CN106554324B - Metal-organic framework material and preparation method based on imidazoles salt form ligand and application - Google Patents

Metal-organic framework material and preparation method based on imidazoles salt form ligand and application Download PDF

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CN106554324B
CN106554324B CN201610966796.5A CN201610966796A CN106554324B CN 106554324 B CN106554324 B CN 106554324B CN 201610966796 A CN201610966796 A CN 201610966796A CN 106554324 B CN106554324 B CN 106554324B
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董育斌
姚丙建
丁罗刚
李江涛
付齐娟
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Shandong Normal University
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Abstract

The invention discloses based on imidazoles salt form ligand metal-organic framework material and preparation method and application, chemical structural formula be：[Zr6O4(OH)4L6]n, wherein L is organic ligand L, and n is the natural number more than 0, or, being formed by Coordinate self-assembly by organic ligand L and zirconates；Wherein, the chemical structural formula of organic ligand L isIonic liquid is fixed on high-molecular organic material or inorganic porous material by the present invention, obtain the characteristic that immobilization ionic liquid has both ionic liquid and carrier material, when for detaching, be conducive to expand interfacial area, shorten diffusion path, promote mass transfer, facilitate recycling, and be expected to realize large-scale application in the method for UF membrane, is more easy to industrialize.

Description

Metal-organic framework material and preparation method based on imidazoles salt form ligand and application
Technical field
The invention belongs to technical field of nanometer material preparation, and in particular to a kind of metal based on imidazoles salt form ligand is organic Frame and the preparation method and application thereof.
Background technology
Metal organic frame (metal-organic frameworks, MOFs) material is by organic ligand and metal ion It is to develop in field of coordinative chemistry in recent decades by a kind of hybrid material with recurrent network structure being self-assembly of It obtains than faster new material.Compared with traditional inorganic porous material, MOFs materials have the voidage and specific surface area of bigger, Especially adjustable aperture and variable functional group, thus MOFs materials divide as porous functionalization material in gas From with storage in terms of application show prodigious advantage.Currently, MOFs materials be applied to hydrogen storage, drug carrier, It catalysis reaction, biosensor, gas absorption and detaches etc..The research of metal-organic framework material be related to organic chemistry, The newest fruits of the subjects such as inorganic chemistry, Coordinative Chemistry, materials chemistry, life science and computer science, thus in recent years MOFs is paid close attention to by more and more research teams.
Ionic liquid refers in room temperature or approaching salt that liquid is presented at room temperature, being made of completely zwitterion, Referred to as low temperature molten salt.For ionic liquid as ionic compound, fusing point is relatively low mainly because of certain substituent groups in its structure Asymmetry prevents ion from being regularly piled into caused by crystal.It is generally made of organic cation and inorganic anion, often The cation seen has quaternary ammonium salt ion, quaternary phosphonium salt ion, imidazolium ion and pyrroles's salt ion etc., anion have halide ion, Tetrafluoroborate ion, hexafluorophosphoricacid acid ions etc..Because ionic liquid has the dissolving of unique gas-selectively and absorbability Can, so the use of ionic liquid and its polymer provides new approach for the separation and purifying of gas, there is important answer With value.
Invention content
It is an object of the present invention to which ionic liquid is fixed on high-molecular organic material or inorganic porous material, obtain Immobilization ionic liquid has both the characteristic of ionic liquid and carrier material, when for detaching, being conducive to expand interfacial area, shortening and expand Path is dissipated, promotes mass transfer, facilitates recycling, and is expected to realize large-scale application in the method for UF membrane, is more easy to industrialize, because And provide a kind of metal organic frame based on imidazoles salt form ligand and preparation method and application.
To achieve the above object, the technical scheme is that：
Organic ligand L for synthesizing the metal organic frame based on corresponding imidazolium salts, chemical structural formula are：
It is named as 3- (3- allyl -1- imidazole radicals) -4,4 '-biphenyl dicarboxylic acid.
