CN103170350B - Preparation method of sulfoxide or sulfone compound, as well as catalyst and catalyst composition used in preparation method - Google Patents
Preparation method of sulfoxide or sulfone compound, as well as catalyst and catalyst composition used in preparation method Download PDFInfo
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Abstract
The invention relates to the field of organic synthesis chemistry, and more particularly relates to a preparation method of a sulfoxide or sulfone compound, as well as a catalyst and a catalyst composition used in the preparation method. The general formula of the catalyst is aFe2O3.bCuO.cMnO2.dAl2O3.eTiO2.fRh2O3.gRuO2, wherein a, b, c, d and e are independently selected from 0-20, and f and g are independently selected from 0.01-10. The catalyst composition comprises the catalyst and a photosensitizer, wherein the mass ratio of the catalyst to the photosensitizer is 0.01-10. The catalyst/catalyst composition has efficient catalytic activity; oxygen is used as a single oxidant in the process of preparing the sulfoxide or sulfone compound by catalyzing thioether; and under an illumination condition, the catalyst/catalyst composition is mild in reaction conditions, free of pollution and environment-friendly and clean, and has no potential safety hazard.
Description
Technical field
The present invention relates to synthetic organic chemical art, more specifically, relate to the preparation method of a kind of sulfoxide type or sulfone compound and the catalyst of use thereof and carbon monoxide-olefin polymeric.
Background technology
Sulfoxide type and sulfone compound are important chemicals.It is as the important intermediate of organic synthesis, is widely used in the reactions such as C-C key forming reactions, molecular recombination.Having different biologically actives after sulfoxide and sulfone compound introduce different group simultaneously, is important medicine intermediate.Sulfoxide type and sulfone compound are generally made by the oxidation of thioether.
In many known synthetic methods, due to eco-friendly requirement, many subsequent treatment difficulty or the serious method of environmental pollution inapplicable, impel the oxidation of thioether to the more green more cost effective future development of environmental protection more.With Green Oxidant, as hydrogen peroxide, ozone, oxygen replace conventional oxidation agent to be realize green committed step of producing.
The people (Angew. Chem. Int. Ed. 2005,44,6871 – 6874) such as Oleg Pestovsky use [Fe (H
2o)
6]
2+for catalyst, make oxidant with ozone, can oxidizing sulfur ether well.But ozone incurred cost is higher, ozone generating speed rate is not enough all limits its application industrially.Having reported them in the document of the people (Tetrahedron 61 (2005) 8315 – 8327) such as Katarzyna Kaczorowska uses hydrogen peroxide to obtain sulfoxide compound as single-oxidizer.If add precious metal salt and chiral ligand, the sulfoxide compound with chirality can be obtained especially, and productive rate, ee value are all satisfied.But the document does not relate to the preparation of sulfone compound.Catalyst is made with silica gel load sulfuric acid (silica sulfuric acid) in the document (Catalysis Communications 8 (2007) 1112 – 1116) of Ahmad Shaabani, by controlling the equivalent of hydrogen peroxide, can optionally obtain sulfoxide type or sulfone compound in several tens minutes.This class methods shortcoming is that hydrogen peroxide shipping storage acquires a certain degree of difficulty and danger, and price comparison is expensive.Han Baek Lee and Tong Ren disclosed (Inorganica Chimica Acta 362 (2009) 1467 – 1470) catalyzed by ruthenium complexes, dioxygen oxidation thioether, control kind and the reaction time of solvent, optionally sulfoxide type and sulfone compound can be obtained necessarily.But the method reaction speed is comparatively slow, and often need 72 hours, efficiency is lower.CN1397533A discloses a kind of reaction method of oxidization of organic sulfide in air.It adopts the immobilized transition metal complex of sol-gel process to make catalyst.But need to use isobutylaldehyde to work as reducing agent simultaneously, greatly increase production cost.CN1546468A utilizes homemade solid catalyst MnFe
1.8cu
0.15ru
0.05o
4, in oxygen atmosphere, sulfide oxidation can be become sulfone by reaction.But this catalyst amount is comparatively large, and selectively cannot prepare sulfoxide compound.
