CN104707651B - Catalyst and its preparation and application of a kind of catalysis silane to silanol Efficient Conversion - Google Patents
Catalyst and its preparation and application of a kind of catalysis silane to silanol Efficient Conversion Download PDFInfo
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- CN104707651B CN104707651B CN201310695169.9A CN201310695169A CN104707651B CN 104707651 B CN104707651 B CN 104707651B CN 201310695169 A CN201310695169 A CN 201310695169A CN 104707651 B CN104707651 B CN 104707651B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses the method that load Au nano particles prepare different-phase catalyst SBA PIL Au in a kind of 15 mesopore orbits of SBA, and use it for the reaction that efficient catalytic silane is converted to silanol.For the active force between enhancing base materials and nanogold particle, we are proposed first by a kind of ion liquid polymer brush：Poly- (1 (4 alkene phenyl) 3 methylimidazole chlorine) situ-formed graft is grown on the hole wall of mesoporous material SBA 15.SBA PIL Au to a series of different types of silane to silanol conversion reaction all show high conversion (>98%) and high selectivity (in product, silanol：Siloxanes>99:1).After catalyst recycles 3 times, there is not at all decline in catalytic performance, only does solvent and oxidant with water, do not use organic solvent, environmental protection in course of reaction.
Description
Technical field
The present invention relates to a kind of preparation of new different-phase catalyst SBA-PIL-Au：Mesoporous material SBA-15 loads Au nanometers
Particle is used to be catalyzed Efficient Conversion of the silane to silanol.
Background technology
It is the important organic reaction of a class that silane selective oxidation prepares silanol, and product silanol can be further used as raw material
Synthesizing organo-silicon polymer.But it is catalyzed such reaction needs and uses the strong oxidizers such as permanganate, ozone, silver salt, instead
The selectivity answered is bad, has substantial amounts of siloxanes and other harmful by-products are generated, both reduced economic benefit, and caused environment again
Pollution.How brand-new catalyst is found, and the selectivity for improving the reaction just becomes the direction that people make great efforts to seek.
Golden nanometer particle is a kind of catalyst of function admirable, but due to size itself too little (only several nanometers), is held
Easily occur to reunite, so it is difficult to using separately as catalyst.Nineteen ninety, Haruta et al. take the lead in《German applied chemistry》It is miscellaneous
Report in will（Bibliography 1.W.Adam, R.Mello, R.Curci, Angew.Chem.Int.Ed., 1990,29,890.）：Adopt
Golden nanometer particle can be loaded to oxidation of the loaded catalyst on metal oxide carrier, obtaining to CO with co-electrodeposition method
Reaction is with very high catalysis activity.Hereafter, golden loaded catalyst starts the concern for causing people, and hydroxyapatite, carbon are received
The carrier all in succession as supported nano-gold particle such as mitron, polymeric colloid microballoon（Bibliography 2.T.Mitsudome,
A.Noujima, T.Mizugaki, K.Jitsukawa, K.Kaneda, Chem.Commun., 2009,5302. bibliography
3.J.John,E.Gravel,A.Hagge,H.Y.Li,T.Gacoin,E.Doris,Angew.Chem.Int.Ed.,2011,50,
7533.）, for being catalyzed the chemical reaction of series of different and achieving good effect.As a rule, the load of selection
Base material needs to meet following two conditions：(1) have than larger specific surface area, be conducive to the abundant load of Au catalyst；(2) it is right
The Au catalyst for having loaded has certain stably dispersing effect, it is to avoid catalysis activity drop caused by reuniting because of gold nano grain
It is low.
SBA-15 is a kind of important two-dimentional hexagonal phase mesopore molecular sieve, is synthesized by the report such as Zhao Dongyuan earliest（With reference to text
4.D.Y.Zhao, J.L.Feng, Q.S.Huo, N.Melosh, G.H.Fredrickson, B.F.Chmelka are offered,
G.D.Stucky,Science,1998,279,548.）.It has higher specific surface area (690～1040m2/ g), Ke Yishi
The now a large amount of loads to catalyst；Periodically duct (4.6～30nm of channel diameter) has size confinement effect, suppression again in order
The reunion of the nano particle in embedded duct is made.Therefore, SBA-15 is particularly well suited as the carrier of supported nano-gold particle.
But, due to lacking effective interaction force between organosilicon and nanogold particle, it is desirable to obtain nanogold particle load
SBA-15 is not easy to.