The synthetic method of above-mentioned organic ligand L is, first, with methyl -4 3-, 4 '-biphenyl dicarboxylic acids and methanol be raw material into Intermediate A is obtained by the reaction in row, secondly, carries out that intermediate B is obtained by the reaction using intermediate A and bromosuccinimide as raw material, then It is secondary, it carries out that intermediate C, last intermediate C is obtained by the reaction by hydrolysis as raw material using intermediate B and allyl imidazole to obtain the final product Organic ligand L.
Wherein, the structural formula of intermediate A is：
It is named as 3- methyl -4,4 '-biphenyl dicarboxylic acid dimethyl ester.
The structural formula of intermediate B is：
The structural formula of intermediate C is：
Methyl -4 3-, 4 '-biphenyl dicarboxylic acids also known as 4- (4- carboxyl phenyls) -3- methyl benzoic acids, No. CAS is 1186048-28-1 can be bought by chemical (Shanghai) Science and Technology Ltd. of nine ancient cooking vessels, can also be by voluntarily synthesizing acquisition.
Preferably, methyl -4 3-, the synthetic method of 4 '-biphenyl dicarboxylic acids are the bromo- 3- methyl benzoic acids of 4- and 4- carboxylics After base phenyl boric acid progress suzuki reaction to obtain the final product.
The suzuki reaction, also referred to as Suzuki coupling reactions, Suzuki-Miyaura reactions (Suzuki-palace Pu reaction), It is a kind of organometallic coupling reaction, under zeroth order palladium complex catalyst, aryl (or alkenyl) boric acid (or borate) and halogenated aryl hydrocarbon Cross-coupling occurs for (or alkenyl halide).It is described halogenated for chloro, bromo or iodo.
It is further preferred that methyl -4 3-, the step of 4 '-biphenyl dicarboxylic acids synthesize is, with the bromo- 3- methyl benzoic acids of 4- with 4- Carboxybenzeneboronic acids are raw material, and alkaline compound (such as potassium carbonate) and palladium catalyst (such as tetra-triphenylphosphine palladium), heating is added Liquid separation is reacted in reflux, is removed layer and is adjusted pH, up to methyl -4 3-, 4 '-biphenyl dicarboxylic acids after suction filtration, drying.
Preferably, methyl -4 3-, 4 '-biphenyl dicarboxylic acids and methanol can obtain intermediate A by esterification, Can be first by methyl -4 3-, 4 '-biphenyl dicarboxylic acids are reacted with halogenating agent (such as phosphorus trichloride, phosphorus pentachloride, thionyl chloride), Make methyl -4 3-, then the converting carboxylate groups in 4 '-biphenyl dicarboxylic acids add methanol progress alcoholysis reaction and obtain centre at carboxylic acid halides Body A.
It is further preferred that the step of esterification is, to methyl -4 3-, methanol is added in 4 '-biphenyl dicarboxylic acids And the concentrated sulfuric acid after heating reflux reaction, adjusts pH, up to intermediate A after suction filtration, washing using the concentrated sulfuric acid as catalyst.
Preferably, the reaction carried out using intermediate A and bromosuccinimide as raw material is straight with aromatic ring in intermediate A Connect the halogenation of connected methyl.
It is further preferred that it is described using intermediate A and bromosuccinimide as raw material, initiator is added, is heated to reflux Intermediate B is obtained by purifying.
The purifying is the process for purifying product.
Process to intermediate B purification is to cool down the liquid after reflux, and vacuum distillation obtains slightly after removing solvent Then product carries out column chromatography for separation to crude product and obtains intermediate B.
The crude product is the lower product of purity.Product purity through column chromatography for separation is more than 99%.
The initiator is organic peroxide evocating agent or azo-initiator (such as azodiisobutyronitrile) etc..
It is further preferred that intermediate A bromosuccinimide and the molar ratio of initiator are 1:(1-1.5):(0.1- 0.2)。
Preferably, the reaction carried out as raw material using intermediate B and allyl imidazole need to carry out in a solvent.
It is further preferred that the condition of the reaction is to be heated to 80 DEG C, flow back 2 hours.
It is further preferred that the solvent is acetonitrile.
