CN104722284A - Microporous material loaded ion liquid composite material or film, and preparation thereof - Google Patents
Microporous material loaded ion liquid composite material or film, and preparation thereof Download PDFInfo
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- CN104722284A CN104722284A CN201310698645.2A CN201310698645A CN104722284A CN 104722284 A CN104722284 A CN 104722284A CN 201310698645 A CN201310698645 A CN 201310698645A CN 104722284 A CN104722284 A CN 104722284A
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Abstract
The invention relates to a microporous material loaded ion liquid composite material or film, and preparation thereof. According to the present invention, the hole cage of a crystallized or amorphous microporous material is adopted as an ion liquid support carrier to prepare the corresponding novel microporous material-ion liquid composite material or microporous material-ion liquid composite film; in-situ synthesis and post-treatment are performed to obtain the novel microporous material loaded ion liquid composite material and the film thereof; and the novel microporous material loaded ion liquid composite material and the film thereof provide special selective adsorption and good separation and purification on small molecule gas.
Description
Technical field
The invention belongs to patent of invention field, be specifically related to a kind of composite by poromerics supported ion liquid or film and preparation thereof.
Background technology
Ionic liquid is a kind of by quaternary ammonium cation, season phosphine cation, the ion salt that pyridylium and glyoxaline cation are formed.The fusing point of usual this kind of salt is lower than 100 DEG C, and some just presents good flow regime even at ambient temperature, is thus called as ionic liquid at room temperature.The anionicsite forming ionic liquid is of a great variety, common are halide ion, nitrate ion, carboxylic acid ion, tetrafluoride boron anion, phosphorus hexafluoride anion, two (fluoroform sulfimide) anion.The vapour pressure of ionic liquid almost can be ignored, its physicochemical property is regulated easily via the kind of conversion zwitterion again simultaneously, can say, ionic liquid is a kind of solvent of environmental protection, the exploitation of ionic liquid is that the mankind are to the essential step that green chemical industry is produced and sustainable development strides forward.In decades recently, about the design of ionic liquid, development and application research emerges in an endless stream.Ionic liquid, plays very important effect in catalysis, organic synthesis, gas absorption, magnetic and fluorescent material, analytical chemistry field.
A series of researchs in recent years show, ionic liquid at room temperature, the ionic liquid at room temperature particularly formed by glyoxaline cation and two (fluoroform sulfimide) anion has good dissolubility to micro-molecular gas such as carbon dioxide, sulfur dioxide, hydrogen sulfide, be described as the carbon dioxide capture agent of a new generation, play a significant role with separation field catching of carbon dioxide.Ionic liquid to the mechanism of action of gas dissolution character and traditional organic solvent (as acetone, the n-hexane etc.) dissolution mechanism to gas very similar, namely rely on interaction and the molecular dispersion power of intermolecular dipole/induced dipole.In the middle of porous carrier, be prepared into support type liquid film by ionic liquid loaded, for the abstraction and purification of micro-molecular gas mixture, also therefore cause the extensive concern of domestic and international scientist.This kind of support type ionic liquid film, except for except gas separaion.Also be widely used in fluid separation applications, ion isolation, seepage slope, electrochemistry, the aspects such as membrane contactor.
Prop carrier usually used as ionic liquid film is organic polymer micro-filtration NF membrane (as permeability polysulfones) or the ceramic material of crystallization (as aluminium oxide, titanium oxide) of amorphous.This kind of carrier material has single or multistage pore structure, and hole dimension is greater than 2nm even more than 50nm.The resistance that ionic liquid enters its hole depth place effectively can be reduced using this kind of material as carrier.But according to Laplace's equation, aperture is inverse ratio with bearing pressure, and aperture is larger, and the pressure that liquid film can bear is less.So adsorb with in the application be separated at the gases at high pressure of reality, just there will be the liquid film losing issue caused because air pressure is excessive, greatly limit the application prospect of liquid film.Some seminar adopt the organic polymer films of nanofiltration as carrier, greatly can improve the use pressure of ionic liquid film.
