CN101259435A - Polyphase catalyst for preparing alcohol and preparation and application - Google Patents

Polyphase catalyst for preparing alcohol and preparation and application Download PDF

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Publication number
CN101259435A
CN101259435A CNA2007100642319A CN200710064231A CN101259435A CN 101259435 A CN101259435 A CN 101259435A CN A2007100642319 A CNA2007100642319 A CN A2007100642319A CN 200710064231 A CN200710064231 A CN 200710064231A CN 101259435 A CN101259435 A CN 101259435A
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catalyst
aryl
carrier
heterogeneous catalyst
alkyl
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李�灿
李军
张艳梅
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention relates to a multi-phase catalyst used for preparing alcohol, a preparation method and application thereof. The preparation steps of the catalyst comprises (a) preparing a functionalized carrier which contains hydrosulphonyl or CH=CH2; (b) simultaneously polymerizing the catalyst and hyamine on the carrier prepared in the step (a); (c) dissolving products obtained in the step (b) into the H2O, adding a precursor of metal catalyst and obtaining the multi-phase catalyst. The multi-phase catalyst of the invention has simple preparation method and convenient reaction operation; when used in aldehyde - hydrogen transfer reaction to prepare alcohol products, the catalyst has specialized chemical selectivity and can show an activity 9 times higher than that of a corresponding homogeneous phase catalyst, furthermore, the catalyst can be recycled for a plurality of times.

Description

A kind of heterogeneous catalyst and preparation method and application that is used to prepare alcohol
Technical field
The present invention relates to a kind of heterogeneous catalyst, specifically, relate to a kind of on carrier the heterogeneous catalyst that is used to prepare alcohol of simultaneously immobilized catalyst and quaternary ammonium salt.
The invention still further relates to the preparation method of above-mentioned heterogeneous catalyst.
The invention still further relates to the application of above-mentioned heterogeneous catalyst in the aldehyde hydrogen transfer reaction.
Background technology
Preparing one of pure important method is by original realize [WO0063143] of going back of aldehyde.Industrial production mainly realizes with the heterogeneous catalyst of carrying metal, is that to be aided with Cr, Mo, W, Co, Mn, Ti etc. be auxiliary agent [Appl.Catal.A 280 (2005) 17] to main component [US5888923] with Raney Ni wherein; And for α, the selective hydration of beta-unsaturated aldehyde is Ir, the Os metal ingredient [Catal.Rev.Sci.Eng.40 (1998) 81] to support mainly.But these catalyst are when the aldehyde compound that a plurality of functional groups of reduction exist, and chemo-selective can not be satisfactory.
Homogeneous catalyst has showed good chemo-selective [Acc.Chem.Res. in the reduction of aldehyde, 35 (2002) 738], but the organic ligand of these catalyst mainly is to contain phosphine compound, to oxygen sensitive, with an organic solvent, cause environmental pollution easily in the reaction.
The up-to-date diamine ligand that studies show that shows very high activity and single-minded chemo-selective [Angew.Chem.Int.Ed.45 (2006) 6718] in the hydrogen transfer reaction of aldehyde, be reflected in the water and carry out, and does not use any organic solvent, environmental protection; Especially to α, beta-unsaturated aldehyde and when containing the hydrogenation of polyfunctional group aldehyde compound has showed good chemo-selective.But the same with other homogeneous catalytic reactions, this reaction system exists that product separates with the catalyst difficulty, product is difficult for purifying and shortcoming such as the difficult recovery of catalyst, and its commercial Application is subjected to certain restriction,
We with this homogeneous catalyst immobilized after, the chemo-selective that has well kept catalyst by modulation carrier surface character, obtained simultaneously than the higher heterogeneous catalyst of corresponding homogeneous catalyst activity, catalyst can be realized recycling, greatly reduce the cost of catalyst, be convenient to heavy industrialization and use.And similar heterogeneous catalyst is international and domesticly all do not appear in the newspapers.
Summary of the invention
The object of the present invention is to provide a kind of heterogeneous catalyst for preparing alcohol.
Another purpose of the present invention is to provide the method for the above-mentioned heterogeneous catalyst of preparation.