Here, we have successfully prepared SBA-15 load Au nano particle different-phase catalyst SBA-PIL-Au first,
And use it for being catalyzed Efficient Conversion of the silane to silanol, structure and catalytic property schematic diagram and the transmission electron microscope of SBA-PIL-Au
Picture is as shown in Figure 1.For the interaction force between enhancing base materials and nanogold particle, we are innovatively proposed one kind
Ion liquid polymer brush (PIL)：Poly- (1- (4- alkene phenyls) -3- methylimidazole chlorine) situ-formed graft grows into the hole wall of SBA-15
On.Chlorion in ion liquid polymer brush and [AuCl4]-Between ion-exchange reactions can occur, it is then anti-by reduction
Should, it is possible among the duct of Au nanometer particle loads to SBA-15.SBA-PIL-Au is to a series of different types of silane
High conversion and high selectivity are shown all to silanol conversion reaction.After catalyst recycles 3 times, catalytic performance does not occur
At all decline, and only solvent and oxidant are done with water in catalytic reaction process, it is not necessary to using other organic solvents, very ring
Protect.
The content of the invention
Here, we have successfully prepared SBA-15 load Au nano particle different-phase catalyst SBA-PIL-Au first,
And use it for being catalyzed Efficient Conversion of the silane to silanol.
To realize the object of the invention, which adopts concrete technical scheme as shown in Equation 1：
It is surface modified firstly the need of carrying out to SBA-15, with 4- (chloromethyl) phenyltrimethoxysila,e (CTS) be
Modifying agent, realizes being chemically bonded by sol gel reaction between the silane epoxide of CTS and the hydroxyl on SBA-15 surfaces, surface
The C atoms for exposing are used to cause follow-up ATRP (ATRP) to react.Described CTS modifying agent can also be by
Other molecules with similar structures are substituted, and its common trait is：Contain simultaneously silane epoxide-Si (OR) and halogen atom (Cl,
Br molecule).Wherein, R represents methyl or ethyl.
Reacted polymerisable ionic liquid monomer (1- (4- alkene phenyls) -3- methylimidazole chlorine) ([VBMI] using ATRP
[Cl]) the SBA-15 surfaces that were modified to CTS of in-situ grafting polymerization, described [VBMI] [Cl] synthesize according to the route of formula 2,
Can be substituted by other molecules with similar structures, its common trait is：Contain carbon-to-carbon double bond simultaneously and imidazoles is pentacyclic
Ionic liquid.Ion liquid polymer brush：Poly- (1- (4- alkene phenyls) -3- methylimidazole chlorine) (PIL) as shown in Equation 1 situ-formed graft
To SBA-15 surfaces.
[AuCl4]-SBA-15 is entered into by exchanging with the chlorion in poly- (1- (4- alkene phenyls) -3- methylimidazole chlorine)
Mesopore orbit, adds NaBH4Reduction makes golden nanometer particle growth in situ in the duct of SBA-15, obtains catalyst SBA-
PIL-Au。
With SBA-PIL-Au as different-phase catalyst, water is oxidant and solvent, is catalyzed different types of silane to silanol
Conversion reaction.Described silane, its common trait is：Molecular formula is SiHR3Or SiH2R2, alkyl or benzene of the wherein R for C1～C4
Base.Described silanol, its common trait is：Molecular formula is Si (OH) R3Or Si (OH)2R2, alkyl or benzene of the wherein R for C1～C4
Base.An example is given in formula 3：SBA-PIL-Au is catalyzed triethyl silicane to triethyl silanol conversion reaction.
Comprise the following steps that：
The first step：As shown in Equation 2, the synthesis of (1- (4- alkene phenyls) -3- methylimidazole chlorine) ([VBMI] [Cl])：4- (chlorine
Methyl) 24h are reacted in 45 DEG C under nitrogen protection after the blending of styrene and 1- methylimidazoles.Reaction is cooled to room temperature after terminating, and sinks
Vacuum drying after starch filtration washing.
Second step：SBA-15 surface modification initiator CTS
SBA-15 mixes backflow 4h with 17%HCl solution, makes SBA-15 surface exposures go out silicone hydroxyl as much as possible.Process
The SBA-15 for crossing mix with CTS, toluene, pyridine after stirred under nitrogen atmosphere backflow 16h.After product successively uses acetone, water washing,
100 DEG C of dried in vacuum overnight.SBA-15 surfaces are successfully grafted chloride ATRP initiator CTS.Intermediate product now is named as
SBA-CTS.Grafting amounts of the CTS in SBA-15 is 0.01-0.1wt%.