The present invention proposes a kind of with the novel microporous material ions liquid composite of poromerics supported ionic liquid and poromerics ionic liquid composite membrane, and relate to a series of efficient composite and preparation method of composite film, comprise in-situ synthetic method and post-processing approach.The regulation of pure according to the world in applied chemistry federation, poromerics refers to that aperture is less than the important porous material of the class of 2nm, effectively can play sieving actoion to liquids and gases molecule.Utilize the hole cage of this class poromerics as prop carrier, by fabricated in situ or post-processing approach, among hole cage ionic liquid being incorporated into this kind of material, prepare poromerics ionic liquid composite material.This kind of material can be used as adsorbent in actual applications, on the basis of original poromerics, utilize the solvent properties of ionic liquid excellence and the higher dissolution characteristics to the micro-molecular gas such as carbon dioxide, sulfur dioxide, selective absorption and purified gases and fluid molecule mixture.Meanwhile, this kind of poromerics is expanded as two-dimensional film, utilizes fabricated in situ or post-processing approach, in the middle of hole cage ionic liquid being incorporated into thin-film material, prepare using poromerics as the compound liquid film, Selective Separation and the purified gaseous mixture that support.The novel microporous material ions liquid composite of this poromerics supported ionic liquid and poromerics ionic liquid composite membrane, utilize the micropore hole cage of reduced size, play effective confinement effect, realize the immobilized of ionic liquid to ionic liquid.According to Laplace's equation, the exploitation of this material, will improve the stability of material greatly, is particularly beneficial to the gas separaion realized under high pressure.Compared to using micro-filtration NF membrane as the ionic liquid film of carrier, this kind of material will have better industrial prospect.
Summary of the invention
The object of the present invention is to provide a kind of advanced composite material (ACM) or film and preparation method thereof by poromerics supported ion liquid, this composite or film utilize the hole cage of poromerics to carry out a kind of advanced composite material (ACM) or the laminated film of supported ion liquid as prop carrier.
The invention provides a kind of advanced composite material (ACM) by poromerics supported ion liquid or film, this composite or film utilize the hole cage of poromerics to carry out composite or the film of supported ion liquid as prop carrier;
Described poromerics is the material of crystallization or amorphous, and its hole cage size is less than 2nm;
Described ionic liquid is quaternary ammonium cation type, season phosphine cationic, pyridylium type, any one in glyoxaline cation type ionic liquid.
The invention provides the preparation method of described advanced composite material (ACM) or film, this composite or film prepare by in-situ synthetic method, and concrete steps are as follows:
(1) improve on the basis of conventional synthesis strategy, the solutrope of the presoma of poromerics and ionic liquid or ionic liquid and other solvents is carried out fabricated in situ, obtain poromerics ionic liquid composite material or poromerics ionic liquid composite membrane;
Wherein, the temperature of fabricated in situ is-30 DEG C ~ 300 DEG C, and the time is 1s ~ 8640000s;
(2) reactant mixture of above-mentioned steps gained is cooled to room temperature, and obtains composite or film by centrifugation;
(3) composite obtained and film are washed, dried.
The invention provides the preparation method of described advanced composite material (ACM) or film, this composite or film prepare by the post-processing approach of solid-liquid contact, and concrete steps are as follows:
(1) conveniently synthetic method poromerics or film, be dissolved in corresponding solvent by the whole presomas needed for materials synthesis, react a period of time at a certain temperature, material is separated with mother liquor, washing and drying is stand-by afterwards, the synthetic method of film is similar, according to it to supporting the requirement of situation, can put into suitable carrier in mother liquor;
(2) again will poromerics described in (1) or film as prop carrier, after it is contacted certain hour with ionic liquid or ionic liquid with the dispersant of other solvents, obtain the composite using poromerics hole cage as prop carrier or film;
Wherein, solid-liquid mass ratio is 0.001 ~ 1000, and the temperature of solid-liquid contact is-30 DEG C ~ 300 DEG C, and the time is 1s ~ 8640000s.
