高效可重复使用N-杂多酸离子液体催化α-甲基苯乙烯与甲醛反应的研究
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- 英文论文题名：Investigation of Efficient and Reusable Catalysts of N-Heteropolyacid Ionic Liquid for Prins Rection of α-Methylstyrene with Formaldehyde
- 论文作者：祁彦龙 ; 张春雨 ; 李广鑫 ; 张学全 ; 白晨曦
- 英文论文作者：Y.Qi ; C.Zhang ; G.Li ; X.Zhang ; C.Bai ; Changchun Institute of Applied Chemistry ; Chinese Academy of Sciences ; University of Chinese Academy of Sciences
- 年：2016
- 作者机构：中国科学院长春应用化学研究所;中国科学院大学;
- 论文关键词：离子液体 ; 无溶剂合成 ; 催化 ; 回收利用
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第三十三分会：绿色化学
- 语种：中文
- 分类号：O621.251
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第三十三分会 ; 绿色化学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：294k
- 原文格式：D
- 会议级别：全国
摘要
本研究以N-甲基吡咯烷酮、N,N-二甲基-四氢-2-嘧啶酮、N-甲基己内酰胺和H_3PW_(12)O_(40)、H_3PMo_(12)O_(40)、H_4SiW_(12)O_(40)等合成了N-杂多酸离子液体型催化剂,用UV、NH_3-TPD、NMR、XRD、TG和元素分析仪进行分析表征。催化α-甲基苯乙烯和甲醛溶液无溶剂合成4-甲基-4-苯基-1,3-二氧六环,选择性和转化率可分别达到94.4%和99.5%。研究了催化剂结构和其有效催化组分,认为酸度是影响选择性的首要因素,其次是酸量,催化剂阳离子的结构对选择性的影响十分明显。此外,对催化剂的行为和可回收原理深入考察,认为温度升高,催化剂在水相(甲醛)中的溶解度增加,甲醛被阳离子质子化后进入油相(α-甲基苯乙烯)。由于阳离子能溶于两相中,搅拌作用下可穿梭在水、油两相中。反应结束,受在水、油两相中分配系数(3.84)的驱动阳离子回到水相;同时,随着温度降低催化剂的溶解度迅速减小,两者共同作用促使阳离子不断回到水相中与阴离子结合析出沉淀,实现催化剂分离回收。回收催化剂可重复9次使用。
A series of catalysts of N-heteropolyacid ionic liquid-like were prepared,which were characterized by UV、NH_3-TPD、NMR、XRD、TG and element analysis,and used for Prins reaction of α-methylstyrene with formaldehyde to solvent-free synthesize 4-methyl-4-phenyl-1,3-dioxane.The conversation and selectivity can reach94.4%and 99.5%,respectively.And it can be concluded that conversation and selectivity much depends on the acidity of catalysts include H_0 and concentration of[H~+],as well as the structure of different cations in catalysts.This paper aimed providing an overview and information useful for approaching the mechanism of catalysis for Prins reaction and recycle of catalyst.It's also suggested that the solubility of catalysts in water and partition-coefficient of cations in water/α-methylstyrene play crucial role in recycle catalyst.Moreover,those catalysts can be used 9 times without significant decreases in conversation and selectivity.
A series of catalysts of N-heteropolyacid ionic liquid-like were prepared,which were characterized by UV、NH_3-TPD、NMR、XRD、TG and element analysis,and used for Prins reaction of α-methylstyrene with formaldehyde to solvent-free synthesize 4-methyl-4-phenyl-1,3-dioxane.The conversation and selectivity can reach94.4%and 99.5%,respectively.And it can be concluded that conversation and selectivity much depends on the acidity of catalysts include H_0 and concentration of[H~+],as well as the structure of different cations in catalysts.This paper aimed providing an overview and information useful for approaching the mechanism of catalysis for Prins reaction and recycle of catalyst.It's also suggested that the solubility of catalysts in water and partition-coefficient of cations in water/α-methylstyrene play crucial role in recycle catalyst.Moreover,those catalysts can be used 9 times without significant decreases in conversation and selectivity.
引文
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[3]Du,Z.;Li,Z.;Guo,S.;Deng,Y.J.Phys.Chem.B,2005,109(41):19542.
[2]Thomazeau,C.;Bourbigou,H.;Magna,L.Gilbert,B.J.Am.Chem.Soc.,2003,125(18):5264.
[3]Du,Z.;Li,Z.;Guo,S.;Deng,Y.J.Phys.Chem.B,2005,109(41):19542.