For achieving the above object, the heterogeneous catalyst that is used to prepare alcohol provided by the invention, its essential characteristic be carrier surface simultaneously immobilized catalyst and quaternary ammonium salt, structural formula as shown in the formula:
Figure A20071006423100061
In the formula:
R 1-R 4Separate;
R 1=C 1-C 10End contains sulfydryl or CH=CH 2The alkyl or aryl estersil;
R 2=H, C 1-C 10Alkyl or aryl;
R 3=C 1-C 16End contains CH=CH 2Alkyl or aryl;
R 4=C 1-C 16Alkyl or aryl;
L=aryl or contain C 1-C 3The phenolic compound of alkyl substituent;
The X=halogen atom;
M is meant metal, is Rh, Ru or Ir;
1≤m≤15，0≤n≤10
Carrier is inorganic or the organic inorganic hybridization porous material.
Described heterogeneous catalyst, wherein, carrier is inorganic silicon dioxide material, hybrid inorganic-organic material, the inorganic silicon dioxide carrier of organic group modified, Fe 3O 4Or silica parcel Fe 3O 4Magnetic nano-particle.
Described heterogeneous catalyst, wherein, the metal precursor structure expression is:
[MX m1L n1] p
Wherein, M=Rh, Ru or Ir; The X=halogen atom; L=aryl or contain C 1-C 3The phenolic compound of alkyl substituent; M1=2,3, n1=0,1; P=1,2.
The method of the above-mentioned heterogeneous catalyst of preparation provided by the invention the steps include:
(a) carrier and R 1Reflux in organic solvent, preparation contains the sulfydryl of weight ratio 4-5% or the CH=CH of weight ratio 3-4% 2Carrier;
(b) carrier that step a is prepared and two amine ligands, quaternary ammonium salt, initator polymerization in solution, washing, dry (percentage is all the weight ratio that whole reaction system feeds intake); Wherein by weight: two amine ligand 8-10%, quaternary ammonium salt 2～10%, initator 0.8-1%;
(c) product with step b is dissolved in H 2Among the O, add the coordination of metal catalyst precursor body, obtain heterogeneous catalyst; Wherein: two amine ligands: the coordination of metal catalyst precursor body is 4-6: 1-2 μ mol;
R among the step a 1Be C 1-C 10End contains sulfydryl or CH=CH 2The alkyl or aryl estersil, its basic structure formula is
(R 5O) 3Si-(CH 2) k-SH (R 5O) 3Si-(CH 2) k-CH＝CH 2
R wherein 5=CH 3, CH 3CH 2, 1≤K≤10;
Carrier among the step a is inorganic or the organic inorganic hybridization porous material
Organic solvent among the step a is toluene, chloroform or ethanol;
Quaternary ammonium salt among the step b is C 1-C 16End contains CH=CH 2Alkyl or aryl;
Initator among the step b is an azodiisobutyronitrile;
Solvent among the step b is N, dinethylformamide, N, at least a in N-dimethylacetylamide, the methyl-sulfoxide.
Described method, wherein, the carrier among the step a is inorganic silicon dioxide material, hybrid inorganic-organic material, the inorganic silicon dioxide carrier of organic group modified, Fe 3O 4Or silica parcel Fe 3O 4Magnetic nano-particle.
Described method, wherein, the represented aryl of metal precursor L or contain C among the step c 1-C 3The phenolic compound of alkyl substituent, molecular formula is as follows:
Figure A20071006423100081
Heterogeneous catalyst provided by the invention is a chirality diamine-metallic complex polyphase catalyzer, can be used in the aldehyde hydrogen transfer reaction, and wherein, the molecular formula of the aldehyde of the reaction substrate that is suitable for is:
Figure A20071006423100091
R wherein 6Be C 1-C 18With contain heteroatomic alkyl or aryl.
Compared with prior art, the present invention has the following advantages:
1, the invention provides heterogeneous catalyst and prepare easily, post-reaction treatment is simple to operate.
2, this heterogeneous catalyst shows than corresponding homogeneous catalyst high activity more.
3, this heterogeneous catalyst shows single-minded chemo-selective.
4, this heterogeneous catalyst can be recycling.
Description of drawings
Fig. 1 is that the heterogeneous catalyst of different proportion quaternary ammonium salt polymerization and homogeneous catalyst specific activity are than schematic diagram.
The specific embodiment
Concrete implementation step of the present invention is as follows:
(1) preparation functional supports,
With macro porous silica gel and R 1Place noble gas protection solvent, reflux 24 hours (h) suction filtration, washing, drying.
(2) polymerization catalyst
Carrier, two amine ligands, quaternary ammonium salt and the initator of step 1 preparation are placed noble gas protection solvent, under suitable temperature, react 24h, suction filtration, washing, drying.