(3) composite obtained and film are washed, dried.
The invention provides the preparation method of described advanced composite material (ACM) or film, this composite or film prepare by immersing the post-processing approach stirred, and concrete steps are as follows:
(1) conveniently synthetic method poromerics or film, be dissolved in corresponding solvent by the whole presomas needed for materials synthesis, react a period of time at a certain temperature, material is separated with mother liquor, washing and drying is stand-by afterwards, the synthetic method of film is similar, according to it to supporting the requirement of situation, can put into suitable carrier in mother liquor;
(2) again the poromerics described in (1) or film are immersed in the middle of the dispersant of ionic liquid or ionic liquid and other solvents, by rapid stirring, form the composite using poromerics hole cage as prop carrier or laminated film;
Wherein, solid-liquid mass ratio is 0.001 ~ 1000, and the temperature of stir process is-30 DEG C ~ 300 DEG C, and the time is 1s ~ 8640000s;
(3) composite obtained and film are washed, dried.
The invention provides the preparation method of described advanced composite material (ACM) or film, the post-processing approach that this composite or film pressurize by inert gas prepares, and concrete steps are as follows:
(1) conveniently synthetic method poromerics or film, be dissolved in corresponding solvent by the whole presomas needed for materials synthesis, react a period of time at a certain temperature, material is separated with mother liquor, washing and drying is stand-by afterwards, the synthetic method of film is similar, according to it to supporting the requirement of situation, can put into suitable carrier in mother liquor;
(2) again the poromerics described in (1) or film are immersed in the middle of the dispersant of ionic liquid or ionic liquid and other solvents, by passing into inert gas pressurized operation, ionic liquid is entered in the middle of the hole cage of porous material, forms the composite using porous material hole cage as prop carrier or laminated film;
Wherein, solid-liquid mass ratio is 0.001 ~ 1000, and the pressure applying inert gas is 0 ~ 50MPa, and treatment temperature is-30 DEG C ~ 300 DEG C, and the time is 1s ~ 8640000s; Inert gas is high-purity helium, the one in high pure nitrogen or high-purity argon gas;
(3) composite obtained and film are washed, dried.
The invention provides the preparation method of described advanced composite material (ACM) or film, this composite or film by after vacuumize negative pressure post-processing approach prepare, concrete steps are as follows:
(1) conveniently synthetic method poromerics or film, be dissolved in corresponding solvent by the whole presomas needed for materials synthesis, react a period of time at a certain temperature, material is separated with mother liquor, washing and drying is stand-by afterwards, the synthetic method of film is similar, according to it to supporting the requirement of situation, can put into suitable carrier in mother liquor;
(2) again the poromerics described in (1) or film are immersed in the middle of the dispersant of ionic liquid or ionic liquid and other solvents, by vacuumizing formation subnormal ambient, the ionic liquid of the difficult volatilization of order is drawn in the middle of the cage of poromerics hole, forms the composite using poromerics hole cage as prop carrier or laminated film;
Wherein, solid-liquid mass ratio is 0.001 ~ 1000, and system vacuum is 0 ~ 0.1MPa, and treatment temperature is-30 DEG C ~ 300 DEG C, and the time is 1s ~ 8640000s;
(3) composite obtained and film are washed, dried.
The preparation method of advanced composite material (ACM) provided by the invention or film, the mass fraction of the solutrope intermediate ion liquid of described ionic liquid or ionic liquid and other solvents is 0 ~ 100%.
A kind of NEW TYPE OF COMPOSITE material that the present invention proposes to utilize the hole cage of poromerics to carry out supported ion liquid as prop carrier comes or laminated film, utilize ionic liquid to the dissolution characteristics of gas and fluid molecule excellence, can on the basis of former poromerics, greatly improve its absorption property to liquids and gases molecule, thus the selective absorption realized liquids and gases molecule and separation and purification.
