碱性离子液体催化甘油合成1,2-甘油碳酸酯

催化学报 , 2014, (5): 757-762. doi: 10.1016/S1872-2067(14)60036-X

碱性离子液体催化甘油合成1,2-甘油碳酸酯

易宇轩 ^1, , 申越 ^2, , 孙建奎 ^3, , 王波 ^4, , 许凤 ^5, , 孙润仓 ^6,

1.北京林业大学材料科学与技术学院，林木生物质化学北京市重点实验室，北京100083

2.北京林业大学材料科学与技术学院，林木生物质化学北京市重点实验室，北京100083

3.北京林业大学材料科学与技术学院，林木生物质化学北京市重点实验室，北京100083

4.北京林业大学材料科学与技术学院，林木生物质化学北京市重点实验室，北京100083

5.北京林业大学材料科学与技术学院，林木生物质化学北京市重点实验室，北京100083

6.北京林业大学材料科学与技术学院，林木生物质化学北京市重点实验室，北京100083; 华南理工大学制浆造纸工程国家重点实验室，广东广州510640

基金项目: 教育部新世纪优秀人才支持(NCET-13-0671) the National Natural Science Foundation of China(31170556) 十二五国家科技计划项目(2012BAD32B06) 国家重点基础研究发展计划(973计划,2010CB732204).This work was supported by the National Science and Technology Program of the Twelfth Five-Year Plan Period(2012BAD32B06) New Century Excellent Talents in University(NCET-13-0671) 北京高等学校“青年英才计划”(YETP0765) 中央高校基本科研业务费专项资金(TD2011-11) China Postdoctoral Science Special Foun-dation(2012T50051) 国家自然科学基金(31170556) the National Basic Research Program of China(973 Program,2010CB732204) Beijing Higher Education Young Elite Teacher Project(YETP0765) 中国博士后科学基金(2012T50051) Fundamental Research Funds for the Central Universities(TD2011-11)

关键词：酯交换 , 甘油 , 甘油碳酸酯 , 碱性离子液体 , 二烷基碳酸酯 , 平台化合物

Basic ionic liquids promoted the synthesis of glycerol 1,2-carbonate from glycerol

Keywords： Transesterification , Glycerol , Glycerol carbonate , Basic ionic liquid , Dialkyl carbonate , Platform chemcial

以离子液体为催化剂,在无溶剂体系中,考察了生物质平台化合物甘油转化1,2-甘油碳酸酯的反应.与酸性离子液体和常用无机碱性催化剂相比,碱性离子液体咪唑基1-丁基-3-甲基咪唑([Bmim]Im)、氢氧化1-丁基-3-甲基咪唑([Bmim]OH)、咪唑基1-烯丙基-3-甲基咪唑([Amim]Im)、氢氧化1-烯丙基-3-甲基咪唑([Amim]OH)在甘油与碳酸二甲酯的酯交换反应中表现出优异的活性.其中,以[Bmim]Im离子液体为催化剂时甘油转化率为98.4%和甘油碳酸酯选择性接近100%.另外,该离子液体可以回收重复利用3次后甘油转化率仍可达92%,甘油碳酸酯选择性可近100%.此碱性离子液体催化方法具有反应结果较好、产物分离简单、条件温和以及环境友好等特点.

Glycerol has been subjected to a transesterification process with dialkyl carbonate to generate glyc-erol 1,2-carbonate (GC) using different ionic liquids as catalysts under solvent-free conditions. The basic ionic liquids 1-butyl-3-methylimidazolium imidazolium ([Bmim]Im), 1-butyl-3-methylimidaz-olium hydroxide ([Bmim]OH), 1-allyl-3-methylimidazolium imidazolium ([Amim]Im), and 1-allyl-3-methylimidazolium hydroxide ([Amim]OH) worked well as catalysts compared with acidic ionic liquid and inorganic basic catalysts. Subsequent optimization of the reaction conditions using [Bmim]Im as a catalyst led to 98.4%glycerol conversion and up to 100%GC selectivity at 70 °C under ambient pressure. The recovery and reuse of these ionic liquids were also satisfactory. [Bmim]Im could be reused three times (i.e., 92.0%glycerol conversion and near 100%GC selectivi-ty). This method exhibited several special features including a simple product isolation procedure, high product yield, exclusive selectivity, and mild conditions, as well as avoiding the use of any toxic catalysts.

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