CN101791573B - Diamine-bridged ordered mesoporous organic base heterogeneous catalyst, and preparation method and applications thereof - Google Patents

Diamine-bridged ordered mesoporous organic base heterogeneous catalyst, and preparation method and applications thereof Download PDF

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CN101791573B
CN101791573B CN2010101150135A CN201010115013A CN101791573B CN 101791573 B CN101791573 B CN 101791573B CN 2010101150135 A CN2010101150135 A CN 2010101150135A CN 201010115013 A CN201010115013 A CN 201010115013A CN 101791573 B CN101791573 B CN 101791573B
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bridged
diamine
heterogeneous catalyst
organic base
ordered mesoporous
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朱凤霞
李和兴
张昉
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Shanghai Normal University
University of Shanghai for Science and Technology
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Abstract

The invention relates to a diamine-bridged ordered mesoporous organic base heterogeneous catalyst, and a preparation method and applications thereof, wherein the preparation method comprises the steps: sufficiently stirring the mixed solution of surfactant, hydrochloric acid, water, diamine-bridged silane and ethyl-bridged silane, then aging the mixed solution and taking precipitates, and removing the surfactant by extraction to prepare a diamine-bridged ordered mesoporous organic base heterogeneous catalyst. The preparation method having simple technology can prepare the heterogeneous catalyst with effective and durable catalytic activity can effectively enhance reaction speed, reduce production cost and promote quality of products, and the prepared heterogeneous catalyst can be recycled so as to reduce environmental pollution. The method according to the invention can prepare organic base catalyst with ordered mesoporous array and base active components highly dispersed in pore channels. The catalyst is capable of effectually catalyzing Knoevenagel condensation reaction in water medium.