Purification process to intermediate C is：After liquid pressure-reducing distillation after back flow reaction is removed solvent, after recrystallization to obtain the final product Intermediate C.
It is further preferred that intermediate B and the molar ratio of allyl imidazole are 1:(1.2-2).
Hydrolysis of the present invention is ester hydrolysis.
Preferably, the step of ester hydrolysis is to be separately added into intermediate C, highly basic (lithium hydroxide) and solvent, in room After the lower stirring of temperature, pH is adjusted, is evaporated under reduced pressure after removal solvent up to organic ligand L.
It is further preferred that the solvent is the mixture of methanol and water.Wherein, the volume ratio of methanol and water is 3:1.
It is further preferred that the time of stirring is 10-14h.
It is further preferred that the adjusting pH is to adjust pH=2-3 using hydrobromic acid.
It is further preferred that the molar ratio of intermediate C and lithium hydroxide is 1:10.
Based on the metal organic frame of imidazoles salt form ligand, chemical structural formula is：[Zr6O4(OH)4L6]n, wherein L is Above-mentioned organic ligand L, n are the natural number more than 0.
Based on the metal organic frame of imidazoles salt form ligand, Coordinate self-assembly is passed through by above-mentioned organic ligand L and zirconates It is formed.
Coordinate self-assembly of the present invention is basic structural unit (zirconium ion in organic ligand L and zirconates) to be coordinated The form of key spontaneously forms the process of ordered structure.
Above-mentioned organic ligand L, acid and zirconates are dissolved in by the preparation method of the metal organic frame based on imidazoles salt form ligand Polar solvent is heated to 120 ± 5 DEG C, keeps temperature 24-48h, up to metal organic frame after reaction.
In the present invention, the acid can be organic acid, such as glacial acetic acid, benzoic acid, preferably glacial acetic acid；Or it is inorganic Acid, such as hydrochloric acid.
Preferably, the polar solvent is the solvent that polarity is strong, dielectric constant is big.Such as N,N-dimethylformamide (DMF), methanol, ethyl alcohol, ether etc..Preferential DMF.
Preferably, the zirconates is zirconium chloride, tetrabormated zirconium, zirconium tetraiodide and zirconium nitrate.It is preferred that zirconium chloride.
Preferably, it needs to cool the temperature to room temperature after reaction.
Heretofore described room temperature is 15-25 DEG C.
Preferably, the ratio of organic ligand L, zirconates, acid and polar solvent addition is 0.01:0.01:0.3:(3-5), mol:mol:mol:L。
Specifically, by taking zirconium chloride as an example, synthesis skeleton symbol is as follows：
A kind of application of above-mentioned metal organic frame in gas absorption, separation or catalyzed conversion.
A kind of catalyst, including above-mentioned metal organic frame.
A kind of application process of above-mentioned metal organic frame in gas absorption or separation, above-mentioned metal organic frame is lived Change, gas absorption is carried out to the metal organic frame after activation or separation is tested.
Preferably, the method for the activation is that metal organic frame is placed in absolute ethyl alcohol and impregnates activation 48h, 60 12h is dried in vacuo at DEG C.
A kind of application process that above-mentioned metal organic frame is reacted in catalytic gas reforming, using Styryl oxide as substrate, Using metal organic frame as catalyst, using tetrabutylammonium bromide as co-catalyst, be passed through CO2Gas is adopted at 90 DEG C, 1atm It is reacted to get corresponding carbonyls with solventless method.
" atm " is writing a Chinese character in simplified form for atmosphere, refers to the standard atmospheric pressure on sea level on the earth, and " atm " is pressure in the present invention Strong unit, 1 [atm]=1.01325Bar=760mmHg.
Specifically, by taking carbon dioxide as an example, reaction skeleton symbol is as follows：
Beneficial effects of the present invention：
(1) feature structure of poly ion liquid is introduced into metal-organic framework material by the present invention, has widened polyion The type of fluent material, and it has been advantageously implemented the integrated of two kinds of materials.
(2) introducing of imidazole salts makes the metal organic frame have higher selective absorption to carbon dioxide gas Matter is conducive to its application in gas separation.
