CN115055066B - Microporous polymer particle/polymer mixed matrix membrane and preparation method and application thereof - Google Patents

Microporous polymer particle/polymer mixed matrix membrane and preparation method and application thereof Download PDF

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CN115055066B
CN115055066B CN202210512246.1A CN202210512246A CN115055066B CN 115055066 B CN115055066 B CN 115055066B CN 202210512246 A CN202210512246 A CN 202210512246A CN 115055066 B CN115055066 B CN 115055066B
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周浩力
赵帅
金万勤
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Nanjing Tech University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/22—Carbon dioxide
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    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/02—Polyamines
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention discloses a preparation method of microporous polymer particles/polymer mixed matrix membrane, which takes aniline compounds as monomers and prepares microporous polymer particles with high porosity and high specific surface area through the synergistic regulation and control of reaction conditions; the microporous polymer particle/polymer mixed matrix membrane with high separation performance is prepared by optimizing the doping ratio between the microporous polymer particles and the polymer. The mixed matrix membrane prepared by the invention has outstanding separation performance on VOCs in enriched VOCs/inert gas, solves the problem of mutual restriction of permeability and selectivity of the traditional polymer membrane, and breaks the limitation of low membrane selectivity.

Description

Microporous polymer particle/polymer mixed matrix membrane and preparation method and application thereof
Technical Field
The invention relates to a microporous polymer particle/polymer mixed matrix membrane and a preparation method and application thereof, belongs to the technical field of polymer membrane preparation technology and environmental protection, belongs to the field of high polymer membranes, and particularly belongs to the field of vapor permeation.
Background
Volatile Organic Compounds (VOCs) are organic compounds with saturation vapor pressure higher than 133.32Pa at normal temperature and boiling point of 50-260 ℃ at standard atmospheric pressure or high volatility at normal temperature and normal pressure. VOCs are extremely complex in composition and their unorganized emissions can have a significant impact on the human body and the environment. The comprehensive treatment strategy of VOCs has three treatment strategies, namely source reduction, process control and terminal treatment. The end treatment technology only needs to collect and treat the end, and is various, so that the emission of VOCs can be well controlled, and is the mainstream research technology at present. The membrane separation technology has the advantages of high efficiency, low energy consumption, compact equipment, environmental friendliness, no secondary pollution and the like, and is considered as an effective separation technology for treating organic pollutants at present.
The advent of microporous organic polymers has contributed significantly to gas storage and separation applications. Because of its remarkable physicochemical stability, microporous organic polymer particles are well suited for high temperature, humid and acid gas capture and separation applications. Microporous organic polymers with polar groups have higher CO 2 Binding energy. Due to hydrogen bond and dipole, there is stronger CO 2 The frames interact. The larger specific surface area, the small pore diameter and the polar functional group are beneficial to the separation of gases. And it has higher gas absorption capacity, chemical non-uniformity and higher physicochemical stability, and shows good prospects in separation application. The microporous polymer has a controllable pore structure and also has strong adsorption capacity on VOCs. The inevitable presence of water in many sources of VOCs, competitive adsorption of VOCs molecules and water molecules severely affects the adsorption capacity. The microporous organic polymer is an excellent moisture-resistant VOCs adsorbent material and exhibits good adsorption capacity at high humidity.
The synthetic method is critical to the separation performance of the polymer. In 2013, petal et al (Unprecedented high-temperature CO 2 selectivity in N 2 The phobic nanoporous covalent organic polymers Nature communications 2013,4 (1): 1357-1357) study shows that the nitrogen double bonds (azo bonds) in the porous polymer backbone play an important role in small gas storage and separation applications. However, the low surface area of azo polymers results in relatively low CO 2 Absorption capacity, which may limit the CO of azo polymers 2 Application in trapping and separation. The conventional method for preparing azo polymers is to synthesize azo monomers in advance and then react the azo monomers by certain groupsAn azo polymer (CN 111303411A, CN 106188387B) was produced. However, the method has the disadvantages of complex reaction process, more reaction components and serious resource waste. At present, a method for synthesizing azo polymers in situ (CN 103936982A, CN 108807939A) is mostly used, but the method needs to synthesize a metal ion photocatalyst in advance, has harsh reaction conditions and has low conversion rate. This study reports another method of constructing azo polymers with high porosity and significant CO 2 Absorption capacity.