Description

A kind of diamine-bridged ordered mesoporous organic base heterogeneous catalyst
Technical field
The present invention relates to a kind of preparation method and the application aspect the Knoevenagel condensation reaction in aqueous medium thereof of diamine-bridged ordered mesoporous organic base heterogeneous catalyst.
Background technology
In recent years, carry out the important branch that organic synthesis becomes Green Chemistry with water to replace organic solvent.The Knoevenagel condensation reaction is to contain the addition of the compound of active methylene hydrogen and carbonyls to eliminate reaction; It is medicine intermediate synthetic in the important method of preparation unsaturated olefin, be catalyst normally with the X type y-type zeolite of pyridine, piperidines, hydrotalcite, alkali ion exchange etc.
In recent years; Utilize the carrier of ordered mesoporous material as solid-carried catalyst; The cleaning organic synthesis that is implemented in the aqueous medium causes extensive concern gradually; Wherein, the ordered mesoporous silicon material of functionalization especially receives the attention of vast chemist because of the advantage of the decentralization of the characteristics raising active sites of its bigger serface, regular pore passage structure.
Summary of the invention
Of the present inventionly be to provide a kind of diamine-bridged ordered mesoporous organic base heterogeneous catalyst.
Another object of the present invention is to provide above-mentioned Application of Catalyst.
For realizing above-mentioned purpose; The preparation method comprises; Diamine-bridged silane and ethyl bridging silane and surfactant are carried out copolycondensation, get deposition after the ageing, surfactant is removed in extraction; With the aqueous slkali washing, at last solid drying is promptly got diamine-bridged ordered mesoporous organic base heterogeneous catalyst again.Be specially, a kind of preparation method of diamine-bridged ordered mesoporous organic base heterogeneous catalyst comprises the following steps:
1) is that surfactant concentration is that 0.45～0.65mM, KCl or NaCl concentration are that 1.0～1.5M, HCl concentration are the solution of 0.4～0.6M with surfactant, KCl or NaCl, HCl and water mixed preparing, under 30～50 ℃ condition, mixes;
Add 1, the two triethoxysilicane ethane of 2-, pre-polymerization 100～150min adds diaminourea bridging silane again, mix and continue reaction 20～26 hours, and under 90～110 ℃ of conditions ageing 24～36h, get deposition;
1, the mol ratio of two triethoxysilicane ethane of 2-and diaminourea bridging silane is 5: 1～100: 1; Be preferably 5: 1～20: 1;
1, the total amount of silicon and the mol ratio of surfactant are 1: 0.015～0.025 in two triethoxysilicane ethane of 2-and the diaminourea bridging silane;
2) surfactant is removed in step 1) products therefrom washing back extraction, used neutralizing treatment again, drying obtains diamine-bridged ordered mesoporous organic base heterogeneous catalyst.
In the step 1), described surfactant is preferably P123.
Step 2) in, described diaminourea bridging silane is selected from two [3-(trimethoxy is silica-based) propyl group] ethylenediamines or two [3-(triethoxy is silica-based) propyl group] ethylenediamine, is preferably two [3-(trimethoxy is silica-based) propyl group] ethylenediamines.
In the step 3), extraction is removed before the surfactant, and deposition is carried out milled processed.Method of extraction is: the mixed solution with hydrochloric acid and ethanol extracts 20～32h under 70～90 ℃ of conditions; The mass volume ratio of solid and liquid is 1g: 800～1200mL;
In the mixed solution of described hydrochloric acid and ethanol, content of hydrochloric acid is 0.8～1.2mol/L, and the content of ethanol is 400～750g/L.
The method of neutralizing treatment does, with 0.05～0.5M NaOH solution, 0.05～0.5MKOH solution, 1M～saturated NaHCO 3Solution or 1M～saturated Na 2CO 3Solution stirs 15～26h under 20～30 ℃ of conditions; The mass volume ratio of solid and liquid is 1g: 6～10mL;
A kind of diamine-bridged ordered mesoporous organic base heterogeneous catalyst that said method obtains, specific area are 400～800m 2/ g has the two-dimentional hexagonal mesoporous structure of high-sequential, and pore volume is 0.5～0.8cm 3/ g; The aperture is 5.5～7.5nm.
Above-mentioned diamine-bridged ordered mesoporous organic base heterogeneous catalyst can be applicable to Knoevenagel condensation reaction in the aqueous medium.The for example condensation reaction of ethyl cyanoacetate and aromatic aldehyde, this course of reaction can be represented by following formula:
Figure GSA00000045207000041
Knoevenagel condensation reaction yield in ordered mesoporous organic base heterogeneous catalyst catalysis aqueous medium can reach 92%, selectivity can reach 100%.And still have catalytic efficiency preferably after can reusing 8 times, the reaction yield reaches 84%.
The heterogeneous catalysis duct of the present invention's preparation is unobstructed, and active sites is evenly distributed, and reactivity is high, can overcome deficiency of the prior art; Even distribution, the substrate that can realize the catalytic activity site fully contact with the activated centre, can realize the recycle of catalyst again, finally realize the target of green catalysis.And the preparation method is simple, and cost is low.
In the alkynes hydration reaction in aqueous medium, has higher catalytic activity.Its superior catalytic activity is mainly owing to following factors:
1. the ordered mesoporous organic base heterogeneous catalyst duct is unobstructed, and active sites is evenly distributed, and reactivity is high, can overcome deficiency of the prior art; Even distribution, the substrate that can realize the catalytic activity site fully contact with the activated centre,
2. ordered mesoporous organic base heterogeneous catalyst is because of the organic backbone of himself has high hydrophobicity, and when making organic reaction in the catalysis aqueous medium, organic substrates more is prone to the duct diffusion, thereby improves catalytic efficiency.
Description of drawings
Fig. 1 is the little angle XRD figure of the diamine-bridged ordered mesoporous organic base heterogeneous catalyst of embodiment 1;
Fig. 2 is the N of the diamine-bridged ordered mesoporous organic base heterogeneous catalyst of embodiment 1 gained 2The adsorption-desorption isollaothermic chart; The longitudinal axis is for absorbing volume, and transverse axis is a relative pressure.