(3) metal organic frame in the present invention has catalytic effect to carbon dioxide under normal pressure, has reaction condition Relatively mild, the reaction time is shorter, the few feature of catalyst amount.
Description of the drawings
Fig. 1 is intermediate A1H-NMR spectrum；
Fig. 2 is intermediate B1H-NMR spectrum；
Fig. 3 is intermediate C's1H-NMR spectrum；
Fig. 4 is organic ligand L's1H-NMR spectrum；
Fig. 5 is the PDXR spectrograms of metal organic frame；
Fig. 6 is the SEM spectrograms of metal organic frame；
Fig. 7 is N under 77K2Adsorption curve；
Fig. 8 is the adsorption curve of gas with various under 195K；
Fig. 9 is the adsorption curve of gas with various under 273K；
Figure 10 is the adsorption curve of gas with various under 298K；
Figure 11 is the PDXR spectrograms of metal organic frame after reusing；
Figure 12 is metal organic frame catalysate1H-NMR spectrum；
Specific implementation mode
Below in conjunction with the accompanying drawings and specific embodiment the invention will be further described.
Embodiment 1：The preparation of intermediate A
With the bromo- 3- methyl benzoic acids (5g, 23.4mmol) of 4- and 4- Carboxybenzeneboronic acids (4.8g, 28.92mmol) for raw material With potassium carbonate (25.79g) and tetra-triphenylphosphine palladium (1.5g) catalyst in toluene：Ethyl alcohol：Water=(1:1:1) heating in (50mL) Reflux 24 hours, layer is removed in liquid separation, is adjusted pH to 2 with dilute hydrochloric acid, is filtered, vacuum drying.Methanol (75mL), the concentrated sulfuric acid is added (5mL) is catalyst, and 78 DEG C are flowed back 12 hours, adjusts pH to 7 with sodium carbonate, filters, be washed with water to get intermediate A, 3- first 4,4 '-biphenyl dicarboxylic acid dimethyl ester of base-,1H-NMR spectrum is as shown in Figure 1.
Embodiment 2：The preparation of intermediate B
3 methyl biphenyl dicarboxylic acid dimethyl esters (2.54g, 8.96mmol), bromo amber are first added in 100mL round-bottomed flasks Acid imide (1.83g, 10.3mmol), azodiisobutyronitrile (AIBN) (0.147g, 0.896mmol), adds benzene (45mL), adds Heat flows back 12 hours to 80 DEG C.It is cooling, it removes solvent under reduced pressure, obtains crude product.It is dissolved, is filtered to get filtrate with dichloromethane, depressurized Remove solvent, column chromatography for separation (petroleum ether：Dichloromethane=1：1) pale yellow semi-solid 1.45g, as intermediate B, yield are obtained It is 45.0%,1H-NMR spectrum is as shown in Figure 2.
Embodiment 3：The preparation of intermediate C
The intermediate B (1.45g, 4.00mmol) in embodiment 2, allyl imidazole are added in the round-bottomed flask of 100mL (8.8mmol), acetonitrile (45mL) are heated to 80 DEG C, flow back 2 hours.It is cooling, it removes solvent under reduced pressure, obtains product, yellow oily Object, as intermediate C, yield 85%,1H-NMR spectrum is as shown in Figure 3.
Embodiment 4：The preparation of organic ligand L
The intermediate C in embodiment 2, lithium hydroxide (10equiv), methanol are added in the round-bottomed flask of 100mL：Water (=3:1) 12h, is stirred at room temperature, and cooling, hydrobromic acid adjusts pH=2~3, removes solvent under reduced pressure, and white product is precipitated, as Organic ligand L, yield 90%,1H-NMR spectrum is as shown in Figure 4.