The invention provides this novel microporous material ions liquid composite or the fabricated in situ of laminated film or the method for post processing, can effectively by the middle of ionic liquid supported to the hole cage of poromerics, effectively limit flowing and the loss of ionic liquid, substantially increase the stability of composite and film.Particularly achieve effective separation of gases at high pressure, prevent the liquid film caused because raw gas pressure is excessive to run off.This kind of material has good prospects for commercial application in the separation and purification of gas liquid.
Accompanying drawing explanation
Fig. 1 is the ZIF-8 nano particle x-ray diffraction pattern that embodiment 1 is synthesized;
Fig. 2 is the ZIF-8 nano particle scanning electron microscope diagram that embodiment 1 is synthesized;
Fig. 3 is ZIF-8 nano particle attenuate total reflection-FFIR figure that embodiment 1 is synthesized;
Fig. 4 is N under the ZIF-8 nano particle 77K of embodiment 1 synthesis
2adsorption isotherm line chart, wherein, filled circles representative absorption, open circles represents desorption;
Fig. 5 is CO under the ZIF-8 nano particle 273K of embodiment 1 synthesis
2adsorption isotherm line chart, wherein, filled circles representative absorption, open circles represents desorption;
Fig. 6 is N under the ZIF-8 nano particle 273K of embodiment 1 synthesis
2adsorption isotherm line chart, wherein, filled circles representative absorption, open circles represents desorption;
Fig. 7 is the x-ray diffraction pattern of the ZIF-8 ionic liquid composite material 1 that embodiment 1 is synthesized;
Fig. 8 is the scanning electron microscope diagram of the ZIF-8 ionic liquid composite material 1 that embodiment 1 is synthesized;
Fig. 9 is the attenuate total reflection-FFIR figure of the ZIF-8 ionic liquid composite material 1 that embodiment 1 is synthesized;
Figure 10 is ZIF-8 ionic liquid composite material 1 N under 77K that embodiment 1 is synthesized
2adsorption isotherm line chart, wherein, filled circles representative absorption, open circles represents desorption;
Figure 11 is ZIF-8 ionic liquid composite material 1 CO under 273K that embodiment 1 is synthesized
2adsorption isotherm line chart, wherein, filled circles representative absorption, open circles represents desorption;
Figure 12 is ZIF-8 ionic liquid composite material 1 N under 273K that embodiment 1 is synthesized
2adsorption isotherm line chart, wherein, filled circles representative absorption, open circles represents desorption;
Figure 13 is that the ZIF-8 ionic liquid composite material 2 of the 2-in-1 one-tenth of embodiment is at attenuate total reflection-FFIR figure;
Figure 14 is ZIF-8 ionic liquid composite material 2 N under 77K of the 2-in-1 one-tenth of embodiment
2adsorption isotherm line chart, wherein, filled circles representative absorption, open circles represents desorption;
Figure 15 is ZIF-8 ionic liquid composite material 2 CO under 273K of the 2-in-1 one-tenth of embodiment
2adsorption isotherm line chart, wherein, filled circles representative absorption, open circles represents desorption;
Figure 16 is ZIF-8 ionic liquid composite material 3 N under 77K of the 2-in-1 one-tenth of embodiment
2adsorption isotherm line chart, wherein, filled circles representative absorption, open circles represents desorption;
Figure 17 is ZIF-8 ionic liquid composite material 3 CO under 273K of the 2-in-1 one-tenth of embodiment
2adsorption isotherm line chart, wherein, filled circles representative absorption, open circles represents desorption;
Figure 18 is ZIF-8 ionic liquid composite material 4 N under 77K of the 2-in-1 one-tenth of embodiment
2adsorption isotherm line chart, wherein, filled circles representative absorption, open circles represents desorption;
Figure 19 is ZIF-8 ionic liquid composite material 4 CO under 273K of the 2-in-1 one-tenth of embodiment
2adsorption isotherm line chart, wherein, filled circles representative absorption, open circles represents desorption;
Figure 20 is that the ZIF-8 ionic liquid composite material 5 of embodiment 3 synthesis is at attenuate total reflection-FFIR figure;
Figure 21 is that the ZIF-8 ionic liquid composite material 6 of embodiment 3 synthesis is at attenuate total reflection-FFIR figure;
Figure 22 is ZIF-8 ionic liquid composite material 5 N under 77K that embodiment 3 is synthesized
2adsorption isotherm line chart, wherein, filled circles representative absorption, open circles represents desorption;
Figure 23 is ZIF-8 ionic liquid composite material 6 N under 77K that embodiment 3 is synthesized
2adsorption isotherm line chart, wherein, filled circles representative absorption, open circles represents desorption;
Figure 24 is ZIF-8 ionic liquid composite material 5 CO under 273K that embodiment 3 is synthesized
2adsorption isotherm line chart, wherein, filled circles representative absorption, open circles represents desorption;
Figure 25 is ZIF-8 ionic liquid composite material 6 CO under 273K that embodiment 3 is synthesized
2adsorption isotherm line chart, wherein, filled circles representative absorption, open circles represents desorption.