Disclosure of Invention
The invention aims at a preparation method and application of a microporous polymer particle/polymer mixed matrix membrane, and the method solves the limitations in the existing method for removing organic matters in organic vapor by vapor permeation, and increases the flux of VOCs while the prepared separation membrane has better stability.
The aim of the invention can be achieved by the following measures:
a method of preparing a microporous polymer particle/polymer mixed matrix membrane, the method comprising the steps of:
(1) Aniline compounds are taken as monomers, added with organic solvent and uniformly mixed for 20-24 hours, and then polymerization reaction is carried out in the organic solvent continuously; filtering the obtained polymer solution, taking a precipitate, washing and drying to obtain microporous polymer particles;
(2) And (3) performing ultrasonic dispersion on the microporous polymer particles, adding the polymer, dissolving in an organic solvent, heating to crosslink the polymer to prepare casting solution, coating the casting solution on a support after defoaming treatment, and drying to obtain the microporous polymer particles/polymer mixed matrix membrane.
A microporous polymer particle/polymer mixed matrix membrane, the separation membrane being prepared by the method comprising:
(1) Aniline compounds are taken as monomers, added with organic solvent and uniformly mixed for 20-24 hours, and then polymerization reaction is carried out in the organic solvent continuously; filtering the obtained polymer solution, taking a precipitate, washing and drying to obtain microporous polymer particles;
(2) And (3) performing ultrasonic dispersion on the microporous polymer particles, adding the polymer, dissolving in an organic solvent, heating to crosslink the polymer to prepare casting solution, coating the casting solution on a support after defoaming treatment, and drying to obtain the microporous polymer particles/polymer mixed matrix membrane.
In the separation membrane and the preparation method of the separation membrane, 3', 5' -tetramethyl benzidine, 3 '-diamino benzidine, 4' -diamino biphenyl and 4, 4-diamino diphenyl ether are taken as monomers to carry out polymerization reaction under the catalysis of cuprous bromide and pyridine. The polymer particles are separated out after the reaction, then the polymer particles are further washed and dried, and then the polymer particles are doped with the VOCs which penetrate preferentially, and the polymer particles are dissolved in an organic solvent to prepare the separation membrane. The microporous organic polymer particles prepared by the method are insoluble in common organic solvents such as tetrahydrofuran, dimethylformamide, dichloromethane, methanol and acetone, and have expected super-crosslinked network, and the separation performance of the separation membrane prepared by the method is better and the flux is higher.
