四叔丁基金属酞菁催化活化CO_2与环氧丙烷的环加成反应  

Cycloaddition of Propylene Oxide with Carbon Dioxide Activated by Tetra-tert-Butyl Metal Phthalocyanine

作　　者：张英菊[1] 梁斌[1] 潘玉珍[1] 何仁[1] 

机构地区：[1]大连理工大学精细化工国家重点实验室,辽宁大连116012

出　　处：《催化学报》2003年第10期765-768,共4页

摘　　要：以四叔丁基金属酞菁与三正丁胺等有机碱组成的二元催化体系催化活化CO2 与环氧丙烷进行环加成反应制备碳酸丙烯酯 .同一种金属酞菁与不同有机碱组成的二元催化体系的催化活性与有机碱的碱性强弱一致 .有机碱的用量和反应时间对反应均有一定影响 ,温度对反应的影响较大 .与未取代的金属酞菁相比 ,四叔丁基金属酞菁表现出更高的催化活性 .四叔丁基酞菁镁的催化活性高于四叔丁基酞菁铁 ,在 14 0℃ ,以四叔丁基金属酞菁镁 /三正丁胺为催化剂 ,碳酸丙烯酯的产率达90 4 % .The cycloaddition of propylene oxide with carbon dioxide activated by catalysts is one of the industrial synthetic processes for the production of propylene carbonate (PC) and very attractive from the viewpoint of 'green chemistry' and 'atom economy'. In this paper, highly soluble tetra tert butyl magnesium phthalocyanine (( t Bu) 4MgPc) and tetra tert butyl ferrous phthalocyanine (( t Bu) 4FePc) are synthesized on the basis of our previous works, and propylene carbonate is prepared by using binary catalytic systems of ( t Bu) 4MPc and organic bases via cycloaddition reaction. The experiments indicate that when only ( t Bu) 4FePc or organic bases such as tributylamine (TBA) is used as catalyst, rather low activity towards the cycloaddition is observed and the yields of PC in the above cases are 7 8% and 1 6%, respectively. However, the binary catalytic system of ( t Bu) 4FePc and TBA can effectively catalyze the cycloaddition of propylene oxide with CO 2 and the yield of PC is 73 2% after reaction at 120 ℃ for 3 h. The higher the basicity of the organic base, the higher the catalytic activity. The catalytic properties of these systems are significantly affected by reaction temperature. As ( t Bu) 4FePc/TBA is used as catalyst, the yield of PC increases linearly with temperature ranging from 100 to 120 ℃. The catalytic activity of ( t Bu) 4MgPc/TBA is higher than that of ( t Bu) 4FePc/TBA under the same experimental conditions. The yields of PC for the two catalysts are 90 4% and 83 3%, respectively, after reaction at 140 ℃ for 3 h. Tert butyl substituted metal phthalocyanine shows higher catalytic activity than unsubstituted metal phthalocyanine because the homogeneous catalytic system resulted from more soluble ( t Bu) 4MPc is beneficial to the reaction and the increased charge density of ( t Bu) 4MPc caused by introducing tert butyl, an electron donor group, facilitates the insertion of CO 2 in cycloaddition. The yiel

关 键 词：四叔丁基酞菁铁 四叔丁基酞菁镁 二氧化碳 环氧丙烷 环加成 碳酸丙烯酯 

分 类 号：O643.3[理学—物理化学]