Detailed description of the invention
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1 utilizes in-situ synthetic method to prepare ZIF-8 ionic liquid composite material
Take 0.367g zinc nitrate hexahydrate (Zn (NO
3)
24H
2o) and 0.811g2-methylimidazole (mim), in above-mentioned solid mixture, 69g [bim] [PF is added
6] ionic liquid.By ultrasonic 7200s in the at room temperature water-bath of this mixture to promote the dissolving of solid mixture in ionic liquid and interaction.Afterwards, mixture is at room temperature stirred 86400s.
Reactant mixture at room temperature centrifugation is obtained corresponding composite.Afterwards with this solid of 20ml methyl alcohol supersound washing to go out the ionic liquid of surface residual.And by above-mentioned washing process in triplicate.Product is fully dry in 60 DEG C of drying boxes the most at last.
For the ease of contrast, utilize methanol as solvent, at room temperature synthesize corresponding ZIF-8 nano particle.Its X-ray diffracting spectrum, scanning electron microscope diagram, decay diffuse reflection-Fourier transform infrared spectroscopy figure, N under 77K
2adsorption isotherm line chart, CO under 273K
2adsorption isotherm line chart, N under 273K
2adsorption isotherm line chart, as shown in Fig. 1 ~ Fig. 6.The specific area of ZIF-8, CO under 273K
2saturated extent of adsorption and under 273K CO
2and N
2absorption Henry's constant and adsorptive selectivity be recited in table 1 respectively.
Characterize through X-ray powder diffraction, determine to utilize [bim] [PF
6] solid particle that at room temperature synthesizes of ionic liquid is ZIF-8(Fig. 7), ESEM shows it for the spherical nano particle (Fig. 8) of class.Attenuate total reflection Fourier transform infrared spectroscopy test under room temperature, shows that this solid is except the characteristic infrared spectrum with ZIF-8, at 830cm
-1there is obvious vibration peak in place, this peak should belong to the P-F key stretching vibration of ionic liquid anion part.This evidence shows that the successful load of ionic liquid enters into the cage of ZIF-8, defines ZIF-8 ionic liquid composite material (Fig. 9).N under 77K is carried out to resulting materials
2absorption (Figure 10), CO under 273K
2absorption (Figure 11), N under 273K
2absorption (Figure 12) characterizes.Result shows, N under prepared ZIF-8 ionic liquid composite material 77K
2adsorbance obviously reduces, and this shows that ionic liquid has entered in the middle of ZIF-8 cage.As shown in table 1, calculating gained composite specific area is 1084m
2/ g, comparing the ZIF-8(specific area of synthesizing in methyl alcohol is 1864m
2/ g), this composite specific area significantly reduces, and this also confirms that ionic liquid enters into ZIF-8 cage, reduces the specific area of material itself further.Compared to ZIF-8 nano particle, ZIF-8 ionic liquid composite material is CO under 273K
2saturated extent of adsorption is almost constant, N under 273K
2adsorbance declines to some extent.The specific area of ZIF-8 ionic liquid composite material, CO under 273K
2saturated extent of adsorption and under 273K CO
2and N
2adsorptive selectivity be recited in table 1 respectively.The above results surface, by ionic liquid loaded in ZIF-8, enter into ZIF-8 cage by restriction nitrogen, effectively can improve ZIF-8 material to CO
2/ N
2adsorptive selectivity.