In some specific technical schemes: in step (1), the aniline compound is selected from 3,3',5,5' -tetramethylbenzidine, 3 '-diaminobenzidine, 4' -diaminodiphenyl ether, o-phenylenediamine, 2, 5-dimethylphosphine, 1, 4-phenylenediamine, m-phenylenediamine, 2-aminobenzonitrile, 3-aminophenol, dichlorobis [ di-tert-butyl- (4-dimethylaminophenyl) phosphine ] palladium (II), 3-nitro-4-hydroxypropanylphenol, 3-N-boc-amino-1- [ 2-amino-1- (2-aminophenyl) -ethyl ] -pyrrolidine 3-N-boc-amino-1- [ 2-amino-1- (3-aminophenyl) -ethyl ] -pyrrolidine, (1-methylcyclohexane) methyl-4-aminophenylether, (3-aminophenoxy) -acetonitrile, 3-aminophenylbenzophenone, 4, 8-dioxo-dodecane-1, 12-diamine, 3,4 '-diaminodiphenyl ether, 1, 3-bis (4-aminophenoxy) benzene, N-methyl-N- (4-aminophenoxy ethyl) -4-aminophenylethylamine, 2, 4-diamino-6-butylamino-1, 3, 5-triazine, 4' -diaminodiphenyl sulfone, 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 5-amino-4-imidazole carboxamide, 4' -diaminobenzidine 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane, 2' -diaminoethylene glycol diphenyl ether bis (4-amino-2, 3-dichlorophenyl) methane, 1, 8-diamino-3, 6-dioxaoctane, 2, 6-diaminopurine, 1-bis (4-aminophenyl) cyclohexane, 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2-bis [4- (4-aminophenoxy) phenyl ] propane 3,3' -diaminodipropylamine, 2, 4-diamino-6-methyl-1, 3, 5-triazine, bis [4- (3-aminophenoxy) phenyl ] sulfone, 4' -bis (4-aminophenoxy) biphenyl, neopentyl glycol bis (4-aminophenyl) ether, 2, 4-diamino-6-dimethylamine-1, 3, 5-triazine, 1, 4-butanediol bis (3-aminobutyrate), 4' -diamino-p-terphenyl, N- (2-ethylamino) -1, 3-propanediamine, bis (3-amino-4-hydroxyphenyl) sulfone, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 2,3,5, 6-tetrafluoro-p-xylylenediamine, 2,4,5, 6-tetrafluoro-1, 3-phenylenediamine, 3, 9-bis (3-aminopropyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane, 2-aminophenyl ether, 3,4' -diaminodiphenyl ether, 3, 4-diaminodiphenyl ether, 4-amino-4 ' -tert-butyldiphenyl ether, 3, 4-triamino-diphenyl ether, 2' -diaminoethylene glycol diphenyl ether, 2-aminodiphenyl ether, neopentyl ethylene glycol bis (4-aminophenyl) ether, bis (3-aminopropyl) ether, bis (2-formylphenyl) ether, resorcinol diglycidyl ether, 2' -bis (trifluoromethyl) -4,4' -diaminophenyl ether 5,5' - (hexafluoroisomethylene) bis (o-toluidine), 3-oxybis [5- (trifluoromethyl) aniline ], 2' -bis (trifluoromethyl) diaminobiphenyl, 2-bis (3-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-methylphenyl) hexafluoropropane 2, 2-bis (4-aminophenyl) hexafluoropropane, 3-bis (trifluoromethyl) - [1, 1-biphenyl ] -4, 4-diamine, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, diaminodiphenylmethane, dibromo-1, 5-diamino-4, 8-dihydroxy-9, 10-anthracenedione, diaminoglyoxime, 3 '-diaminodiphenyl sulfone, 2, 4-diaminoanisole, 2, 6-diaminopimelic acid, 4' -diaminoanilide, 1, 8-diamino-3, 6-dioxaoctane, 2,4, 6-triaminopyrimidine, 2,4, 6-triamino-5-pyrimidinecarbonitrile, 2, 4-diamino-6-diallylamino-1, 3, 5-triazine, (S) -2, 6-diamino-4, 5,6, 7-tetrahydrobenzothiazole, 1, 4-diamino-2, 3-dicyano-9, 10-anthraquinone, 2-chloro-4, 6-diamino-1, 3, 5-triazine any one of 3, 5-diamino-1, 2, 4-triazole, 1, 2-diamino-2-methylpropane, 3-aminopropionamide, malonamide, 4-diamino-1, 1-biphenyl-3, 3-dicarboxylic acid, 4-diaminobiphenyl-2, 2-dicarboxylic acid, 4-fluoro-1, 3-diaminobenzene, 2, 5-diamino-4-nitro-4 '-dimethylaminostilbene, 4' -diamino-2, 2 '-dimethyl-1, 1' -biphenyl, and 2, 4-diaminophenoxyethanol hydrochloride;
Preferably: the aniline compound is selected from 3,3', 5' -tetramethyl benzidine, 3' -diamino benzidine, 4' -diamino benzidine and 4,4' -diamino diphenyl ether.