Fig. 3 is the TEM figure of the diamine-bridged ordered mesoporous organic base heterogeneous catalyst of embodiment 1 gained.
Fig. 4 applies mechanically the graph of a relation of number of times and yield for the diamine-bridged ordered mesoporous organic base heterogeneous catalyst of embodiment 1 gained; The longitudinal axis is a productive rate, and transverse axis is for repeating to apply mechanically number of times.
The specific embodiment
Below in conjunction with accompanying drawing and specific embodiment content of the present invention is further specified.
Embodiment 1
A kind of preparation method of diamine-bridged ordered mesoporous organic base heterogeneous catalyst comprises the following steps:
1) with 1.0g P123 (EO 20PO 70EO 20) (0.17mmol), 2.95g KCl (39.6mmol) and 31mL 0.5M HCl solution mixes, and in the folder hot jacket, stirs 3h under 40 ℃ of conditions; Add (4.7mmol) 1 then; The two triethoxysilicane ethane (BTES) of 2-; After treating BTES pre-polymerization 120min, (BTSPED (0.3mmol) continues to stir 24h to add two [3-(trimethoxy is silica-based) propyl group] ethylenediamines again; Ageing 24h under 100 ℃ of conditions obtains the white solid powder after filtration washing, the vacuum drying;
2) above-mentioned material is ground with agate mortar, again with HCl/C 2H 5The OH mixed solution extracts, and removes surfactant, and the mass volume ratio of solid and liquid is 1g: 1000mL; In the mixed solution of described hydrochloric acid and ethanol, content of hydrochloric acid is 1.0mol/L, and the content of ethanol is 750g/L.
Alkali cleaning then: under 25 ℃ of conditions, products therefrom is joined saturated Na 2CO 3(mass volume ratio of solid and liquid is 1g: 10mL), suction filtration, 80 ℃ of dry vacuum drying obtains diamine-bridged ordered mesoporous organic base heterogeneous catalyst behind the solution stirring 12h.Its little angle XRD figure is as shown in Figure 1, N 2The adsorption-desorption isollaothermic chart is as shown in Figure 2, and TEM figure is as shown in Figure 3.
Measure the foregoing description 1 by the BET method and obtain diamine-bridged ordered mesoporous organic base heterogeneous catalyst, specific area is 788m 2/ g, aperture 7.2nm, pore volume are 0.80cm 3/ g.
As depicted in figs. 1 and 2 little angle XRD figure and N 2The adsorption-desorption thermoisopleth can find out, prepared heterogeneous catalysis all have orderly two-dimentional hexagonal mesoporous structure, pore-size distribution comparatively homogeneous, have bigger specific area.
Embodiment 2
A kind of preparation method of diamine-bridged ordered mesoporous organic base heterogeneous catalyst comprises the following steps:
1) with 0.9g P123 (EO 20PO 70EO 20) (0.16mmol), 2.95g KCl (39.6mmol) and 29mL 0.5M HCl solution mixes, and in the folder hot jacket, stirs 3h under 40 ℃ of conditions, adds 4.5mmol 1 then; The two triethoxysilicane ethane (BTES) of 2-; After treating BTES pre-polymerization 120min, add two [3-(trimethoxy the is silica-based) propyl group] ethylenediamines (BTSPED) of 0.5mmol again, continue to stir 24h; Ageing 24h under 100 ℃ of conditions obtains the white solid powder after filtration washing, the vacuum drying;
2) above-mentioned material is ground with agate mortar, at last with HCl/C 2H 5OH extracts, and removes surfactant, and the mass volume ratio of solid and liquid is 1g: 900mL; In the mixed solution of described hydrochloric acid and ethanol, content of hydrochloric acid is 1.1mol/L, and the content of ethanol is 680g/L.
Alkali cleaning then: under 25 ℃ of conditions, products therefrom is joined saturated Na 2CO 3(mass volume ratio of solid and liquid is 1g: 6mL), suction filtration, 80 ℃ of dry vacuum drying obtains diamine-bridged ordered mesoporous organic base heterogeneous catalyst behind the solution stirring 12h.
Embodiment 3
A kind of preparation method of diamine-bridged ordered mesoporous organic base heterogeneous catalyst comprises the following steps:
1) with 1.1g P123 (EO 20PO 70EO 20) (0.19mmol), 3.0g KCl (40mmol) and 33mL 0.5M HCl solution mixes, and in the folder hot jacket, stirs 3h under 38 ℃ of conditions, adds (4.6mmol) 1 then; The two triethoxysilicane ethane (BTES) of 2-; After treating BTES pre-polymerization 120min, (BTSPED (0.3mmol) continues to stir 24h to add two [3-(trimethoxy is silica-based) propyl group] ethylenediamines again; Ageing 24h under 110 ℃ of conditions obtains the white solid powder after filtration washing, the vacuum drying;
2) above-mentioned material is ground with agate mortar, at last with HCl/C 2H 5OH extracts, and removes surfactant, and the mass volume ratio of solid and liquid is 1g: 800mL; In the mixed solution of described hydrochloric acid and ethanol, content of hydrochloric acid is 0.8mol/L, and the content of ethanol is 550g/L.
Alkali cleaning then: under 25 ℃ of conditions, products therefrom is joined saturated Na 2CO 3(mass volume ratio of solid and liquid is 1g: 8mL), suction filtration, 80 ℃ of dry vacuum drying obtains diamine-bridged ordered mesoporous organic base heterogeneous catalyst behind the solution stirring 12h.
Embodiment 4
Embodiment 1 resulting diamine-bridged ordered mesoporous organic base heterogeneous catalyst is used for aqueous medium Knoevenagel condensation reaction; Detailed process is following: in the 10ml round-bottomed flask, add 0.4mmol ethyl cyanoacetate and 0.5mmol benzaldehyde or substituted benzaldehyde, the ordered mesoporous organic base heterogeneous catalyst that 0.10g 6mol% is diamine-bridged; React 3h under 40 ℃ of conditions, products therefrom with the 10ml extracted in toluene after, carry out product analysis by GC, reaction equation as shown in the formula, active result such as table 1.
Figure GSA00000045207000081
The diamine-bridged ordered mesoporous organic base heterogeneous catalyst of table 1. is to the catalytic activity table of Knoevenagel condensation reaction in the aqueous medium:
Figure GSA00000045207000082
Data can find out that the diamine-bridged ordered mesoporous organic base heterogeneous catalyst of preparation shows higher activity to Knoevenagel condensation reaction in the aqueous medium from table.
Remaining heterogeneous catalysis is with toluene, deionized water and washing with alcohol 2～4 times, and 60～80 ℃ of following vacuum drying are reused next time, apply mechanically experiment, and its catalytic activity is seen Fig. 4.
As can be seen from Figure 4, repeat to apply mechanically 8 times after, diamine-bridged ordered mesoporous organic base heterogeneous catalyst still has catalytic activity preferably, efficiency of pcr product is 84%.

