GB2225963A - Supported oxidation catalyst - Google Patents

Supported oxidation catalyst Download PDF

Info

Publication number
GB2225963A
GB2225963A GB8926625A GB8926625A GB2225963A GB 2225963 A GB2225963 A GB 2225963A GB 8926625 A GB8926625 A GB 8926625A GB 8926625 A GB8926625 A GB 8926625A GB 2225963 A GB2225963 A GB 2225963A
Authority
GB
United Kingdom
Prior art keywords
catalyst according
porphyrin
metallo
support material
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB8926625A
Other versions
GB8926625D0 (en
GB2225963B (en
Inventor
Pamela Ann Casson
Terence John Goodwin
Andrew Thomas Chadwick
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
UK Atomic Energy Authority
Original Assignee
UK Atomic Energy Authority
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by UK Atomic Energy Authority filed Critical UK Atomic Energy Authority
Publication of GB8926625D0 publication Critical patent/GB8926625D0/en
Publication of GB2225963A publication Critical patent/GB2225963A/en
Application granted granted Critical
Publication of GB2225963B publication Critical patent/GB2225963B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/72—Epoxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese

Abstract

A supported catalyst comprises a metallo-porphyrin (eg Mn-porphyrin) carried on a support material such as high surface area alumina. The metallo-porphyrin and the support material may be bonded by an interposed bifunctional molecule such as a silylating reagent. The catalyst is useful, for example in the catalysis of liquid-phase oxygen insertion reactions under mild conditions. An example is epoxidation of an aromatic substrate.

Description

Supported Oxidation Catalyst This invention relates to a supported catalyst and its use in oxidation reactions.
In one aspect of the invention, a supported catalyst comprises a metallo-porphyrin carried on a solid support material.
The metallo-porphyrin may, for example, be a transition metal-porphyrin (e.g. manganese porphyrin) and the porphyrin may be substituted or unsubstituted, for example the porphyrin may be substituted with one or more groups such as phenyl groups which may themselves be substituted or unsubstituted. A specific example of a metallo-porphyrin for use in the invention is manganese-tetracarboxytetraphenylporphyrin.
The solid support material may, for example, be an inorganic material such as a ceramic material. One form of ceramic material that can be used is a high surface area ceramic material where "high" includes 70 m 2g -l or greater, for example 80-100 m2g-1 A specific example is an alumina whose specific surface area at a temperature below 11000C is not less than 70 m29-1 (e.g. in the range 80 m2g -l to 100 m2g-1) and whose total pore volume at a temperature below 11000C is not less than 0.50 dm3kg-l (e.g. in the range from 0.50 dm3kg'l to 0.85 dm3kg1).
The ceramic material may, for example, be a ceramic oxide, preferably aluminium oxide, and, when in high surface area form, preferably has a structure comprising loose aggregates of primary-particles, in which structure there are spaces and point to point contacts between the primary-particles. Such a high surface area form may be made by drying a dispersion of colloidal particles of the ceramic material in a liquid medium, followed by firing, the colloidal particles having been made by a vapour phase condensation method such as flame hydrolysis. The preparation of such a high surface area form is described in GB-A-1 567 003 (equivalent to US-A-4 389 385).
The metallo-porphyrin may be carried on the support material by being attached thereto, e.g. by bonding. If desired, the metallo-porphyrin can be attached to the support material by means of an interposed bonding material bonded to each of the metallo-porphyrin and the support material. Such an interposed bonding material may, for example, be constituted by a bifunctional molecule having a first functional group or groups bonded to the metallo-porphyrin and a second functional group or groups bonded to the support material. Examples of such bifunctional molecules are silane derivatives (e.g.
silylating reagents) such as represented, before bonding, by the general formula R3Si(CH2)nX, where R is Oalkyl (such as methoxy or ethoxy), Oaryl, Oheterocyclic, alkyl, aryl or heterocyclic; n is o,l, 2 or higher integer; and X is alkyl, aryl, heterocyclic, amino, halogen, or hydroxy. Bonding to the support material is via the R group or groups and bonding to the metallo-porphyrin is via the X group. The metallo-porphyrin may have to be provided with an appropriate functional group to enable it to be bonded via the X group. A specific example of a silane derivative of the above general formula is (EtO)3Si(CH2)3NH2.
The supported catalysts of the invention have been found to be effective in the catalysis of oxidation reactions, which is a second aspect of the invention. For example, the catalysts have been found useful as heterogeneous catalysts in liquid-phase oxygen insertion reactions, for example where selectivity is required to give a unique product and under mild reaction conditions.
Thus, the catalysts of the invention have been found to give promising results in epoxidation of an aromatic substrate using an oxidant, for example in epoxidising styrene using hydrogen peroxide or sodium hypochlorite.