Summary of the invention
Primary technical problem to be solved by this invention is, in order to overcome the above-mentioned deficiency of prior art, provides a kind of
oneplant catalyst.The advantages such as this catalyst has efficiently, environmental protection, can reclaiming and repeat to apply mechanically, can take air or oxygen as single-oxidizer, preparing sulfoxide through catalytic oxidation class or sulfone compound under relatively mild condition, and realizes zero-emission.
Secondary technical problem to be solved by this invention provides the preparation method of described catalyst.
Another technical problem to be solved by this invention provides a kind of carbon monoxide-olefin polymeric.
A technical problem more to be solved by this invention provides a kind of preparation method of carbon monoxide-olefin polymeric.
A technical problem more to be solved by this invention provides the preparation method of a kind of sulfoxide type or sulfone compound.
Above-mentioned technical problem to be solved by this invention is achieved by the following technical programs:
A kind of catalyst, its general formula is aFe
2o
3bCuOcMnO
2dAl
2o
3eTiO
2fRh
2o
3gRuO
2; Wherein, a, b, c, d, e are independently selected from 0 ~ 20, f, g is independently selected from 0.01 ~ 10.
As a kind of preferred version, a, b, c, d, e are independently selected from 0 ~ 5, f, g is independently selected from 0.05 ~ 3.
As the further preferred version of one, a is 0 ~ 1, b be 0 ~ 2, c be 0 ~ 3, d be 0 ~ 4, e be 0 ~ 5, f be 0.05 ~ 1, g is 0.05 ~ 1.
As one most preferably scheme, a is 0.01 ~ 0.5, b be 0.01 ~ 1, c be 0.01 ~ 2, d be 0.01 ~ 3, e be 0.01 ~ 4, f be 0.5 ~ 1, g is 0.5 ~ 1.
Prepare a method for above-mentioned catalyst, comprise the steps: the catalyst aFe by required preparation
2o
3bCuOcMnO
2dAl
2o
3eTiO
2fRh
2o
3gRuO
2mol ratio, take di-iron trioxide, cupric oxide, manganese dioxide, aluminium oxide, titanium oxide, ruthenium-oxide and rhodium oxide, roasting 0.5 ~ 24 hour at 50 ~ 500 DEG C after mixing, cooling obtains.
As a kind of preferred version, above-mentioned sintering temperature is 100 ~ 400 DEG C, and roasting time is 0.5 ~ 10 hour.
A kind of carbon monoxide-olefin polymeric, comprise above-mentioned catalyst and sensitising agent, the mass ratio of described catalyst and sensitising agent is 1:0.01 ~ 10.
Sensitising agent is the luminous energy of the certain wavelength of Absorbable rod, Light energy transfer to some on the insensitive reactant of light, improve the material of its reactivity.
As a kind of preferred version, described sensitising agent is selected from the mixing of one or more in transient metal complex, porphyrin substance, phthalocyanines material, chlorophyll, vitamin, purine, phenolphthalein, organic dyestuff, pigment, pigment and styrax ether material.
As one most preferably scheme, described sensitising agent is selected from phthalocyanine, fluorescein, eosin, acridine red, methylene blue, curcumin, benzophenone, 9,10-dintrile anthracenes, 1,2,4,5-four cyano benzene, 2,3, the mixing of one or more in the chloro-Isosorbide-5-Nitrae-benzoquinones of 5,6-tetra-, rose-red and haematoporphyrin.
A preparation method for carbon monoxide-olefin polymeric, comprises the steps: above-mentioned catalyst and sensitising agent to mix, grinds to form uniform powder.
Above-mentioned catalyst or the application of carbon monoxide-olefin polymeric in the synthesis of catalysis dimethyl sulfoxide (DMSO).
