院哈尔滨150080

5.哈尔滨工业大学城市水资源与水环境国家重点实验室哈尔滨150080;哈尔滨工业大学基础与交叉科学研究院哈尔滨150080

基金项目: the National Natural Science Foundation of China(21073049,21373069) 国家自然科学基金(21073049,21373069) 教育部新世纪人才(NCET-10-0064) 哈尔滨工业大学城市水资源与水环境国家重点实验室基金项目(2013TS01) New Century Excellent Talents in University(NCET-10-0064) State Key Lab of Urban Water Resource and Environment of Harbin Institute of Technology(HIT2013TS01)

关键词： Co-MCM-41 , 溴化四丁基铵 , 苯乙烯 , 二氧化碳 , 苯乙烯环状碳酸酯

Direct Oxidative Carboxylation of Styrene to Styrene Carbonate over Cobalt-containing Mesoporous Molecular Sieves (Co-MCM-41) and Tetrabutylammonium Bromide Co-catalysts

Keywords： Co-MCM-41/tetrabutylammonium bromide , styrene , carbon dioxide , oxidative carboxylation , styrene carbonate

以苯乙烯为起始物,经催化环氧化然后环氧化物与二氧化碳环加成反应“串联一锅”制备苯乙烯环状碳酸酯,反应工艺简单(避免了中间体环氧化物的事先合成与分离)且绿色经济(原料苯乙烯比苯乙烯环氧化物价格低廉且毒性小),工艺具有潜在的工业应用前景.探讨了掺杂不同金属(Co,Fe,Ni,Mn,Cu,Ti)的MCM-41介孔分子筛催化剂对苯乙烯环氧化的转化率和选择性,研究表明以含钴介孔分子筛Co-MCM-41为最佳,并以Co-MCM-41耦合溴化四丁基铵(TBAB)为催化剂,考察了苯乙烯直接氧化碳酰化制苯乙烯环状碳酸酯反应.从影响反应活性和产物选择性的因素来优化反应,在80℃、4 MPa、CO2压力下,反应7h,碳酸酯的收率达到46.1％.Co-MCM-41催化第一步苯乙烯环氧化反应,溴化四丁基铵催化第二步环加成反应.

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