3rd step：SBA-CTS surface grafting ion liquid polymers (PIL)
Using ATRP polymerization method in SBA-CTS surface grafting ion liquid polymer brushes.From monomer be formula 2
[VBMI] [Cl] of synthesis, method is as follows：By SBA-CTS and stannous chloride (CuCl), 2,2 '-bipyridyl (BiPy), [VBMI]
Vacuumize after the stirring mixing of [Cl], dimethylformamide (DMF), be warmed up to 50 DEG C of reaction 12h afterwards under nitrogen protection.Product
With 100 DEG C of dried in vacuum overnight after DMF, water washing.Intermediate product now is named as SBA-PIL.PIL connecing in SBA-15
Branch amount is 0.1-2wt%.
4th step：The preparation of SBA-PIL-Au catalyst
SBA-PIL is dispersed in water, a certain amount of HAuCl is poured into4The aqueous solution, stirs 30min, makes [AuCl4]-With
Chlorion in SBA-PIL is fully exchanged.After filtering washing, product is dispersed in water again, a certain amount of NaBH is poured into4
The aqueous solution, is stirred vigorously reaction 30min, makes Au of the absorption in SBA-PIL3+It is reduced to golden nanometer particle.80 after product washing
DEG C dried in vacuum overnight obtains final product SBA-PIL-Au.Load capacity of the Au in SBA-15 is 0.5-2.3wt%.
5th step：SBA-PIL-Au is catalyzed Efficient Conversion of the silane to silanol as different-phase catalyst.Catalyst is in solvent
In mass concentration be 0.5-2wt%.
Water is stirred vigorously at 40 DEG C with silane mixture, adds a certain amount of SBA-PIL-Au catalyst, continues stirring
Reaction.Catalytic reaction products gas chromatographic detection, conversion ratio are drawn from experiment curv with selective.
SBA-PIL-Au of the present invention：A kind of promotion catalyst of the silane to silanol Efficient Conversion, its advantage
In terms of being mainly reflected in following four:
1) supporting substrates of the golden nanometer particle selected are SBA-15, and it has higher specific surface area, the load to Au
Amount reaches 2.3wt%；Periodically duct has size confinement effect in order, it is suppressed that the group of the nano particle in embedded duct
Poly-, golden nanometer particle is uniformly dispersed in SBA-15, and average-size is about 2.5nm.
2) propose first a kind of ion liquid polymer brush (PIL) situ-formed graft to be grown on the hole wall of SBA-15.Again
Reacted by ion-exchange reactions and in-situ reducing, it is possible among the duct of Au nanometer particle loads to SBA-15, solved
Lack the problem of active force before this between organosilicon and gold grain.
3) SBA-PIL-Au to a series of different types of silane to silanol conversion reaction all show high conversion (>
98%) with high selectivity (silanol：Siloxanes>99:1).After catalyst recycles 3 times, there is not at all decline in catalytic performance.
4) solvent and oxidant are done with water only in catalytic reaction process, it is not necessary to using other organic solvents, very environmentally friendly.
To sum up, SBA-PIL-Au of the present invention：A kind of promotion catalyst of the silane to silanol Efficient Conversion, which is to Au
Catalyst loadings height, syntheti c route deft design, catalytic reaction there is high conversion and high selectivity, can be recycled and not
Reduce catalytic performance, environmental protection.
Description of the drawings
The structure of Fig. 1 .SBA-PIL-Au and catalytic property schematic diagram and transmission electron microscope picture.
Specific embodiment
The present invention is further described with reference to specific embodiment, but protection scope of the present invention is not limited to that.
Embodiment 1
The first step：The synthesis of [VBMI] [Cl]：4- (chloromethyl) styrene (1.53g, 10mmol) and 1- methylimidazoles
24h is reacted in 45 DEG C under nitrogen protection after (0.82g, 10mmol) blending.Reaction is cooled to room temperature after terminating, and sediment crosses diafiltration
Wash rear vacuum drying.
Second step：SBA-15 surface modification initiator CTS
SBA-15 mixes backflow 4h with 17%HCl solution, makes SBA-15 surface exposures go out silicone hydroxyl as much as possible.Process
The SBA-15 (2.0g) for crossing mix with CTS (1.0g), toluene (40mL), pyridine (1.0g) after stirred under nitrogen atmosphere backflow 16h.