Claims (6)

1. a diamine-bridged ordered mesoporous organic base heterogeneous catalyst is characterized in that the preparation method comprises the steps:
1) is that surfactant concentration is that 0.45～0.65mM, KCl or NaCl concentration are that 1.0～1.5M, HCl concentration are the solution of 0.4～0.6M with surfactant, KCl or NaCl, HCl and water mixed preparing, under 30～50 ℃ condition, mixes; Add 1, the two triethoxysilicane ethane of 2-, pre-polymerization 100～150min adds diaminourea bridging silane again, mix and continue reaction 20～26 hours, and under 90～110 ℃ of conditions ageing 24～36h, get deposition;
1, the mol ratio of two triethoxysilicane ethane of 2-and diaminourea bridging silane is 5: 1～100: 1;
1, the total amount of silicon and the mol ratio of surfactant are 1: 0.015～0.025 in two triethoxysilicane ethane of 2-and the diaminourea bridging silane;
Described surfactant is P123;
Described diaminourea bridging silane is selected from two [3-(trimethoxy is silica-based) propyl group] ethylenediamines or two [3-(triethoxy is silica-based) propyl group] ethylenediamine;
2) surfactant is removed in step 1) products therefrom washing back extraction, used neutralizing treatment again, drying obtains diamine-bridged ordered mesoporous organic base heterogeneous catalyst.
2. the said diamine-bridged ordered mesoporous organic base heterogeneous catalyst of claim 1 is characterized in that, step 1) is described 1, and the mol ratio of two triethoxysilicane ethane of 2-and diaminourea bridging silane is 5: 1～20: 1.
3. the said diamine-bridged ordered mesoporous organic base heterogeneous catalyst of claim 1 is characterized in that step 2) described in the method for neutralizing treatment do, with 0.05～0.5M NaOH solution, 0.05～0.5M KOH solution, 1M～saturated NaHCO 3Solution or 1M～saturated Na 2CO 3Solution stirs 15～26h under 20～30 ℃ of conditions; The mass volume ratio of solid and liquid is 1g: 6～10mL.
4. the said diamine-bridged ordered mesoporous organic base heterogeneous catalyst of claim 1 is characterized in that step 2) described in the extraction method of removing surfactant be under 70～90 ℃ of conditions, to extract 20～32h with the mixed solution of hydrochloric acid and ethanol; The mass volume ratio of solid and liquid is 1g: 800～1200mL;
In the mixed solution of described hydrochloric acid and ethanol, content of hydrochloric acid is 0.8～1.2mol/L, and the content of ethanol is 400～750g/L.
5. the said diamine-bridged ordered mesoporous organic base heterogeneous catalyst of claim 1 is characterized in that, has the two-dimentional hexagonal mesoporous structure of high-sequential, and specific area is 400～800m 2/ g, pore volume are 0.5～0.8cm 3/ g; The aperture is 5.5～7.5nm.
6. the application aspect the said diamine-bridged Knoevenagel condensation reaction of ordered mesoporous organic base heterogeneous catalyst in the catalysis aqueous medium of claim 1～4.
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EP1358873A1 (en) * 2002-04-30 2003-11-05 National Institute of Advanced Industrial Science and Technology Mesoporous silica having controlled-release on-off control function, production method thereof and method using same
CN101214966A (en) * 2007-12-27 2008-07-09 中国人民解放军国防科学技术大学 High amino content ordered mesoporous silicon dioxide film and its preparation method and application
WO2008137502A1 (en) * 2007-05-04 2008-11-13 University Of Massachusetts Highly condensed mesoporous silicate compositions and methods

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* Cited by examiner, † Cited by third party
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EP1358873A1 (en) * 2002-04-30 2003-11-05 National Institute of Advanced Industrial Science and Technology Mesoporous silica having controlled-release on-off control function, production method thereof and method using same
WO2008137502A1 (en) * 2007-05-04 2008-11-13 University Of Massachusetts Highly condensed mesoporous silicate compositions and methods
CN101214966A (en) * 2007-12-27 2008-07-09 中国人民解放军国防科学技术大学 High amino content ordered mesoporous silicon dioxide film and its preparation method and application

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