The preparation method of a kind of sulfoxide type or sulfone compound, comprising the steps: in raw material, add solvent and catalysts, is under the illumination of 190 ~ 780nm at wavelength, reacts in the air or oxygen atmosphere of 1 ~ 10MPa, reaction temperature is 0 ~ 200 DEG C, and the reaction time is 1 ~ 72 hour; The weight ratio of raw material, solvent and catalysts is 1:0 ~ 40:0.01 ~ 1; Described catalysts is above-mentioned catalyst or carbon monoxide-olefin polymeric; Described raw material is thio-ether type compounds or sulfoxide compound.
The structural formula of sulphur ether material is, R
1, R
2aryl or alkyl substituent.
The structural formula of sulfoxides is
, R
1, R
2aryl or alkyl substituent.
The structural formula of sulfone class material is
, R
1, R
2aryl or alkyl substituent.
As a kind of preferred version, when described need synthesis sulfoxide compound time, take thio-ether type compounds as raw material; Reaction temperature is 0 ~ 100 DEG C, and the reaction time is 1 ~ 48 hour.
As a kind of preferred version, when described need synthesis sulfone compound time, with thio-ether type compounds or sulfoxide compound for raw material; Reaction temperature is 60 ~ 200 DEG C, and the reaction time is 2 ~ 72 hours.
As a kind of preferred version, the weight ratio of described raw material, solvent and catalysts is 1:5 ~ 10:0.01 ~ 0.5; Described solvent is selected from one or more mixtures in carrene, 1,2-dichloroethanes, oxolane, ethyl acetate, methyl alcohol, ethanol, toluene, acetone, ether, Isosorbide-5-Nitrae-dioxane, acetonitrile, nitromethane, water.
As a kind of preferred version, described carbon monoxide-olefin polymeric forms support type or non-loading type catalysts composition.
As a kind of preferred version, carrying method can be chemical load, or physical load.
As a kind of preferred version, above-mentioned light-struck wavelength is 380 ~ 780nm.
Compared with prior art, the present invention has following effect of optimization:
(1) catalyst/carbon monoxide-olefin polymeric of the present invention has high-efficiency catalytic activity, in the process that catalysis thioether prepares sulfoxide type and sulfone compound, using oxygen as single-oxidizer, under illumination condition, reaction condition is gentle, pollution-free, green clean, without potential safety hazard.
(2) preparation method's conversion ratio disclosed by the invention and productive rate high, by control temperature and time, sulfoxide type and the sulfone compound of different proportion can be obtained.
(3) catalyst/carbon monoxide-olefin polymeric of the present invention is recyclable applies mechanically.
Detailed description of the invention
Explain the present invention further below in conjunction with specific embodiment, but embodiment is not limited in any way to the present invention.
Embodiment 1
Get 16g di-iron trioxide, 8g cupric oxide, 8.7g manganese dioxide, 10g aluminium oxide, 8g titanium dioxide, 2.5g rhodium oxide and 1.3g ruthenium-oxide, put into 150 DEG C, baking oven and activate 5 hours, after cooling, after grinding evenly, obtain Fe
2o
3cuOMnO
2al
2o
3tiO
20.1Rh
2o
30.1RuO
2.
Embodiment 2
Get 8g cupric oxide, 8.7g manganese dioxide, 10g aluminium oxide, 8g titanium dioxide, 1.3g rhodium oxide and 0.6g ruthenium-oxide, put into Muffle furnace 300 DEG C and activate 3 hours, after cooling, after grinding evenly, obtain CuOMnO
2al
2o
3tiO
20.05Rh
2o
30.05RuO
2.
Embodiment 3
Take 2.5g rhodium oxide, 1.3g ruthenium-oxide, put into Muffle furnace 300 DEG C activation 3 hours after mixing, after cooling, grinding is even obtains Rh
2o
3ruO
2.
Embodiment 4
Get 79.9g di-iron trioxide, 39.8g cupric oxide, 1.3g rhodium oxide and 0.7g ruthenium-oxide, put into 150 DEG C, baking oven and activate 5 hours, after cooling, after grinding evenly, obtain 5Fe
2o
35CuO0.05Rh
2o
30.05RuO
2.