In the step (1), a catalyst is added and uniformly mixed for 20-30 hours, wherein the catalyst is any one or two of sodium nitrite, potassium carbonate, nano gold particles, 4-dimethylaminopyridine, sodium cyanide, potassium cyanide, dibutyltin dilaurate, cuprous chloride, cuprous bromide and pyridine; the mass ratio of the catalyst to the monomer is 1:0.2-6.0;
preferably: the mass ratio of the catalyst to the monomer is 1:0.5 to 2;
further preferred is: the catalyst is cuprous bromide and pyridine with the mass ratio of 1:3-6.
In a preferred scheme, the mass ratio of the catalyst to the monomer in the step (1) is 1:0.6-2.0, the catalyst is cuprous bromide and pyridine, and the mass ratio is 1:3.0-6.0.
The invention relates to a separation membrane and a preparation method thereof, wherein: in the step (1), the organic solvent is any two of tetrahydrofuran, toluene, chloroform, methanol, acetone, methyl pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, m-cresol, acetonitrile, dioxane, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether, triethanolamine, carbon tetrachloride, trichloroethylene, tetrachloroethylene, trichloropropane and dichloroethane; preferably: the organic solvent is selected from any one or two of tetrahydrofuran, toluene, chloroform, methanol and acetone; further preferred is: the organic solvent is tetrahydrofuran and toluene with the volume ratio of 1-3:1-3.
The invention relates to a separation membrane and a preparation method thereof, wherein: the polymerization reaction temperature is 30-120 ℃ and the reaction time is 20-144 h; preferably: the polymerization reaction temperature is 60-100 ℃ and the reaction time is 20-84 h; further preferred is: the polymerization condition is that firstly, the reaction is carried out for 10 to 14 hours under the condition that the temperature is 55 to 65 ℃, and then the reaction is carried out for 10 to 14 hours under the condition that the temperature is 75 to 85 ℃; or firstly reacting for 10-14 h at 55-65 ℃, and then reacting for 36-72 h at 75-85 ℃; or firstly reacting for 10-14 h at 80-100 ℃, and then reacting for 10-14 h at 100-120 ℃.
The invention relates to a separation membrane and a preparation method thereof, wherein: the polymer in the step (2) is any one of Polydimethylsiloxane (PDMS), polyoctylmethylsiloxane (POMS), polytrifluoropropylmethylsiloxane (PTFPMS), polyether copolyamide (PEBA), fluorine-containing polymer, self-microporous Polymer (PIMs) and hyperbranched polymer;
the invention relates to a separation membrane and a preparation method thereof, wherein: the mass ratio between the microporous polymer particles and the polymer in the step (2) is 1:0.4-1000.0.
In a preferred embodiment, in step (2), the mass ratio between the microporous polymer particles and the polymer is 1:0.4 to 1000.0; preferably: the mass ratio of the microporous polymer particles to the polymer is 1:4.0 to 250; further preferred is: the mass ratio of the microporous polymer particles to the polymer is 1:25 to 110.
The invention relates to a separation membrane and a preparation method thereof, wherein: carrying out ultrasonic treatment on the microporous polymer particles in the step (2) for 0.1-1 h; preferably: the ultrasonic treatment time is 0.3-0.5 h.
The invention relates to a separation membrane and a preparation method thereof, wherein: the organic solvent is any one of n-hexane, n-heptane, toluene, tetrahydrofuran, chloroform, methanol, acetone, methyl pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, m-cresol, acetonitrile, dioxane, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether, triethanolamine, carbon tetrachloride, trichloroethylene, tetrachloroethylene, n-butanol, trichloropropane and dichloroethane; preferably: the organic solvent is selected from any one of n-butanol, methyl pyrrolidone, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide and n-heptane.