Claims (20)

Claims
1. A supported catalyst comprising a metallo-porphyrin carried on a solid support material.
2. A catalyst according to claim 1 wherein the porphyrin is substituted or unsubstituted.
3. A catalyst according to claim 2 wherein the porphyrin is substituted with one or more phenyl groups which may themselves be substituted or unsubstituted.
4. A catalyst according to any of the preceding claims wherein the metallo-porphyrin is a transition metal-porphyrin.
5. A catalyst according to claim 4 wherein the transition metal is manganese.
6. A catalyst according to claim 5 wherein the metallo-porphyrin is manganese-tetracarboxytetraphenylporphyrin.
7. A catalyst according to any of the preceding claims wherein the solid support material is inorganic.
8. A catalyst according to claim 7 wherein the support material is a ceramic material.
9. A catalyst according to claim 8 wherein the ceramic material is a ceramic oxide.
10. A catalyst according to claim 9 wherein the ceramic oxide is aluminium oxide.
11. A catalyst according to any of claims 8 to 10 wherein the surface area of the ceramic material is 70 m2g~l or greater.
12. A catalyst according to claim 11 wherein the ceramic material has a structure comprising loose aggregates of primary-particles, in which structure there are spaces and point to point contacts between the primary-particles.
13. A catalyst according to any of the preceding claims wherein the metallo-porphyrin is attached to the support material by an interposed bonding material bonded to each of the metallo-porphyrin and the support material.
14. A catalyst according to claim 13 wherein the bonding material is a bifunctional molecule having a first functional group or groups bonded to the metallo-porphyrin and a second functional group or groups bonded to the support material.
15. A catalyst according to claim 14 wherein the bifunctional molecule is a silylating reagent.
16. A catalyst according to claim 15 wherein the silylating reagent has, before bonding, the general formula R3Si(CH2)nX wherein R is 0 alkyl, 0 alkyl, 0 heterocyclic, alkyl, aryl or heterocyclic; n is O, 1, 2, or a higher integer; and X is alkyl, aryl, heterocyclic, amino, halogeno, or hydroxy.
17. A catalyst according to claim 16 wherein the silylating reagent has the formlula (EtO)3Si(CH2)3NH2.
18. A method of catalysing a liquid-phase oxygen insertion reaction using a catalyst as claimed in any of the preceding claims.
19. A method according to claim 18 wherein the reaction is the epoxidation of an aromatic substrate using an oxidant.
20. A method according to claim 19 wherein the aromatic substrate is styrene and the oxidant is hydrogen peroxide or sodium hypochlorite.
GB8926625A 1988-11-21 1989-11-20 Supported oxidation catalyst Expired - Fee Related GB2225963B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB888827123A GB8827123D0 (en) 1988-11-21 1988-11-21 Supported oxidation catalyst

Publications (3)

Publication Number Publication Date
GB8926625D0 GB8926625D0 (en) 1990-01-17
GB2225963A true GB2225963A (en) 1990-06-20
GB2225963B GB2225963B (en) 1992-07-29

Family

ID=10647163

Family Applications (2)

Application Number Title Priority Date Filing Date
GB888827123A Pending GB8827123D0 (en) 1988-11-21 1988-11-21 Supported oxidation catalyst
GB8926625A Expired - Fee Related GB2225963B (en) 1988-11-21 1989-11-20 Supported oxidation catalyst