Embodiment 5：The preparation of metal organic frame
By ZrCl4(28.8mg, 0.12mmol) and glacial acetic acid (0.342mL) is dissolved in by supersound process (20 minutes) In the DMF of 4.8mL.Then organic ligand L (43.56mg, 0.12mmol) is added in autoclave, and will be at the solution ultrasound Manage 10~30min.Then 24~48h is maintained under the conditions of heating the mixture to 120 DEG C.It is cooled to room temperature, is then centrifuged, White crystalline powder is obtained, is washed successively with fresh DMF (~10-20 milliliters × 3), organic solvent (~10-20 milliliters × 3) It washs, centrifuges, be then dried in vacuo to get powdery metal organic frame crystalline material at 40~80 DEG C.PXRD spectrograms such as Fig. 5 Shown, SEM spectrograms are as shown in Figure 6.
Embodiment 6：The gas absorption performance of metal organic frame
Metal organic frame in embodiment 4 is placed in absolute ethyl alcohol and impregnates activation 48h, is dried in vacuo at 60 DEG C 12h carries out gas absorption test to it：The sample of 200mg is placed in pre-weighed sample cell, and deaerate 10h at 120 DEG C, so The absorption of laggard promoting the circulation of qi body is tested with desorption, is tested respectively：N under 77K2CO under adsorption curve (Fig. 7), 195K2、N2And CH4 Adsorption curve (Fig. 8), the CO under 273K2、N2And CH4Adsorption curve (Fig. 9) and 298K under CO2、N2And CH4Absorption it is bent Line (Figure 10).Fig. 7 shows that the MOFs materials have porous structure.The MOFs materials are to carbon dioxide in Fig. 8, Fig. 9 and Figure 10 Adsorbance be significantly greater than CH at same temperature4And N2.For example, at 195K, the crystal is to CO2、CH4And N2Adsorbance successively For 72,27 and 6cm3/ g, it is shown that the material is to CO2The selective absorption advantage of gas..
Embodiment 7：The catalytic performance of metal organic frame
25mL single necked round bottom flask is added in 3mL Styryl oxides, 87mg metal organic frames, 80mg tetrabutylammonium bromide In, magnetic agitation at 90 DEG C is passed through CO by vacuum line2Gas, thin-layer chromatography carry out reaction tracking, after reaction, reaction Liquid is purified by column chromatography for separation, nucleus magnetic hydrogen spectrum calculates yield, and as a result as shown in Table 1 and Table 2, the metal for reusing 5 times has Machine frame catalyst still keeps original topological structure, and PDXR spectrograms are as shown in figure 11, catalysate1H-NMR spectrum is such as Shown in Figure 12.
1 metal organic frame of table is catalyzed the reaction result of carbon dioxide conversion
2 metal organic frame of table is catalyzed the recycling test result of carbon dioxide conversion
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not to invention protection domain Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not required to It is still within the scope of the present invention to make the creative labor the various modifications or changes that can be made.

Claims (30)

1. the organic ligand L for synthesizing the metal organic frame based on corresponding imidazolium salts, characterized in that its chemical structural formula For：
2. the synthetic method of organic ligand L as described in claim 1, characterized in that first, with methyl -4 2-, 4 '-biphenyl two Formic acid and methanol are that raw material carries out that intermediate A is obtained by the reaction, and secondly, are carried out as raw material using intermediate A and bromosuccinimide Intermediate B is obtained by the reaction, again, carries out that intermediate C is obtained by the reaction using intermediate B and allyl imidazole as raw material, it is last intermediate Body C is by hydrolysis up to organic ligand L.
3. synthetic method as claimed in claim 2, characterized in that methyl -4 2-, the synthetic method of 4 '-biphenyl dicarboxylic acids For after the bromo- 3- methyl benzoic acids of 4- and 4- Carboxybenzeneboronic acids progress suzuki reaction to obtain the final product.
4. synthetic method as claimed in claim 2, characterized in that methyl -4 2-, 4 '-biphenyl dicarboxylic acids and methanol pass through Esterification obtains intermediate A.
5. synthetic method as claimed in claim 2, characterized in that first by methyl -4 2-, 4 '-biphenyl dicarboxylic acids and halogenating agent Reaction, makes methyl -4 2-, then the converting carboxylate groups in 4 '-biphenyl dicarboxylic acids add methanol progress alcoholysis reaction and obtain at carboxylic acid halides To intermediate A.
