CN1970148A - aA novel epoxy catalyst and preparation method thereof - Google Patents
aA novel epoxy catalyst and preparation method thereof Download PDFInfo
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- CN1970148A CN1970148A CN 200510096398 CN200510096398A CN1970148A CN 1970148 A CN1970148 A CN 1970148A CN 200510096398 CN200510096398 CN 200510096398 CN 200510096398 A CN200510096398 A CN 200510096398A CN 1970148 A CN1970148 A CN 1970148A
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Abstract
The new type oxide catalyst relates to an inorganic and organic composite nanometer making method with nanometer metal composite as the core, metalloporphyrin as the shell, linking metalloporphyrin to form organic or inorganic composite material showing high catalytic performance and catalytic revolution (TON).
Description
Affiliated field:
Patent of the present invention relates to a kind of new epoxidation catalyst and preparation method thereof.
Background technology:
Epoxidation reaction is a kind of reaction type that is widely used on chemical industry, all be widely used in departments such as high score industry, medical industry, fine chemistry industry, the new catalyst that research and development has the efficient catalytic performance just has very important scientific meaning and practical value.At present, bibliographical information many are that the metalloporphyrin of coordination center ion is an epoxidation catalyst with the manganese metal, but the catalytic performance of this catalyst is lower, the easy inactivation of catalyst (the turnover number TON of catalyst is lower).
Summary of the invention
Patent of the present invention relates to the compound preparation of nanomaterials of a kind of new organic-inorganic, can be used as the catalyst of alkene epoxidation with the nano material of this method preparation, and this catalyst has high catalytic activity and high catalyst turnover number (TON).
Description of drawings (seeing Figure of description)
The implementation method of patent of the present invention is:
With a kind of nano level (1-3 nanometer) metal atomic cluster (material 1 in the accompanying drawing) is nuclear, and this metal atomic cluster periphery has the protection part to prevent the polymerization of this nano particle.The difunctional part (material 2 in the accompanying drawing) that has a functional group with a kind of two ends carries out ligand exchange with the protection part of this metal atomic cluster; make of having the difunctional part and metal atomic cluster coordination mutually; the other end of this difunctional part then is in the periphery (material 3 in the accompanying drawing) of this metal atomic cluster; make this part and another metalloporphyrin (material 4 in the accompanying drawing) coordination mutually then, so just formed the outer square shape and structure (material 5 in the accompanying drawing) that is with the opening of six metalloporphyrins compositions at this metal atomic cluster.
Six faces of this square are made up of metalloporphyrin, and the kernel of square then is that metal atomic cluster is formed.Because this metalloporphyrin has special substituted radical (material 4 in the accompanying drawing), under the effect of special catalyst, make the mutual key of these metalloporphyrins connect-promptly form the porphyrin ball that connects by chemistry, so just having formed with metal atomic cluster (inorganic matter) is nuclear, with metalloporphyrin (organic matter) aggregate is the organic matter and the composite (material 7 in the accompanying drawing) of shell, and the size range of this nano material is between the 2-3 nanometer.
This nano material and special acid are done in order to remove the center coordination metal of porphyrin, and then import manganese metal and porphyrin coordination again with epoxidation catalytic performance, forming manganese metal porphyrin aggregate is shell, metal atomic cluster is the compound nano material of organic-inorganic (material 8 in the accompanying drawing) of nuclear, and this nano material (material 8 in the accompanying drawing) presents high catalytic performance to the epoxidation catalytic reaction of alkene.
Concrete implementation method is:
(1) metal of this nano level metal atomic cluster (material 1 in the accompanying drawing) employing is: the cluster of metal rhodium, ruthenium, platinum, palladium or gold.Between the size Jie and 1-3 nanometer of selected cluster.
(2) the protection part of metal atomic cluster periphery generally adopts triphenyl phosphorus.
(3) two ends have the difunctional part (material 2 in the accompanying drawing) of functional group general what adopt are that an end has the pyridine group, link to each other with another functional group at the contraposition of the nitrogen-atoms of the pyridine group chain hydrocarbon by certain-length, this functional group selects for use to being advisable with the functional group that metal atomic cluster forms coordinate bond.For example the cluster to Metal Palladium, metallic gold adopts sulfydryl functional group for this reason, as Py-(CH
2)
n-SH.Metal atomic cluster and this difunctional part (this part is excessive greatly) are reacted in dichloromethane solvent, ligand exchange reaction takes place.Form the new nanometer cluster (material 3 in the accompanying drawing) that difunctional part thus replaces the part of original protection metal atomic cluster
(4) have the metal atomic cluster (material 3 in the accompanying drawing) of difunctional again by nitrogen-atoms in its pyridine group that has and metallic zinc porphyrin (material 4 in the accompanying drawing) coordination mutually, this metallic zinc porphyrin has special carbon-carbon double bond, material 3 and material 4 are reacted in carrene with 1/6 ratio, form the material 5 in the accompanying drawing, in the presence of the GRUBBS catalyst, stirred 24 hours, separate with the GPC post then and obtain pure product, make the carbon-carbon double bond phase binding of different porphyrins, forming with metalloporphyrin (organic matter) aggregate is the organic matter and the composite (material 7 in the accompanying drawing) of shell.
(5) this material (material 7 in the accompanying drawing) with in dichloromethane solvent with acid reaction (trifluoroacetic acid), remove the metallic zinc atom in the porphyrin, form with the porphyrin molecular network of coordination metal and the nano particle of central metal atom bunch formation.Through separation and purification, then this particle and anhydrous manganous bromide refluxed 5 days in the DMF solvent, obtained end product at last, were shell with manganese metal porphyrin aggregate, and metal atomic cluster is the compound nano material of organic-inorganic (material 8 in the accompanying drawing) of nuclear.