After product successively uses acetone, water washing, 100 DEG C of dried in vacuum overnight.SBA-15 surfaces are successfully grafted chloride ATRP initiators
CTS。
3rd step：SBA-CTS surface grafting PIL
Using ATRP polymerization method in SBA-CTS surface grafting ion liquid polymer brushes.From monomer be formula 2
[VBMI] [Cl] of synthesis, method is as follows：By SBA-CTS (1.0g) and CuCl (3.5mg), BiPy (7.8mg), 40mL [VBMI]
Vacuumize after the DMF solution stirring mixing of [Cl], be warmed up to 50 DEG C of reaction 12h afterwards under nitrogen protection.Product DMF, water
100 DEG C of dried in vacuum overnight after washing.
4th step：The preparation of SBA-PIL-Au catalyst
SBA-PIL (1.0g) is dispersed in 5mL water, HAuCl is poured into4(15.0mL, 3mM) aqueous solution, stirs 30min,
Make [AuCl4]-Fully exchange with the chlorion in SBA-PIL.After filtering washing, product is dispersed in water again, is poured into
NaBH4(10.0mL, 0.2M) aqueous solution, is stirred vigorously reaction 30min, makes Au of the absorption in SBA-PIL3+It is reduced to gold nano
Particle.After product washing, 80 DEG C of dried in vacuum overnight obtain final product SBA-PIL-Au.
5th step：SBA-PIL-Au is catalyzed Efficient Conversion of the silane to silanol as different-phase catalyst
3mL water is stirred vigorously at 40 DEG C with 1mmol silane mixtures, adds the SBA-PIL-Au catalyst of 0.03g, after
Continuous stirring reaction 1h.Catalytic reaction products gas-chromatography (model：Agilent7890A, chromatographic column：HP-5) detect, conversion ratio
Draw from experiment curv with selectivity.SBA-PIL-Au is showed to silanol conversion reaction to a series of different types of silane
Go out high conversion (>98%) with high selectivity (silanol：Siloxanes>99:1).After catalyst recycles 3 times, catalytic performance does not have
Occur at all declining.
Embodiment 2-4
SBA-PIL-Au is catalyzed conversion reaction of the triethyl silicane to triethyl silanol, catalytic performance after recycling 3 times
It is no to occur at all declining, according to described in table 1, other prepare, react, test condition, with embodiment 1.
Table 1
Embodiment 5-11
SBA-PIL-Au shows high conversion and Gao Xuan to silanol conversion reaction to a series of different types of silane
Selecting property, according to described in table 2, other prepare, react, test condition, with embodiment 1.
Table 2
The present invention successfully prepared first SBA-15 load Au nano particle different-phase catalyst SBA-PIL-Au, and by its
For being catalyzed Efficient Conversion of the silane to silanol.For the interaction force between enhancing base materials and nanogold particle, Wo Menchuan
New property ground is proposed a kind of ion liquid polymer brush (PIL)：Poly- (1- (4- alkene phenyls) -3- methylimidazole chlorine) situ-formed graft life
Grow on the hole wall of SBA-15.SBA-PIL-Au shows high turn to silanol conversion reaction to a series of different types of silane
Rate and high selectivity.After catalyst recycles 3 times, there is not at all decline in catalytic performance, and in catalytic reaction process
Only solvent and oxidant are done with water, it is not necessary to using other organic solvents, very environmentally friendly.
Claims (6)
- It is 1. a kind of to be catalyzed preparation method of the silane to the catalyst of silanol Efficient Conversion, it is characterised in that：Firstly the need of to mesoporous Material SBA-15 carry out it is surface modified, with contain silane epoxide-Si (OR) and halogen atom simultaneously molecule as modifying agent, Realize being chemically bonded by sol gel reaction between the silane epoxide of modifying agent and the hydroxyl on SBA-15 surfaces, surface is exposed Halogen atom be used for cause follow-up ATRP (ATRP) to react；The polymerisable ionic liquid monomer of ATRP reactions is adopted for while containing carbon-to-carbon double bond and the pentacyclic ionic liquid of imidazoles Body monomer；Grafting amount of the modifier molecules in SBA-15 is 0.01-0.1wt%；Polymerisable ionic liquid monomer is in SBA-15 Grafting amount be 0.1-2wt%；2)[AuCl4]-By entering into SBA-15 mesopore orbits with the anion exchange of polymerisable ionic liquid monomer, then plus Enter NaBH4Reduction makes golden nanometer particle growth in situ in the duct of SBA-15；The product for obtaining is mesoporous material SBA-15 The different-phase catalyst of load Au nano particles, is named as SBA-PIL-Au；Load capacity of the Au in SBA-15 is 0.5-2.3wt%.