The contrast of table 1ZIF-8 and ZIF-8 ionic liquid composite material
ZIF-8 immerses in ionic liquid and fully stirs preparation ZIF-8 ionic liquid composite material by embodiment 2
Synthesize ZIF-8 nano particle under room temperature, synthesis liquid mole consist of Zn (NO
3)
24H
2o:mim:MeOH=1:8:700.To Zn (NO
3)
24H
2add a certain amount of methyl alcohol in the solid mixture of O and mim, and at room temperature stir 86400s.After should terminating, mixture centrifugation is obtained corresponding solid, and supersound washing has neither part nor lot in the raw material of reaction with removing in methyl alcohol, washing process repeats three times, finally that gained solid is fully dry in 60 DEG C of drying boxes.
0.5g ZIF-8 is immersed in 10g [bim] [PF
6] in ionic liquid, stir 86400s respectively at normal temperatures and pressures.Afterwards by material from mixture centrifugation out, and with 20ml methyl alcohol supersound washing three times, gained solid is fully dry in 60 DEG C of drying boxes the most at last.Gained solid composite material is carried out N under decay diffuse reflection-Fourier transform infrared spectroscopy (Figure 13), 77K
2isothermal adsorption characterizes the CO of (Figure 14) and 273K
2absorption representation (Figure 15).Specific area is listed in table 2.Characterization result and ZIF-8 nano particle contrast, and confirm that ionic liquid has loaded in the middle of ZIF-8 cage and formed ZIF-8 ionic liquid composite material.
Investigated the experimental result stirring 518400s and 691200s, N under its 77K simultaneously
2the CO of isothermal adsorption sign and 273K
2absorption representation is respectively as shown in Figure 16,18 and Figure 17,19.
ZIF-8 immerses in ionic liquid/carbinol mixture and fully stirs preparation ZIF-8 ionic liquid composite material by embodiment 3
Synthesize ZIF-8 nano particle under room temperature, synthesis liquid mole consist of Zn (NO
3)
24H
2o:mim:MeOH=1:8:700.To Zn (NO
3)
24H
2add a certain amount of methyl alcohol in the solid mixture of O and mim, and at room temperature stir 86400s.After should terminating, mixture centrifugation is obtained corresponding solid, and supersound washing has neither part nor lot in the raw material of reaction with removing in methyl alcohol, washing process repeats three times, finally that gained solid is fully dry in 60 DEG C of drying boxes.
By 1.2g [bim] [PF
6] ionic liquid and the mutual mixed dissolution of 3.75g methyl alcohol obtain solutrope, ionic liquid mass fraction is 24%.0.5g ZIF-8 is immersed in the mixture of ionic liquid and methyl alcohol, stirs 3600s and 86400s respectively at normal temperatures and pressures.Afterwards by material from mixture centrifugation out, and with 20ml methyl alcohol supersound washing three times, gained solid is fully dry in 60 DEG C of drying boxes the most at last.Gained solid composite material is carried out N under decay diffuse reflection-Fourier transform infrared spectroscopy (Figure 20, Figure 21), 77K
2the CO of isothermal adsorption (Figure 22, Figure 23) and 273K
2absorption representation (Figure 24, Figure 25).Characterization result and ZIF-8 nano particle contrast, and confirm that ionic liquid has loaded in the middle of ZIF-8 cage and formed ZIF-8 ionic liquid composite material.Specific area is listed in table 2.Characterization result and ZIF-8 nano particle contrast, and confirm that ionic liquid has loaded in the middle of ZIF-8 cage and formed ZIF-8 ionic liquid composite material.