Embodiment 5
Get 39.8g cupric oxide, 43.5g manganese dioxide, 61g aluminium oxide, 1.3g rhodium oxide and 0.7g ruthenium-oxide, put into Muffle furnace 300 DEG C and activate 3 hours, after cooling, after grinding evenly, obtain 5CuO5MnO
25Al
2o
30.05Rh
2o
30.05RuO
2.
Embodiment 6
Get 79g di-iron trioxide, 39.8g cupric oxide, 43.5g manganese dioxide, 61g aluminium oxide, 40g titanium dioxide, 1.3g rhodium oxide and 0.7g ruthenium-oxide, put into 180 DEG C, baking oven and activate 5 hours, after cooling, after grinding evenly, obtain 5Fe
2o
35CuO5MnO
25Al
2o
35TiO
20.05Rh
2o
30.05RuO
2.
Embodiment 7
Get 160g di-iron trioxide, 79.6g cupric oxide, 86.9g manganese dioxide, 122g aluminium oxide, 80g titanium dioxide, 0.25g rhodium oxide and 0.13g ruthenium-oxide, put into 180 DEG C, baking oven and activate 5 hours, after cooling, after grinding evenly, obtain 10Fe
2o
310CuO10MnO
210Al
2o
310TiO
20.01Rh
2o
30.01RuO
2.
Embodiment 8
Get 160g di-iron trioxide, 79.6g cupric oxide, 86.9g manganese dioxide, 122g aluminium oxide, 80g titanium dioxide, 0.13g rhodium oxide and 0.07g ruthenium-oxide, put into 180 DEG C, baking oven and activate 5 hours, after cooling, after grinding evenly, obtain 20Fe
2o
320CuO20MnO
220Al
2o
320TiO
20.01Rh
2o
30.01RuO
2.
Embodiment 9
Get 8g di-iron trioxide, 8g cupric oxide, 13g manganese dioxide, 20g aluminium oxide, 20g titanium dioxide, 2.5g rhodium oxide and 1.3g ruthenium-oxide, put into the activation of 120 DEG C, baking oven and obtain 72.8g catalyst Fe in 10 hours
2o
32CuO3MnO
24Al
2o
35TiO
20.2Rh
2o
30.2RuO
2, add 0.73g eosin after cooling, after grinding evenly, obtain composite catalyst A.
Embodiment 10
Get 8g cupric oxide, 8.7g manganese dioxide, 10g aluminium oxide, 8g titanium dioxide, 1.3g rhodium oxide and 0.6g ruthenium-oxide, put into Muffle furnace 300 DEG C activation 3 hours, obtained 36.6g Catalysts Cu OMnO
2al
2o
3tiO
20.05Rh
2o
30.05RuO
2, add 36.6g fluorescein after cooling, grind to obtain composite catalyst B.
Embodiment 11
Get 1.6g di-iron trioxide, 0.8g cupric oxide, 0.9g manganese dioxide, 1g aluminium oxide, 0.8g titanium dioxide, 0.25g rhodium oxide and 0.13g ruthenium-oxide, put into Muffle furnace 400 DEG C activation 1 hour, obtained 5.48g catalyst Fe
2o
3cuOMnO
2al
2o
3tiO
20.1Rh
2o
30.1RuO
2, add 27.4g phthalocyanine after cooling, obtained composite catalyst C after grinding evenly.
Embodiment 12
Get 1.6g di-iron trioxide, 0.8g cupric oxide, 0.9g manganese dioxide, 1g aluminium oxide, 0.8g titanium dioxide, 0.25g rhodium oxide and 0.13g ruthenium-oxide, put into Muffle furnace 400 DEG C activation 1 hour, obtained 5.48g catalyst Fe
2o
3cuOMnO
2al
2o
3tiO
20.1Rh
2o
30.1RuO
2, it is rose-red to add 54.8g after cooling, obtained composite catalyst D after grinding evenly.