- It is 2. as claimed in claim 1 to be catalyzed preparation method of the silane to the catalyst of silanol Efficient Conversion, it is characterised in that:It is described contain silane epoxide-Si (OR) and halogen atom simultaneously molecule be：4- (chloromethyl) phenyltrimethoxysila,e (CTS), wherein, R represents methyl or ethyl；The SBA-15 surfaces polymerisable ionic liquid monomer in-situ grafting polymerization to CTS being modified using ATRP reactions；Can Can be with [AuCl in the ionic liquid monomer of polymerization4]-Occur ion exchange anion be chlorion, fluorine ion, bromide ion, [PF6]-In one or more；The cationic moiety of ionic liquid monomer is (1- (4- alkene phenyls) -3- methylimidazoles).
- 3. catalyst from the catalysis silane that prepared by preparation method described in a kind of claim 1 or 2 to silanol Efficient Conversion should With, it is characterised in that:With the SBA-PIL-Au as different-phase catalyst, water is oxidant and solvent, is catalyzed different types of silicon Conversion reaction of the alkane to silanol；Described silane, its common trait is：Molecular formula is SiHR3Or SiH2R2, alkyl or phenyls of the wherein R for C1～C4；Described silanol, its common trait is：Molecular formula is Si (OH) R3Or Si (OH)2R2, wherein R for C1～C4 alkyl or Phenyl.
- 4. catalysis application of the silane to the catalyst of silanol Efficient Conversion described in a kind of claim 3, it is characterised in that:Catalysis Agent mass concentration in a solvent is 0.5-2wt%.
- 5. catalysis application of the silane to the catalyst of silanol Efficient Conversion described in a kind of claim 3 or 4, it is characterised in that:Described SBA-PIL-Au catalyst is more than 98% to silanol conversion reaction conversion ratio to above-mentioned silane, selects in product Property：Silanol:Siloxanes>99:1, after catalyst recycles 3 times, there is not at all decline in catalytic performance.
- 6. catalysis catalyst of the silane to silanol Efficient Conversion that prepared by the preparation method described in a kind of claim 1 or 2, which is special Levy and be:Being catalyzed silane to the final composition and relative amount of the catalyst of silanol Efficient Conversion is：SBA-15(96- 99wt%), the ionic liquid (0.1-2wt%) of polymerization, Au (0.5-2.3wt%).
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| JP6917020B2 (en) | 2017-05-15 | 2021-08-11 | 国立大学法人大阪大学 | Method for producing silanol compound and hydrogen |
| KR102036521B1 (en) | 2018-03-22 | 2019-10-25 | 서울대학교산학협력단 | The Method for preparing Silanol and Methanol from silyl formate using hydrogenation |
| CN112098584B (en) * | 2020-09-15 | 2022-10-18 | 南京工业大学 | Assembling method and catalytic application of carbon nanotube/gold nanoparticle composite |
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| CN102671701A (en) * | 2011-12-08 | 2012-09-19 | 河南科技大学 | Catalyst for synthesizing vinyl chloride monomer and preparation method thereof |
| CN103140285A (en) * | 2010-09-30 | 2013-06-05 | 赢创奥克森诺有限责任公司 | Use of supported ionic liquid phase (silp) catalyst systems in the hydroformylation of olefin-containing mixtures to give aldehyde mixtures with a high proportion of 2-unbranched aldehydes |
| CN103406146A (en) * | 2013-07-16 | 2013-11-27 | 常州大学 | Preparation method of immobilized alkaline ionic liquid catalyst |
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| CN103140285A (en) * | 2010-09-30 | 2013-06-05 | 赢创奥克森诺有限责任公司 | Use of supported ionic liquid phase (silp) catalyst systems in the hydroformylation of olefin-containing mixtures to give aldehyde mixtures with a high proportion of 2-unbranched aldehydes |
| CN102671701A (en) * | 2011-12-08 | 2012-09-19 | 河南科技大学 | Catalyst for synthesizing vinyl chloride monomer and preparation method thereof |
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