The contrast of table 2ZIF-8 and ZIF-8 ionic liquid composite material
Claims (12)
1. by composite or the film of poromerics supported ion liquid, it is characterized in that: this composite or film utilize the hole cage of poromerics to carry out composite or the film of supported ion liquid as prop carrier;
Described poromerics is the material of crystallization or amorphous, and its hole cage size is less than 2nm;
Described ionic liquid is quaternary ammonium cation type, season phosphine cationic, pyridylium type, any one in glyoxaline cation type ionic liquid.
2. described in claim 1 by the composite of poromerics supported ion liquid or the preparation method of film, it is characterized in that: this composite or film prepare by in-situ synthetic method, and concrete steps are as follows:
(1) improve on the basis of conventional synthesis strategy, the solutrope of the presoma of poromerics and ionic liquid or ionic liquid and other solvents is carried out fabricated in situ, obtain poromerics ionic liquid composite material or poromerics ionic liquid composite membrane;
(2) reactant mixture of above-mentioned steps gained is cooled to room temperature, and obtains composite or film by centrifugation;
(3) composite obtained and film are washed, dried.
3. described in claim 1 by the composite of poromerics supported ion liquid or the preparation method of film, it is characterized in that: this composite or film prepare by the post-processing approach of solid-liquid contact, and concrete steps are as follows:
(1) conveniently synthetic method poromerics or film, be dissolved in corresponding solvent by the whole presomas needed for materials synthesis, react a period of time at a certain temperature, material is separated with mother liquor, washing and drying is stand-by afterwards, the synthetic method of film is similar, according to it to supporting the requirement of situation, can put into suitable carrier in mother liquor;
(2) again will poromerics described in (1) or film as prop carrier, after it is contacted certain hour with ionic liquid or ionic liquid with the dispersant of other solvents, obtain the composite using poromerics hole cage as prop carrier or film;
(3) composite obtained and film are washed, dried.
4. described in claim 1 by the composite of poromerics supported ion liquid or the preparation method of film, it is characterized in that: this composite or film prepare by immersing the post-processing approach stirred, and concrete steps are as follows:
(1) conveniently synthetic method poromerics or film, be dissolved in corresponding solvent by the whole presomas needed for materials synthesis, react a period of time at a certain temperature, material is separated with mother liquor, washing and drying is stand-by afterwards, the synthetic method of film is similar, according to it to supporting the requirement of situation, can put into suitable carrier in mother liquor;
(2) again the poromerics described in (1) or film are immersed in the middle of the dispersant of ionic liquid or ionic liquid and other solvents, by rapid stirring, form the composite using poromerics hole cage as prop carrier or laminated film;
(3) composite obtained and film are washed, dried.
5. described in claim 1 by the composite of poromerics supported ion liquid or the preparation method of film, it is characterized in that: the post-processing approach that this composite or film pressurize by inert gas prepares, and concrete steps are as follows:
(1) conveniently synthetic method poromerics or film, be dissolved in corresponding solvent by the whole presomas needed for materials synthesis, react a period of time at a certain temperature, material is separated with mother liquor, washing and drying is stand-by afterwards, the synthetic method of film is similar, according to it to supporting the requirement of situation, can put into suitable carrier in mother liquor;
(2) again the poromerics described in (1) or film are immersed in the middle of the dispersant of ionic liquid or ionic liquid and other solvents, by passing into inert gas pressurized operation, ionic liquid is entered in the middle of the hole cage of porous material, forms the composite using porous material hole cage as prop carrier or laminated film;
(3) composite obtained and film are washed, dried.