Family Applications Before (1)

Application Number Title Priority Date Filing Date
GB888827123A Pending GB8827123D0 (en) 1988-11-21 1988-11-21 Supported oxidation catalyst

Country Status (1)

Country Link
GB (2) GB8827123D0 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0618202A1 (en) * 1993-03-30 1994-10-05 National Starch and Chemical Investment Holding Corporation Epoxidation of olefins via certain manganese complexes
US5493017A (en) * 1992-08-14 1996-02-20 The Trustees Of The University Of Pennsylvania Ring-metalated porphyrins
WO1996008311A1 (en) * 1994-09-14 1996-03-21 Hoechst Celanese Corporation D4-symmetric porphyrin-based catalysts, processes for preparing same, and processes for using same
US5756723A (en) * 1992-08-14 1998-05-26 The Trustees Of The University Of Pennsylvania Metal-mediated cross-coupling with ring-metalated porphyrins
US5817830A (en) * 1992-08-14 1998-10-06 Trustees Of The University Of Pennsylvania Pyrrolic compounds
US5856515A (en) * 1992-08-14 1999-01-05 Trustees Of The University Of Pennsylvania Electron-deficient porphyrins and processes and intermediates for preparing same
EP0970951A1 (en) * 1998-07-09 2000-01-12 K.U. Leuven Research & Development A manganese oxidation catalyst, a method for its preparation and use thereof for catalytic epoxidation, catalytic cis-dihydroxylation and combined expoxidation-cis-dihydroxylation of olefins
US6028025A (en) * 1996-10-21 2000-02-22 Massachusetts Institute Of Technology Metalloporphyrin oxidation catalyst covalently coupled to an inorganic surface and method making same
WO2003000774A1 (en) * 2001-06-21 2003-01-03 The Victoria University Of Manchester Organic microporous materials
CN105712849A (en) * 2014-12-04 2016-06-29 中国科学院大连化学物理研究所 Method for preparing aromatic ketone by oxidation of aromatic hydrocarbon under catalytic action of metalloporphyrin framework catalyst

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1288546A (en) * 1969-02-06 1972-09-13
EP0118801A2 (en) * 1983-03-09 1984-09-19 Sumitomo Chemical Company, Limited A catalyst for isomerization reaction
JPS63279151A (en) * 1987-05-11 1988-11-16 Nibetsukusu Kk Carbon monoxide sensor

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2456730A2 (en) * 1979-05-15 1980-12-12 Ugine Kuhlmann PROCESS FOR THE PREPARATION OF ORGANIC ISOCYANATES FROM NITER DERIVATIVES
FR2633925B1 (en) * 1988-07-06 1990-10-26 Elf Aquitaine PROCESS FOR OXIDATION BY BIOMIMETIC CATALYSIS OF BENZYL ALCOHOLS AND RELATED COMPOUNDS
GB2232067B (en) * 1989-05-01 1992-10-28 Alperk Ltd A food processing apparatus
JPH03279151A (en) * 1990-03-23 1991-12-10 Nippon Sekisoo Kogyo Kk Sheet product piling device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1288546A (en) * 1969-02-06 1972-09-13
EP0118801A2 (en) * 1983-03-09 1984-09-19 Sumitomo Chemical Company, Limited A catalyst for isomerization reaction
JPS63279151A (en) * 1987-05-11 1988-11-16 Nibetsukusu Kk Carbon monoxide sensor