Embodiment 13
Get 16g di-iron trioxide, 8g cupric oxide, 8.7g manganese dioxide, 10g aluminium oxide, 8g titanium dioxide, 2.5g rhodium oxide and 1.3g ruthenium-oxide, put into Muffle furnace 350 DEG C activation 1.5 hours, obtained Fe
2o
3cuOMnO
2al
2o
3tiO
20.1Rh
2o
30.1RuO
2, for subsequent use after cooling.Get 10g active carbon, boil 30 minutes with 5% sodium hydroxide solution, be filtered dry, be washed till neutrality, then boil 1 hour with 5% nitric acid, be filtered dry, be washed till neutral rear 110 DEG C of oven dry.The active carbon of oven dry is joined containing in the rosy ethanolic solution of 3g.Stir 12 hours, suction filtration, dry at 100 DEG C.Dried active carbon is mixed with metal oxide, obtained loaded catalyst after grinding evenly.
Embodiment 14
Diethyl thioether (the Et of 200g
2s), the catalyst Fe of embodiment 1 preparation of 15g
2o
3cuOMnO
2al
2o
3tiO
20.1Rh
2o
30.1RuO
2mix in the toluene of 1L, adjustment oxygen pressure is 1atm, and 20 DEG C are stirred 8 hours.By catalyst filtration, after distillating recovering solvent, obtain diethyl sulfoxide 190g, productive rate is 80%, purity 98%.
Embodiment 15
Diphenyl sulfide (the Ph of 100g
2s), the Catalysts Cu OMnO of embodiment 2 preparation of 10g
2al
2o
3tiO
20.05Rh
2o
30.05RuO
2mix in 1L acetonitrile, adjustment oxygen pressure is 1atm, and 25 DEG C are stirred 10 hours.By catalyst filtration, after distillating recovering solvent, obtain diphenyl sulfoxide 92g, productive rate is 85%, purity 99%.
Embodiment 16
Phenyl methyl sulfide (the PhSCH of 300g
3), the catalyst Rh for preparing of the embodiment 3 of 5g
2o
3ruO
2mix in 1.5L methyl alcohol, adjustment oxygen pressure is 1.2atm, irradiates with common fluorescent lamp, and 25 DEG C are stirred 12 hours.Reaction terminates rear decompression distillation, and obtain phenyl methyl sulfoxide 239g, productive rate is 71%, purity 97%.
Embodiment 17
Phenyl propyl thioether (the PhSCH of 100g
2cH
2cH
3), the catalyst 5Fe for preparing of the embodiment 4 of 10g
2o
35CuO0.05Rh
2o
30.05RuO
2mix in 1.5L ethanol, react in air atmosphere, with ultra violet lamp, 30 DEG C are stirred 18 hours.Reaction terminates rear decompression distillation and obtains phenyl propyl sulfoxide 69g, and productive rate is 63%, purity 99%.
Embodiment 18
Diethyl thioether (the Et of 200g
2s), the catalyst 5CuO5MnO of embodiment 5 preparation of 10g
25Al
2o
30.05Rh
2o
30.05RuO
2mix in the toluene of 1L, adjustment oxygen pressure is 1.2atm, and 35 DEG C are stirred 8 hours.By catalyst filtration, after distillating recovering solvent, obtain diethyl sulfoxide 190g, productive rate is 80%, purity 98%.
Embodiment 19
Diphenyl sulfide (the Ph of 200g
2s), the catalyst 5Fe of embodiment 6 preparation of 10g
2o
35CuO5MnO
25Al
2o
35TiO
20.05Rh
2o
30.05RuO
2mix in 1L oxolane, adjustment oxygen pressure is 1.1atm, and 30 DEG C are stirred 12 hours.By catalyst filtration, after distillating recovering solvent, obtain diphenyl sulfoxide 175g, productive rate is 81%, purity 99%.
Embodiment 20
Phenyl methyl sulfide (the PhSCH of 300g
3), the catalyst 10Fe for preparing of the embodiment 7 of 10g
2o
310CuO10MnO
210Al
2o
310TiO
20.01Rh
2o
30.01RuO
2mix in 1.5L methyl alcohol, adjustment oxygen pressure is 1.2atm, irradiates with incandescent lamp, and 25 DEG C are stirred 15 hours.Reaction terminates rear decompression distillation, and obtain phenyl methyl sulfoxide 262g, productive rate is 78%, purity 97%.
