手性钛络合物在中孔硅分子筛上的组装  

Assembles of Chiral Titanium Tartrate Complex over Mesoporous Molecular Sieves

作　　者：伏再辉[1] 徐友志[2] 曾雷[1] 周四清[1] 张鲁西[2] 尹笃林[1] 

机构地区：[1]湖南师范大学精细催化合成研究所,中国长沙410081 [2]湖南师范大学分析测试中心,中国长沙410081

出　　处：《湖南师范大学自然科学学报》2002年第1期41-46,共6页Journal of Natural Science of Hunan Normal University

基　　金：国家自然科学基金 (2 97730 13);湖南省自然科学基金 ([湘科计字 2 0 0 0 ] 2 37 0 0JJY2 0 0 1)资助项目

摘　　要：合成了纯硅和含骨架钛的HMS ,MCM 41两类中孔硅分子筛 ,利用它们的表面羟基与钛酸异丙酯(Ti(OiPr) 4)或 d 酒石酸二乙酯 (DET)的交换反应 ,用四种组装方法成功地将Ti(OiPr) 4+DET手性络合物接枝到纯硅的HMS和MCM - 41中孔分子筛上 ,从而首次制备出固载手性钛的中孔催化剂 .用FT -IR表征了中孔材料与手性钛络合物的交换作用 ,并测定了钛的负载量 .在用固载化的手性催化剂催化苯乙烯环氧化反应中发现 :DET配体对钛中心的调变作用将造成其催化活性的下降和环氧物选择性的上升 ;DET配体的手性诱导作用将使环氧产物具有一定的光学选择性 (其中d 型环氧物异构体过剩ee .%最高可达 32 .4% ) .Pure silicon and Ti-substituted mesoporous molecular sieves(HMS and MCM-41) have been synthesized by surfactant templpating pathway. A type of Ti(OiPr)4 + DET chiral complex has been successfully assembled to mesoporous carriers by use of exchange reaction of the surface hydroxyls of mesoporous carriers with Ti compound or d-diethyl tartrate(DET). Though four assembled pathways, chiral Ti anchored mesoporous catalysts have been first prepared. These anchored chiral catalysts are characterized by FT-IR. Its Ti contents are measured. In catalyzing the epoxidation of styrene with tertbutyl hydroperoxide(TBHP) as an oxidant, these chiral catalysts have the better catalytic activity and the selectivity for the epoxides. The adjusting interaction of DET ligand to the Ti sites anchored on the mesoporous carriers will cause the decrease in the catalytic activity and the increase in the epoxidation selectivity of the Ti sites. The chiral inducting interaction of DET will induce to produce the enantiomeric excess of d -epoxide(ee. % is up to 32.4%).

关 键 词：中孔硅分子筛 手性钛络合物 苯乙烯 不对称环氧化 固载化手性催化剂 交换反应 组装方法 

分 类 号：TQ426.81[化学工程]