In the step (2), the concentration of the film casting solution is 0.5-80 wt%, and the heating temperature is 20-180 ℃; preferably, the concentration of the casting solution is 1-15 wt%, the heating temperature is 75-85 ℃ and the heating time is 1-3 h.
The invention relates to a separation membrane and a preparation method thereof, wherein: the support in the step (2) is selected from an organic material base film or an inorganic material base film; preferably: the support is selected from any one of polytetrafluoroethylene, polyamide, cellulose acetate, ceramic, silicon carbide, alumina, polyvinylidene fluoride and polyacrylonitrile.
In some specific technical schemes: in the step (2), the casting solution is coated on a support body and then is dried in an oven to obtain a microporous polymer particle/polymer mixed matrix film; wherein the oven is a blast drying oven.
In the technical scheme of the invention, the drying and solvent removal method is a heating method for volatilizing, the heating temperature is 20-200 ℃, and the preferable method is that: the heating temperature is 50-80 ℃ below the boiling point temperature of the solvent.
In the technical scheme of the invention, the solvent is volatilized after drying and removing is controlled to be 0.3-48 h, and the preferred volatilization time is 10-15 h.
The invention relates to a separation membrane and a preparation method thereof, wherein: the microporous polymer particles/polymer mixed matrix membrane is used for VOCs/inert gas separation and preferentially permeates VOCs, and the VOCs are at least one of alkanes, aromatic hydrocarbons, esters, aldehydes, alcohols and benzenes; the feeding concentration of the raw material side is 200-500000 ppm, the temperature is-30-120 ℃, and the pressure measured by permeation is 100-30000 Pa
Further preferred is: the feeding concentration of the raw material side is 2000-30000 ppm, the temperature is 20-80 ℃, and the osmotic pressure is 200-1000 Pa.
The beneficial effects of the invention are as follows: the separation membrane prepared by the invention is used for separationSeparation C 2 H 5 OH/CO 2 The system has higher permeability coefficient and selectivity. The polymer film material has better stability, ductility, thermal stability and chemical stability and excellent solvent resistance. However, the polymer membrane material has certain problems, such as general anti-swelling performance, general gas separation selectivity and mutual balance of gas permeability coefficient and selectivity. The invention introduces microporous polymer particles, improves the flux and selectivity of VOCs while meeting the separation requirement of the polymer membrane on the VOCs, can achieve the treatment effect with less membrane area under the same unit treatment capacity condition, improves the efficiency and reduces the investment cost.
Drawings
FIG. 1 is an FT-IR chart of the polymer powder in example 1 of the invention;
FIG. 2 is an electron microscopic view of the polymer powder in example 1 of the present invention;
FIG. 3 is a surface view of a microporous polymer particle/PDMS mixed matrix membrane according to example 1 of the present invention;
FIG. 4 is a cross-sectional view of a microporous polymer particle/PDMS mixed matrix membrane according to example 1 of the present invention.
Detailed Description
The invention is further illustrated below with reference to examples, but the scope of the invention is not limited thereto:
the flux (J) of the microporous polymer particles/polymer mixed matrix membrane is calculated as follows:
Figure SMS_1
wherein W is the mass (g) of the permeate component, A is the effective area (m 2 ) T is the time interval(s) of the permeation process.
The osmotic coefficient of the microporous polymer particles/polymer blend matrix membrane was calculated as follows:
Figure SMS_2
wherein: l is the film thickness (cm), X feed And X perm Mole fractions of component i, J, measured as raw material and measured as permeate, respectively i Is the permeation flux of component i, P feed And P perm The pressures measured for the feed and for the permeate (cmHg), respectively.
The selectivity of the microporous polymer particles/polymer blend matrix membrane is calculated as follows:
Figure SMS_3
wherein: p (P) voc And P CO2 Respectively correspond to VOC and CO 2 Is used for the permeability coefficient of (a).
The separation factor of the microporous polymer particles/polymer mixed matrix membrane is calculated as follows:
Figure SMS_4
wherein: x is X feed And X perm The mole fractions of component i were measured for the raw material and for the osmometry, respectively.