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5493017A (en) * 1992-08-14 1996-02-20 The Trustees Of The University Of Pennsylvania Ring-metalated porphyrins
US5756723A (en) * 1992-08-14 1998-05-26 The Trustees Of The University Of Pennsylvania Metal-mediated cross-coupling with ring-metalated porphyrins
US5817830A (en) * 1992-08-14 1998-10-06 Trustees Of The University Of Pennsylvania Pyrrolic compounds
US5856515A (en) * 1992-08-14 1999-01-05 Trustees Of The University Of Pennsylvania Electron-deficient porphyrins and processes and intermediates for preparing same
EP0618202A1 (en) * 1993-03-30 1994-10-05 National Starch and Chemical Investment Holding Corporation Epoxidation of olefins via certain manganese complexes
WO1996008311A1 (en) * 1994-09-14 1996-03-21 Hoechst Celanese Corporation D4-symmetric porphyrin-based catalysts, processes for preparing same, and processes for using same
US6028025A (en) * 1996-10-21 2000-02-22 Massachusetts Institute Of Technology Metalloporphyrin oxidation catalyst covalently coupled to an inorganic surface and method making same
EP0970951A1 (en) * 1998-07-09 2000-01-12 K.U. Leuven Research & Development A manganese oxidation catalyst, a method for its preparation and use thereof for catalytic epoxidation, catalytic cis-dihydroxylation and combined expoxidation-cis-dihydroxylation of olefins
WO2000002872A1 (en) * 1998-07-09 2000-01-20 K.U. Leuven Research & Development A manganese oxidation catalyst, a method for its preparation and use thereof for the oxydation of olefins
WO2003000774A1 (en) * 2001-06-21 2003-01-03 The Victoria University Of Manchester Organic microporous materials
CN105712849A (en) * 2014-12-04 2016-06-29 中国科学院大连化学物理研究所 Method for preparing aromatic ketone by oxidation of aromatic hydrocarbon under catalytic action of metalloporphyrin framework catalyst

Also Published As

Publication number Publication date
GB8926625D0 (en) 1990-01-17
GB2225963B (en) 1992-07-29
GB8827123D0 (en) 1988-12-29

Similar Documents

Publication Publication Date Title
GB2225963A (en) Supported oxidation catalyst
US5194333A (en) Packing material for reversed phase chromatography and process for its preparation
CA1303010C (en) Structures surface modified with bidentate silanes
CA1252002A (en) Porous materials having two different reaction surfaces
EP0331283A1 (en) High stability porous zirconium oxide spherules
JP4750280B2 (en) Porous inorganic / organic hybrid particles for chromatographic separation and process for their preparation
EP0200260A2 (en) Catalyst on the basis of silicon and titanium having high mechanical strength
US5104547A (en) Separating materials for chromatography comprising cyclodextrin chemically bonded to a support via a carbamic acid group
IE59080B1 (en) Acylated polyethylenimine bound chromatographic packing
ATE182087T1 (en) SUPPORTED CATALYST FOR GAS PHASE OXIDATION REACTIONS
AU1091899A (en) Methods of making a molecular sieve containing catalyst
GB2313597A (en) Inorganic carrier, for the immobilisation of enzymes, comprising a coupling agent having a carboxylic ester linkage
AU5407198A (en) Ink-jet transfer systems, process for their preparation and use thereof for a printing process
US4661248A (en) Sulfonic derivatives of acylated polyethyleneimine bonded phase silica products
DK0791558T3 (en) Silica / zeolite composite materials in spherical form and process for their preparation
Corma et al. Electrostatic and covalent immobilisation of enzymes on ITQ-6 delaminated zeolitic materials
AU2003216717A1 (en) Zeolite/sic composites and the use thereof as a catalyst
AU3672089A (en) Chemical process and catalyst
KR20020059850A (en) Catalysts Which are Based on Organic-Inorganic Hybrid Materials Containing Noble Metals and Titanium and Which are Used for Selectively Oxidizing Hydrocarbons
US4721573A (en) Use of sulfonic derivatives of acylated polyethyleneimine bonded phase silica products
CA2370815A1 (en) Sol-gel hybrid materials containing precious metals as catalysts for partial oxidation of hydrocarbons
US5869724A (en) Asymmetric bidentate silanes
CA2265643A1 (en) Fischer-tropsch catalyst and process for preparing hydrocarbons
CA2205790A1 (en) Process for preparing amino-silane compounds, and novel amino-silane compounds
CA2099791A1 (en) Method for the Preparation of 1-Aza-2-Silacyclopentane Compounds

Legal Events

Date Code Title Description
732E Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977)
732E Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977)
PCNP Patent ceased through non-payment of renewal fee