Embodiment 21
Phenyl methyl sulfide (the PhSCH of 300g
3), the catalyst 20Fe for preparing of the embodiment 8 of 30g
2o
320CuO20MnO
220Al
2o
320TiO
20.01Rh
2o
30.01RuO
2mix in 1.5L ethanol, adjustment oxygen pressure is 1.5atm, irradiates with incandescent lamp, and 30 DEG C are stirred 30 hours.Reaction terminates rear decompression distillation, and obtain phenyl methyl sulfoxide 272g, productive rate is 81%, purity 98%.
Embodiment 22
The propyloxy phenyl base thioether (PhSCH (CH of 300g
3)
2), the composite catalyst A for preparing of 10g embodiment 9 mixes in 1.5L toluene, regulate oxygen pressure 1.5atm, irradiate with common fluorescent lamp, 40 DEG C are stirred 12 hours.Reaction terminates rear decompression distillation and obtains propyloxy phenyl base sulfoxide, and productive rate is 98%, purity 99%.
Embodiment 13
Diethyl thioether (the Et of 200g
2s), the composite catalyst A for preparing of 8g embodiment 9 mixes in the ethanol of 1L, and regulate oxygen pressure 2atm, 80 DEG C are stirred 8 hours.Filtering catalyst, obtain diethyl sulfone 224g except after desolventizing, productive rate is 83%, purity 99%.
Embodiment 24
Phenyl methyl sulfide (the PhSCH of 300g
3), the composite catalyst B for preparing of 10g embodiment 10 mixes in 1L methyl alcohol, regulate oxygen pressure 1.5atm, irradiate with common fluorescent lamp, 70 DEG C are stirred 12 hours, and obtain phenyl methyl sulfone 330g through crystallization, productive rate is 88%, purity 99%.
Embodiment 25
Butyl sulfide (the C of 500g
4h
9sC
4h
9), composite catalyst C prepared by 50g embodiment 11, mixes in 2L toluene, regulates 1.5atm oxygen atmosphere, irradiates with common fluorescent lamp, and 100 DEG C are stirred 10 hours, and after filtering catalyst, concentrated and crystallization obtains dibutyl maple 585g, and productive rate is 96%, purity 99%.
Embodiment 26
Composite catalyst D prepared by the dimethyl sulfoxide (DMSO) of 100g, 5g embodiment 12,500ml ethanol mixes, and regulates oxygen pressure 1.5atm, irradiate with common fluorescent lamp, 80 DEG C are stirred 12 hours, and after filtering, mother liquor obtains dimethyl sulfone 148g, productive rate 98% through repeatedly crystallization.
Embodiment 27
Benzyl phenyl thioether (the PhSCH of 500g
2ph), the loaded catalyst prepared of 20g embodiment 13,3L toluene mixes in reactor, regulates oxygen pressure 0.2MPa, irradiates with incandescent lamp, and 110 DEG C are stirred 24 hours, and mother liquor crystallization obtains benzyl phenyl sulfone 570g after filtration, productive rate 98%.
Embodiment 28
Diethyl thioether (the Et of 200g
2s), composite catalyst A prepared by 10g embodiment 9,1L ethanol mixes in reactor, and adjustment oxygen pressure is 2atm, irradiates with common fluorescent lamp, and 50 DEG C are stirred 5 hours, distill to obtain diethyl sulfoxide 233g, productive rate 98%, purity 99% after reclaiming ethanol.After distillation, residual catalyst directly repeats to apply mechanically, and result is as follows:
Embodiment 29
Diphenyl sulfide (the Ph of 100g
2s), the metallic catalyst CuOMnO of embodiment 2 preparation of 10g
2al
2o
3tiO
20.05Rh
2o
30.05RuO
2mix in 1L toluene, adjustment oxygen pressure is 3atm, and 110 DEG C are stirred 10 hours.By catalyst filtration, after distillating recovering solvent, obtain diphenyl sulphone (DPS) 113g, productive rate is 97%, purity 98%.Catalyst repeats to apply mechanically, and result is as follows:
Claims (9)
1. for the preparation of sulfoxide type or sulfone compound a catalyst, it is characterized in that, the general formula of described catalyst is aFe
2o
3bCuOcMnO
2dAl
2o
3eTiO
2fRh
2o
3gRuO
2; Wherein, a, b, c, d, e are independently selected from 0 ~ 20, f, g is independently selected from 0.01 ~ 10; And be 0 during a, b, c difference.