Example 1
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Drying in a vacuum oven at 110deg.C for 12h to obtain polymer powder as shown in FIGS. 1 and 2.
0.005g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.995g of PDMS and 29g of n-heptane were added, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to obtain a casting solution. The obtained casting solution was coated on a polytetrafluoroethylene support, allowed to stand at room temperature for 3 hours, and then baked in a forced air drying oven at 80℃for 12 hours to obtain a microporous polymer particle/PDMS mixed matrix membrane as shown in FIGS. 3 and 4.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 2000ppm on the feed side to 21128ppm on the permeate side, with a permeability of 23414barrer and a selectivity of 11.17.
Example 2
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 29390ppm on the permeate side, with a permeation of 30074barrer and a selectivity of 15.93.
Example 3
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.015g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and PDMS 0.985g and n-heptane 29g were added, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h to give a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 2000ppm on the feed side to 27889ppm on the permeate side, with a permeability of 29323barrer and a selectivity of 15.05.
Example 4
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.02g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.98g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 2000ppm on the feed side to 26849ppm on the permeate side, with a permeability of 31184barrer and selectivity of 14.44.
Example 5
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.03g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.97g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 2000ppm on the feed side to 27033ppm on the permeate side, with a permeability of 28380barrer and a selectivity of 14.55.
Example 6
1g of 3,3' -diaminobenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 2000ppm on the feed side to 13270ppm on the permeate side, with a permeability of 22694barrer and a selectivity of 6.8.
Example 7
1g of 3,3' -diaminobenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.03g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.97g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 2000ppm on the feed side to 17587ppm on the permeate side, with a permeability of 35388barrer and a selectivity of 9.2.
Example 8
1g of 4,4' -diaminobenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 2000ppm on the feed side to 17971ppm on the permeate side, with a permeability of 50419 barrerer, selectivity was 9.41.
Example 9
1g of 4,4' -diaminodiphenyl ether was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 2000ppm on the feed side to 19779ppm on the permeate side, with a permeability of 49806barrer and a selectivity of 10.41.
Example 10
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of toluene solvent. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 2000ppm on the feed side to 27033ppm on the permeate side, with a permeability of 50434barrer and a selectivity of 11.87.
Example 11
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 1.2g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was 2000ppm liter from the raw material sideUp to 27033ppm on the permeate side, the ethanol permeability was 30433barrer, selectivity 15.36.
Example 12
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 36 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 2000ppm on the feed side to 27033ppm on the permeate side, with a permeability of 29987barrer and a selectivity of 15.88.
Example 13
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 72 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 2000ppm on the feed side to 27033ppm on the permeate side, with a 30104barrer, selectivity to ethanol of 16.
Example 14
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 80℃for 12 hours, and then at 100℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material was measured at a concentration of 2000ppm and a temperature of 30℃and the pressure was supplied by a vacuum pump by osmosis measurement, and the pressure by osmosis measurement (gaugePressure) is always maintained at around 200 pa. After membrane separation, the ethanol concentration was increased from 2000ppm on the feed side to 26849ppm on the permeate side, with a 30184barrer permeability and a selectivity of 15.79.
Example 15
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 100℃for 12 hours, and then at 120℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 2000ppm on the feed side to 26849ppm on the permeate side, with a permeability of 30786barrer and a selectivity of 15.9.
Example 16
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 5000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 5000ppm on the feed side to 45458ppm on the permeate side, with a permeability of 18242barrer and a selectivity of 9.77.
Example 17
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 Measuring concentration of raw materialsAt 8000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was maintained around 200pa at all times. After membrane separation, the ethanol concentration increased from 8000ppm on the feed side to 56208ppm on the permeate side, with a permeability of 13702barrer and a selectivity of 7.36.
Example 18
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 12000ppm, the temperature was 30deg.C, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 12000ppm on the feed side to 93727ppm on the permeate side, with a 15815barrer for ethanol permeability and a selectivity of 8.74.