(3) product with step 2 is dissolved in H 2Among the O, add the metal catalyst precursor body, proper temperature stirs 1h down, obtains heterogeneous catalyst of the present invention.
In the said method:
Step 1 noble gas is meant nitrogen or argon gas, preferred argon gas.Solvent is meant toluene, chloroform or ethanol, preferred toluene.
Step 2 initator is an azodiisobutyronitrile.Solvent is N, dinethylformamide, N, N-dimethylacetylamide, methyl-sulfoxide, preferred N, dinethylformamide.Proper temperature is 60～65 ℃.
The heterogeneous catalyst structure of step 3 preparation is
Figure A20071006423100101
Metal precursor structural formula wherein is
[MX m1L n1] p
M=Rh, Ru or Ir; The X=halogen atom; L=aryl or contain C 1-C 3The phenolic compound of alkyl substituent; M1=2,3; N1=0,1; P=1,2.
R wherein 1-R 4Separate; R 1=C 1-C 10End contains sulfydryl or CH=CH 2The alkyl or aryl estersil; R 2=H, C 1-C 10Alkyl or aryl; R 3=C 1-C 16End contains CH=CH 2Alkyl or aryl; R 4=C 1-C 16Alkyl or aryl; The X=halogen atom; M=Rh, Ru or Ir, preferred Ir; Carrier is inorganic material or organic inorganic hybridization porous material, Fe 3O 4Or silica parcel Fe 3O 4Magnetic nano-particle; L=aryl or contain C 1-C 3The phenolic compound of alkyl substituent, molecular formula is as follows:
Figure A20071006423100111
In order to further specify the present invention, adopting ethylenediamine is two amine ligands, [LIrCl 2] 2(L=pentamethyl cyclopentadiene) be metal precursor as hydrogen transfer reaction embodiment, but it does not limit the defined invention scope of each accessory claim.
Embodiment 1: the preparation heterogeneous catalyst
1) prepares mercapto-functionalized carrier
The 10g macro-pore SiO 2(specific surface position 400m 2/ g, the aperture is 9.3nm) 70 ℃ of degassing 4h under vacuum,, under argon shield, add dry toluene 150ml and 1ml triethoxy mercapto propyl group estersil, be warmed up to 110 ℃, the 24h that under violent stirring, refluxes, suction filtration, washing, vacuum drying.
2) two amine ligands (VTsEN) preparation [referring to Chem.Eur.J.6 (2000) 4604)
At room temperature will be to the CH of styrene sulfonic acid chloride (1mmol) 2Cl 220ml slowly is added drop-wise to the CH of ethylenediamine (100mmol) 2Cl 280ml stirs 2h, pickling, and alkali cleaning is spin-dried for solvent and obtains VTsEN.
3) polymerization catalyst
With step 1) carrier 0.7g, step 2) 0.15g (0.66mmol) VTsEN, in right amount to ethylene benzyl trimethyl ammonium chloride (VTAC) [the relative different mol ratio (0.00 of VTsEN, 0.17,0.42,0.63,0.83,1.00) and 20mg AIBN (azodiisobutyronitrile) be dissolved among the DMF of 10ml degassing dehydration, under argon gas, react 24h at 60～65 ℃, suction filtration, washing, vacuum drying obtain catalyst S iO 2-SH-VTAC x-VTsEN (the wherein mol ratio of x=VTAC/VTsEN)
4) heterogeneous catalyst that contains 6 μ mol, two amine ligands and the [LIrCl that step 3 is prepared 2] 2(L=pentamethyl cyclopentadiene) 2 μ mol are dissolved in 15ml H 2O stirs 1h under 80 ℃ of argon gas, generate heterogeneous catalyst of the present invention.
Embodiment 2: the heterogeneous catalyst of different proportion quaternary ammonium salt polymerization and homogeneous catalyst reactivity are relatively
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15ml water, adds 40mmol benzaldehyde, 6.8g NaCOOH, stops in 10 minutes in 80 ℃ of reactions, uses ethyl acetate extraction, analyzes conversion ratio with gas chromatograph behind the filtrate column chromatography purification, the results are shown in Figure 1.
Embodiment 3: heterogeneous catalyst is used for the circulation experiment of benzaldehyde hydrogen transfer reaction, and (annotate: following example is all SiO 2-SH-VTAC 0.83-VTsEN, VTAC: VTsEN=0.83: the heterogeneous catalyst of 1 polymerization)
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15m water, add 20mmol benzaldehyde, 6.8gNaCOOH in 80 ℃ of reactions, after reaction finishes, the centrifugation catalyst, with be used for reacting after alcohol-water (1: 1) the 10ml washed twice next time, the results are shown in Table 1.