6. synthetic method as claimed in claim 2, characterized in that carried out as raw material using intermediate A and bromosuccinimide Reaction be intermediate A in the methyl being connected directly with aromatic ring halogenation.
7. synthetic method as claimed in claim 6, characterized in that it is described using intermediate A and bromosuccinimide as raw material, Initiator is added, intermediate B is obtained through purifying after being heated to reflux.
8. synthetic method as claimed in claim 6, characterized in that intermediate A, bromosuccinimide and initiator mole Than being 1:(1-1.5):(0.1-0.2).
9. synthetic method as claimed in claim 2, characterized in that carried out using intermediate B and allyl imidazole as raw material anti- It should need to carry out in a solvent.
10. synthetic method as claimed in claim 9, characterized in that the condition of the reaction is to be heated to 80 DEG C, and reflux 2 is small When.
11. synthetic method as claimed in claim 9, characterized in that the solvent is acetonitrile.
12. synthetic method as claimed in claim 9, characterized in that intermediate B and the molar ratio of allyl imidazole are 1: (1.2-2)。
13. synthetic method as claimed in claim 2, characterized in that the step of hydrolysis is to be separately added into intermediate C, highly basic and solvent after being stirred at room temperature, adjust pH, are evaporated under reduced pressure after removal solvent up to organic ligand L.
14. synthetic method as claimed in claim 13, characterized in that the solvent is the mixture of methanol and water.
15. synthetic method as claimed in claim 14, characterized in that the volume ratio of methanol and water is preferably 3:1.
16. synthetic method as claimed in claim 13, characterized in that the time of stirring is 10-14h.
17. synthetic method as claimed in claim 13, characterized in that the adjusting pH is to adjust pH=2-3 using hydrobromic acid.
18. synthetic method as claimed in claim 13, characterized in that the molar ratio of intermediate C and highly basic is 1:10.
19. the metal organic frame based on imidazoles salt form ligand, characterized in that its chemical structural formula is：[Zr6O4(OH)4L6]n, Wherein, L is organic ligand L described in claim 1, and n is the natural number more than 0.
20. the preparation method of the metal organic frame based on imidazoles salt form ligand, characterized in that have described in claim 1 Machine ligand L, acid and zirconates are dissolved in polar solvent, are heated to 120 ± 5 DEG C, keep temperature 24-48h, organic up to metal after reaction Frame.
21. preparation method as claimed in claim 20, characterized in that the polar solvent is n,N-Dimethylformamide, first Alcohol, ethyl alcohol.
22. preparation method as claimed in claim 21, characterized in that the polar solvent is n,N-Dimethylformamide.
23. preparation method as claimed in claim 20, characterized in that the zirconates is zirconium chloride, tetrabormated zirconium, tetraiodide Zirconium and zirconium nitrate.
24. preparation method as claimed in claim 23, characterized in that the zirconates is zirconium chloride.
25. preparation method as claimed in claim 20, characterized in that need to cool the temperature to room temperature after reaction.
26. preparation method as claimed in claim 20, characterized in that organic ligand L, zirconates, acid and polar solvent addition Ratio be 0.01:0.01:0.3:(3-5), mol:mol:mol:L.
27. the metal organic frame described in a kind of claim 19 is in carbon dioxide gas absorption, separation or catalyzed conversion Using.
28. a kind of catalyst, characterized in that including the metal organic frame described in claim 19.
29. application process of the metal organic frame in carbon dioxide gas adsorbs or detaches described in a kind of claim 19, It is characterized in that the metal organic frame described in claim 19 is activated, titanium dioxide is carried out to the metal organic frame after activation Carbon gas absorption or separation test.
30. the application process that the metal organic frame described in a kind of claim 19 is reacted in catalytic gas reforming, with epoxy benzene Ethane is substrate, using metal organic frame as catalyst, using tetrabutylammonium bromide as co-catalyst, is passed through CO2Gas, 90 DEG C, under 1atm, reacted to get corresponding carbonyls using solventless method, the structural formula of corresponding carbonyls is
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