This catalyst (material 8 in the accompanying drawing) is to the catalytic performance of epoxidation reaction of olefines:
1:2ml concentration is 0.075mM material 8 dichloromethane solution of (being equivalent to the every manganoporphyrin molecular cell of 0.075 * 6=0.45mM/) for example, adds under blanket of nitrogen and contains 2ml CH
2Cl
2Reaction bulb, adding 0.125ml (1125 μ mol) styrene and 49.5mg (225 μ mol) PhIO (catalyst/styrene/PhIO=1/7500/1500), to connect benzene is interior mark, yield with gas-chromatography check reaction, 5min (40%), 15min (63%), 30 (68%), 45min (78%).
2:2ml concentration is the same manganoporphyrin unimolecule dichloromethane solution of 0.45mM for example, adds under blanket of nitrogen under blanket of nitrogen and contains 2ml CH
2Cl
2Reaction bulb, adding 0.125ml (1125 μ mol) styrene and 49.5mg (225 μ mol) PhIO (catalyst/styrene/PhIO=1/1250/250), to connect benzene is interior mark, yield with gas-chromatography check reaction, 5min (12%), 15min (21%), 30 (23%), 45min (25%).
Give an example 3: the oligomer for preparing the manganoporphyrin molecule with same method, determine the porphyrin number of oligomerization then with UV (479nm is the characteristic absorption peak of manganoporphyrin), adopt then and same ratio and reaction condition in 2 for example, the reaction yield that obtains is the same substantially with 2 the yield of giving an example.
Give an example 4: react under the condition that (11250 μ mol) styrene of 1.25ml under blanket of nitrogen and 495mg (2250 μ mol) PhIO are having 50 μ l (concentration is 0.45mM/ manganoporphyrin unit) material 8 to exist, to connect benzene is interior mark, with the yield of gas-chromatography check reaction, the turnover number of reflection (TON) is the molal quantity of the molal quantity of epoxidation product divided by initial catalyst.Reaction 40min, TON is 25300.
Give an example 5: react under the condition that (11250 μ mol) styrene of 1.25ml under blanket of nitrogen and 495mg (2250 μ mol) PhIO are having 50 μ l (concentration is 0.45mM/ manganoporphyrin unit) manganoporphyrin to exist, to connect benzene is interior mark, with the yield of gas-chromatography check reaction, the turnover number of reflection (TON) is the molal quantity of the molal quantity of epoxidation product divided by initial catalyst.Reaction 40min, TON is 4515.
The innovation part of patent of the present invention is to have prepared this inorganic organic composite nanoparticle (accompanying drawing material 8) with new preparation method, and this particle has high reaction yield and high catalyst turnover number to epoxidation reaction of olefines.
Claims (5)
1, a kind of new epoxidation catalyst and preparation method thereof, it is characterized in that with inorganic metal atomic cluster be nuclear, with the metalloporphyrin is shell, by supramolecular method the porphyrin molecule is combined with metal atomic cluster, method by chemistry makes the porphyrin molecule form netted porphyrin molecular network then, and finally forming with the metal atomic cluster is nuclear, is inorganic/organic composite nano materials of shell with the porphyrin molecular aggregate.
2, this inorganic/organic composite nano materials has high catalytic performance and high catalyst turnover number (TON) to epoxidation reaction of olefines
3, according to claim 1, the employed metal atomic cluster of this patent is characterized in that range scale at nano level precious metal atom bunch, and can form the metal atomic cluster of coordinations with coordinating groups such as sulphur, phosphorus.
4, according to claim 1, the employed metalloporphyrin of this patent is a kind of substituent porphyrin of carbon-carbon double bond that has on phenyl ring, and this substituting group comprises the carbochain of different length.
5, according to claim 2, the related inorganic/organic composite nano materials of this patent refers to surpassing the epoxidation Reaction of Alkenes of four six carbon atoms the catalytic performance of epoxidation reaction of olefines.The catalyst concentration scope comprises various concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510096398 CN1970148A (en) | 2005-11-22 | 2005-11-22 | aA novel epoxy catalyst and preparation method thereof |
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|---|---|---|---|
| CN 200510096398 CN1970148A (en) | 2005-11-22 | 2005-11-22 | aA novel epoxy catalyst and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584836A (en) * | 2011-12-31 | 2012-07-18 | 中国科学院化学研究所 | Porphyrin cage compound, and preparation method and application thereof |
| CN103044435A (en) * | 2012-12-14 | 2013-04-17 | 辽宁师范大学 | Novel coordination polymer nano-material and preparation method thereof |
| CN103665011A (en) * | 2013-11-26 | 2014-03-26 | 辽宁师范大学 | Quadri-pyridyl zinc protoporphyrin coordination polymer and preparation method thereof |
-
2005
- 2005-11-22 CN CN 200510096398 patent/CN1970148A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584836A (en) * | 2011-12-31 | 2012-07-18 | 中国科学院化学研究所 | Porphyrin cage compound, and preparation method and application thereof |
| CN103044435A (en) * | 2012-12-14 | 2013-04-17 | 辽宁师范大学 | Novel coordination polymer nano-material and preparation method thereof |
| CN103665011A (en) * | 2013-11-26 | 2014-03-26 | 辽宁师范大学 | Quadri-pyridyl zinc protoporphyrin coordination polymer and preparation method thereof |
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