6. described in claim 1 by the composite of poromerics supported ion liquid or the preparation method of film, it is characterized in that: this composite or film by after vacuumize negative pressure post-processing approach prepare, concrete steps are as follows:
(1) conveniently synthetic method poromerics or film, be dissolved in corresponding solvent by the whole presomas needed for materials synthesis, react a period of time at a certain temperature, material is separated with mother liquor, washing and drying is stand-by afterwards, the synthetic method of film is similar, according to it to supporting the requirement of situation, can put into suitable carrier in mother liquor;
(2) again the poromerics described in (1) or film are immersed in the middle of the dispersant of ionic liquid or ionic liquid and other solvents, by vacuumizing formation subnormal ambient, the ionic liquid of the difficult volatilization of order is drawn in the middle of the cage of poromerics hole, forms the composite using poromerics hole cage as prop carrier or laminated film;
(3) composite obtained and film are washed, dried.
7. according to described in claim 2 by the composite of poromerics supported ion liquid or the preparation method of film, it is characterized in that: in step (1), the temperature of fabricated in situ poromerics ionic liquid composite material or film is-30 DEG C ~ 300 DEG C, and the time is 1s ~ 8640000s.
8. according to described in claim 3 by the composite of poromerics supported ion liquid or the preparation method of film, it is characterized in that: in step (2), solid-liquid mass ratio is 0.001 ~ 1000, and the temperature of solid-liquid contact is-30 DEG C ~ 300 DEG C, and the time is 1s ~ 8640000s.
9. according to described in claim 4 by the composite of poromerics supported ion liquid or the preparation method of film, it is characterized in that: in step (2), solid-liquid mass ratio is 0.001 ~ 1000, and the temperature of stir process is-30 DEG C ~ 300 DEG C, and the time is 1s ~ 8640000s.
10. according to described in claim 5 by the composite of poromerics supported ion liquid or the preparation method of film, it is characterized in that: in step (2), solid-liquid mass ratio is 0.001 ~ 1000, and the pressure applying inert gas is 0 ~ 50MPa, treatment temperature is-30 DEG C ~ 300 DEG C, and the time is
1s ~ 8640000s; Inert gas is high-purity helium, the one in high pure nitrogen or high-purity argon gas.
11. according to described in claim 6 by the composite of poromerics supported ion liquid or the preparation method of film, it is characterized in that: in step (2), solid-liquid mass ratio is 0.001 ~ 1000, system vacuum is 0 ~ 0.1MPa, treatment temperature is-30 DEG C ~ 300 DEG C, and the time is 1s ~ 8640000s.
12. according to described in claim 2-6 any one by the composite of poromerics supported ion liquid or the preparation method of film, it is characterized in that: the mass fraction of the solutrope intermediate ion liquid of described ionic liquid or ionic liquid and other solvents is 0 ~ 100%.
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| CN105597706A (en) * | 2015-12-23 | 2016-05-25 | 北京化工大学 | Preparation method for porous polymeric ionic liquid for carbon dioxide adsorption |
| CN106582328A (en) * | 2015-10-20 | 2017-04-26 | 中国科学院大连化学物理研究所 | Composite separation film |
| CN107638870A (en) * | 2016-07-22 | 2018-01-30 | 浙江大学 | A kind of preparation method and application of ionic liquid and metal organic frame compound adsorbent |
| CN108114567A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | Accurate screening CO2/N2Method |
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| CN105597706B (en) * | 2015-12-23 | 2017-12-12 | 北京化工大学 | A kind of preparation method of porous polymeric ionic liquid for carbon dioxide adsorption |
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| CN108114567A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | Accurate screening CO2/N2Method |
| CN108114695A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | The zeolitic imidazolate framework material of solid-loaded ionic-liquid and its application in cage |
| CN108114698A (en) * | 2016-11-30 | 2018-06-05 | 中国科学院大连化学物理研究所 | Composite material by porous material loading ionic liquid and its preparation method and application |
| CN109847702A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A method of the cage diameter modulation of the poromerics containing basket structure |
| CN113041827A (en) * | 2021-03-16 | 2021-06-29 | 西安建筑科技大学 | Calcium-based ionic liquid for flue gas desulfurization, desulfurizer and preparation method thereof |
| CN113041826A (en) * | 2021-03-16 | 2021-06-29 | 西安建筑科技大学 | Zinc-based supported desulfurizer for flue gas desulfurization and preparation method thereof |
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