Embodiment 4: heterogeneous catalyst is used for the benzaldehyde hydrogen transfer reaction
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15m water, adds 20mmol benzaldehyde, 6.8gNaCOOH in 80 ℃ of reactions, the results are shown in Table 2.
Embodiment 5: heterogeneous catalyst is used for the m-nitrobenzaldehyde hydrogen transfer reaction
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15m water, adds 20mmol m-nitrobenzaldehyde, 6.8gNaCOOH in 80 ℃ of reactions, the results are shown in Table 2.
Embodiment 6: heterogeneous catalyst is used for the 4-chloro-benzaldehyde hydrogen transfer reaction
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15m water, adds 20mmol 4-chloro-benzaldehyde, 6.8gNaCOOH in 80 ℃ of reactions, the results are shown in Table 2.
Embodiment 7: heterogeneous catalyst is used for the p-tolyl aldehyde hydrogen transfer reaction
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15m water, adds 20mmol p-tolyl aldehyde, 6.8gNaCOOH in 80 ℃ of reactions, the results are shown in Table 2.
Embodiment 8: heterogeneous catalyst is used for the p-bromobenzaldehyde hydrogen transfer reaction
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15m water, adds 20mmol p-bromobenzaldehyde, 6.8gNaCOOH in 80 ℃ of reactions, the results are shown in Table 2.
Embodiment 9: heterogeneous catalyst is used for the P-methoxybenzal-dehyde hydrogen transfer reaction
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15m water, adds 20mmol P-methoxybenzal-dehyde, 6.8gNaCOOH in 80 ℃ of reactions, the results are shown in Table 2.
Embodiment 10: heterogeneous catalyst is used for the furfural hydrogen transfer reaction
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15m water, adds 20mmol furfural, 6.8gNaCOOH in 80 ℃ of reactions, the results are shown in Table 2.
Embodiment 11: heterogeneous catalyst is used for the hydrogen transfer reaction of acetophenone formaldehyde
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15m water, and adding 20mmol in 80 ℃ of reactions, the results are shown in Table 2 to acetophenone formaldehyde, 6.8gNaCOOH.
Embodiment 12: heterogeneous catalyst is used for 2, the hydrogen transfer reaction of 5-dimethoxy benzaldehyde
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15m water, adds 20mmol2.5-dimethoxy benzaldehyde, 6.8g NaCOOH in 80 ℃ of reactions, the results are shown in Table 2.
Embodiment 13: heterogeneous catalyst is used for the cinnamic acid hydrogen transfer reaction
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15m water, adds 4mmol cinnamic acid, 6.8gNaCOOH in 80 ℃ of reactions, the results are shown in Table 2.
Embodiment 14: heterogeneous catalyst is used for a nitro cinnamaldehyde hydrogen transfer reaction
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15m water, and nitro cinnamaldehyde, 6.8gNaCOOH the results are shown in Table 2 in 80 ℃ of reactions between adding 4mmol.
Embodiment 15: heterogeneous catalyst is used for the hydrogen transfer reaction of acetyl cinnamic acid
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15m water, and adding 4mmol in 80 ℃ of reactions, the results are shown in Table 2 to acetyl cinnamic acid, 6.8gNaCOOH.
Embodiment 16: heterogeneous catalyst is used for the citral hydrogen transfer reaction
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15m water, adds 4mmol citral, 6.8gNaCOOH in 80 ℃ of reactions, the results are shown in Table 2.
Embodiment 17: heterogeneous catalyst is used for the crotonaldehyde hydrogen transfer reaction
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15m water, adds 4mmol crotonaldehyde, 6.8gNaCOOH in 80 ℃ of reactions, the results are shown in Table 2.
Embodiment 18: heterogeneous catalyst is used for the hydrogen transfer reaction of cyclohexyl aldehyde
Heterogeneous catalyst in the preparation of embodiment 1 step 4 is dissolved in the 15m water, adds 4mmol cyclohexyl aldehyde, 6.8gNaCOOH in 80 ℃ of reactions, the results are shown in Table 2.