2. catalyst according to claim 1, it is characterized in that, a, b, c, d, e are independently selected from 0 ~ 5, f, g is independently selected from 0.05 ~ 3; And be 0 during a, b, c difference.
3. catalyst according to claim 1, is characterized in that, a is 0 ~ 1, b be 0 ~ 2, c be 0 ~ 3, d be 0 ~ 4, e be 0 ~ 5, f be 0.05 ~ 1, g is 0.05 ~ 1; And be 0 during a, b, c difference.
4. the preparation method of catalyst described in claim 1,2 or 3, it is characterized in that, comprise the steps: to take di-iron trioxide, cupric oxide, manganese dioxide, aluminium oxide, titanium oxide, ruthenium-oxide and rhodium oxide in proportion, roasting 0.5 ~ 24 hour at 50 ~ 500 DEG C after mixing, cooling obtains.
5., for the preparation of a carbon monoxide-olefin polymeric for sulfoxide type or sulfone compound, it is characterized in that, described carbon monoxide-olefin polymeric comprises catalyst and sensitising agent described in claim 1,2 or 3, and the mass ratio of described catalyst and sensitising agent is 1:0.01 ~ 10; Described sensitising agent is selected from the mixing of one or more in transient metal complex, porphyrin substance, phthalocyanines material, chlorophyll, vitamin, purine, phenolphthalein, organic dyestuff, pigment, pigment and styrax ether material.
6. the preparation method of carbon monoxide-olefin polymeric described in claim 5, comprises the steps: catalyst described in claim 1,2 or 3 and sensitising agent to mix, grinds to form uniform powder.
7. the preparation method of a sulfoxide type or sulfone compound, it is characterized in that, comprise the steps: in raw material, add solvent and catalysts, be under the illumination of 190 ~ 780nm at wavelength, react in the air or oxygen atmosphere of 1 ~ 10MPa, reaction temperature is 20 ~ 200 DEG C, and the reaction time is 1 ~ 72 hour; The weight ratio of raw material, solvent and catalysts is 1:2.67 ~ 40:0.01 ~ 1; Described catalysts is carbon monoxide-olefin polymeric described in catalyst described in claim 1,2 or 3 or claim 5; Described raw material is thio-ether type compounds or sulfoxide compound.
8. preparation method according to claim 7, is characterized in that, the weight ratio of described raw material, solvent and catalysts is 1:5 ~ 10:0.01 ~ 0.5; Described solvent is selected from one or more mixtures in carrene, 1,2-dichloroethanes, oxolane, ethyl acetate, methyl alcohol, ethanol, toluene, acetone, ether, Isosorbide-5-Nitrae-dioxane, acetonitrile, nitromethane and water.
9. the preparation method according to claim 7 or 8, is characterized in that, described carbon monoxide-olefin polymeric is support type or non-loading type catalysts composition.
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| CN102580726A (en) * | 2012-02-13 | 2012-07-18 | 北京神雾环境能源科技集团股份有限公司 | Coal pyrolysis catalyst and preparation method thereof |
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| DE1912729A1 (en) * | 1969-03-13 | 1970-10-01 | Basf Ag | Process for the production of sulfoxides |
| CN1226285C (en) * | 2003-12-15 | 2005-11-09 | 华南理工大学 | Method for preparing sulfone by catalytic oxidation of thioether |
| TWI381883B (en) * | 2006-03-10 | 2013-01-11 | Nippon Catalytic Chem Ind | Catalyst for wastewater treatment and method for wastewater treatment using said catalyst |
| CN102249959B (en) * | 2011-05-19 | 2014-05-21 | 浙江工业大学 | Method for preparing sulfoxide through catalytic oxidation |
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