Preparation of silica-immobilized titanium-containing silsesquioxane catalysts and activity for the epoxidation of alkenes

被引：7

作者：

Wada, Kenji ^{[1
]}

Watanabe, Naoki ^{[1
]}

Kondo, Teruyuki ^{[1
]}

Mitsudo, Take-aki ^{[1
]}

机构：

[1] Kyoto Univ, Grad Sch Engn, Dept Energy & Hydrocarbon Chem, Nishikyo Ku, Kyoto 6158510, Japan

来源：

CHEMICAL ENGINEERING SCIENCE | 2008年 / 63卷 / 20期

关键词：

Titanium-containing silsesquioxane; Tethered catalysts; Epoxidation of alkenes; Hydrogen peroxide; Hydrosilylation;

D O I：

10.1016/j.ces.2007.11.015

中图分类号：

TQ [化学工业];

学科分类号：

0817 ;

摘要：

Silsesquioxanes containing tetrapodal titanium species and alkenylsilyl groups were immobilized onto dimethylsilyl-functionalized silica having mesopores by chemical tethering via hydrosillylative reaction in the presence of a Pt catalyst. The immobilized catalysts showed higher activity than their corresponding homogeneous catalyst towards the epoxidation of cyclooctene by tert-butylhydroperoxide, probably because of the improvement of the micro-environment around the titanium center. The reaction was found to be truly heterogeneous, since no further reaction proceeded after the separation of the catalyst by filtration. These catalysts also showed excellent catalytic activity for the epoxidation using hydrogen peroxide as an oxidant, while the parent homogeneous catalysts did not show any activity at all. (C) 2007 Elsevier Ltd. All rights reserved.

引用

页码：4917 / 4923

页数：7

共 16 条

[1] Modelling the active sites of heterogeneous titanium epoxidation catalysts using titanium silasequioxanes: Insight into specific factors that determine leaching in liquid-phase processes [J].

Abbenhuis, HCL ;

Krijnen, S ;

vanSanten, RA .

CHEMICAL COMMUNICATIONS, 1997, (03) :331-332

[2] Macromolecular materials in heterogeneous catalysis: An aluminium silasesquioxane gel as active catalyst in Diels-Alder reactions of enones [J].

Abbenhuis, HCL ;

vanHerwijnen, HWG ;

vanSanten, RA .

CHEMICAL COMMUNICATIONS, 1996, (16) :1941-1942

[3] SILSESQUIOXANES [J].

BANEY, RH ;

ITOH, M ;

SAKAKIBARA, A ;

SUZUKI, T .

CHEMICAL REVIEWS, 1995, 95 (05) :1409-1430

[4] Double organic modification by 3-chloropropyl and methyl groups on pure silica MCM-41 and Ti-MCM-41: efficient catalyst for epoxidation of cyclododecene [J].

Bhaumik, A ;

Tatsumi, T .

CATALYSIS LETTERS, 2000, 66 (03) :181-184

[5] SILASESQUIOXANES AS LIGANDS IN INORGANIC AND ORGANOMETALLIC CHEMISTRY [J].

FEHER, FJ ;

BUDZICHOWSKI, TA .

POLYHEDRON, 1995, 14 (22) :3239-3253

[6] The dynamic status quo of polyhedral silsesquioxane coordination chemistry [J].

Hanssen, RWJM ;

van Santen, RA ;

Abbenhuis, HCL .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2004, (04) :675-683

[7]

Krijnen S, 1998, ANGEW CHEM INT EDIT, V37, P356, DOI 10.1002/(SICI)1521-3773(19980216)37:3<356::AID-ANIE356>3.0.CO

[8]

2-5

[9]

Skowronska-Ptasinska MD, 2002, ANGEW CHEM INT EDIT, V41, P637

[10] Active catalysts prepared using a vanadium-containing oligosilsesquioxane for selective photo-assisted oxidation of methane into methanal [J].

Wada, K ;

Nakashita, M ;

Yamamoto, A ;

Mitsudo, T .

CHEMICAL COMMUNICATIONS, 1998, (01) :133-134

← 1 2 →