The circular response result of table 1. heterogeneous catalyst catalysis benzaldehyde hydrogen migration
Figure A20071006423100141
The reaction result of the different aldehyde hydrogen transfer reactions of table 2. heterogeneous catalyst catalysis
Figure A20071006423100151

Claims (8)

1. heterogeneous catalyst that is used to prepare alcohol, its essential characteristic be carrier surface simultaneously immobilized catalyst and quaternary ammonium salt, structural formula as shown in the formula:
In the formula:
R 1-R 4Separate;
R 1=C 1-C 10End contains sulfydryl or CH=CH 2The alkyl or aryl estersil;
R 2=H, C 1-C 10Alkyl or aryl;
R 3=C 1-C 16End contains CH=CH 2Alkyl or aryl;
R 4=C 1-C 16Alkyl or aryl;
L=aryl or contain C 1-C 3The phenolic compound of alkyl substituent;
The X=halogen atom;
M is meant metal, is Rh, Ru or Ir;
1≤m≤15，0≤n≤10
Carrier is inorganic or the organic inorganic hybridization porous material.
2. heterogeneous catalyst as claimed in claim 1, wherein, carrier is inorganic silicon dioxide material, hybrid inorganic-organic material, the inorganic silicon dioxide carrier of organic group modified, Fe 3O 4Or silica parcel Fe 3O 4Magnetic nano-particle.
3. heterogeneous catalyst as claimed in claim 1, wherein, the metal precursor structure expression is:
[MX mlL nl] P
Wherein, M=Rh, Ru or Ir; The X=halogen atom; L=aryl or contain C 1-C 3The phenolic compound of alkyl substituent; M1=2,3; N1=0,1; P=1,2.
4. prepare the method for the described heterogeneous catalyst of claim 1, the steps include:
(a) carrier and R 1Reflux in organic solvent, preparation contains the sulfydryl of weight ratio 4-5% or the CH=CH of weight ratio 3-4% 2Carrier;
(b) carrier that step a is prepared and two amine ligands, quaternary ammonium salt, initator polymerization in solution, washing, dry (percentage is all the weight ratio that whole reaction system feeds intake); Wherein by weight: two amine ligand 8-10%, quaternary ammonium salt 2～10%, initator 0.8-1%;
(c) product with step b is dissolved in H 2Among the O, add the coordination of metal catalyst precursor body, obtain heterogeneous catalyst; Wherein: two amine ligands: the coordination of metal catalyst precursor body is 4-6: 1-2 μ mol;
R among the step a 1Be C 1-C 10End contains sulfydryl or CH=CH 2The alkyl or aryl estersil, its basic structure formula is
(R 5O) 3Si-(CH 2) k-SH (R 5O) 3Si-(CH 2) k-CH＝CH 2
R wherein 5=CH 3, CH 3CH 2, 1≤K≤10;
Carrier among the step a is inorganic or the organic inorganic hybridization porous material
Organic solvent among the step a is toluene, chloroform or ethanol;
Quaternary ammonium salt among the step b is C 1-C 16End contains CH=CH 2Alkyl or aryl;
Initator among the step b is an azodiisobutyronitrile;
Solvent among the step b is N, dinethylformamide, N, at least a in N-dimethylacetylamide, the methyl-sulfoxide.
5. method as claimed in claim 4, wherein, the carrier among the step a is inorganic silicon dioxide material, hybrid inorganic-organic material, the inorganic silicon dioxide carrier of organic group modified, Fe 3O 4Or silica parcel Fe 3O 4Magnetic nano-particle.
6. method as claimed in claim 4, wherein, the represented aryl of metal precursor L or contain C among the step c 1-C 3The phenolic compound of alkyl substituent, molecular formula is as follows:
Figure A2007100642310004C1
7. each the application of heterogeneous catalyst in the aldehyde hydrogen transfer reaction among the claim 1-3.
8. application as claimed in claim 7, wherein, the molecular formula of reaction substrate aldehyde is:
R wherein 6Be C 1-C 18With contain heteroatomic alkyl or aryl.
CNA2007100642319A 2007-03-07 2007-03-07 Polyphase catalyst for preparing alcohol and preparation and application Pending CN101259435A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140054162A1 (en) * 2012-08-24 2014-02-27 The University Of Akron Magnetic macroinitiators and magnetically induced chain reactions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140054162A1 (en) * 2012-08-24 2014-02-27 The University Of Akron Magnetic macroinitiators and magnetically induced chain reactions
US9545611B2 (en) * 2012-08-24 2017-01-17 The University Of Akron Magnetic macroinitiators and magnetically induced chain reactions

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