Example 19
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 17000ppm, the temperature was 30deg.C, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 17000ppm on the feed side to 80808ppm on the permeate side, with a permeability of 9784barrer and a selectivity of 5.15.
Example 20
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 21000ppm, the temperature was 30deg.C, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 21000ppm on the feed side to 10060ppm on the permeate side, with a permeability of 9663barrer and a selectivity of 5.29.
Example 21
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 24000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 24000ppm on the feed side to 11589ppm on the permeate side, with a permeability of 9981barrer and a selectivity of 5.41.
Example 22
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 20 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 38192ppm on the permeate side, with a permeability of 40670barrer and selectivity of 19.81.
Example 23
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 40 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 28437ppm on the permeate side, with a permeation of 26678barrer and a selectivity of 15.13.
Example 24
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 50 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 27937ppm on the permeate side, with a permeability of 25347barrer and a selectivity of 14.13.
Example 25
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 60 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 2000ppm on the feed side to 18000ppm on the permeate side, with a permeability of 21928barrer and a selectivity of 11.92.
Example 26
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was maintained around 600pa all the time. After membrane separation, the ethanol concentration was increased from 2000ppm on the feed side to 25919ppm on the permeate side, with a permeability of 26776barrer and a selectivity of 14.2.
Example 27
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 800 pa. After membrane separation, the ethanol concentration was increased from 2000ppm on the feed side to 21327ppm on the permeate side, with a permeability of 2179 barrer and selectivity of 11.79.
Example 28
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then 0.99g of PDMS and 29g of n-heptane were added thereto, followed by stirring at room temperature for 0.5h and then stirring at 80℃for 2h, to thereby obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was maintained around 1000pa all the time. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 18747ppm on the permeate side, with a permeability of 20373barrer and a selectivity of 10.39.
Example 29
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
Dispersing 0.01g of polymer powder in 20g of n-butanol, carrying out ultrasonic treatment for 0.5h, adding 0.99g of PEBA2533 and 29g of n-butanol, stirring at room temperature for 0.5h, and then stirring at 80 ℃ for 2h to obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PEBA mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 21891ppm on the permeate side, with a permeability of 6756.3barrer and a selectivity of 10.89.
Example 30
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then added with 0.99g of PDMS and 29g of n-heptane, stirred at room temperature for 0.5h, and then stirred at 80℃for 2h to obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/N 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 42204ppm on the permeate side, with a permeability of 9327.03barrer and a selectivity of 38.8.
Example 31
1g of 3,3', 5' -tetramethylbenzidine was taken and added to 220mL of a tetrahydrofuran/toluene (v/v=1:1) solvent mixture. 0.235g of cuprous bromide and 0.94g of pyridine were added. The resulting mixture was stirred under an air atmosphere at room temperature for 24 hours, at 60℃for 12 hours, and then at 80℃for 12 hours. After that, the mixture was filtered and washed with tetrahydrofuran and water. The resulting powder was soaked in dilute hydrochloric acid for 24h, then filtered and the resulting powder was further washed with water and ethanol. Baking in a vacuum drying oven at 110 ℃ for 12h.
0.01g of polymer powder was dispersed in 20g of n-heptane, sonicated for 0.5h, and then added with 0.99g of PDMS and 29g of n-heptane, stirred at room temperature for 0.5h, and then stirred at 80℃for 2h to obtain a casting solution. Coating the obtained casting film liquid on a polytetrafluoroethylene support, standing for 3 hours at room temperature, and then drying for 12 hours in a blowing drying oven at 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix film.
Test of the composite film obtained in this example for C 2 H 5 OH/N 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 20000ppm, the temperature was 30deg.C, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration was increased from 20000ppm on the feed side to 47799ppm on the permeate side, with a permeability of 12934barrer and a selectivity of 49.9.
Example 32
PDMS 1g and n-heptane 50g were taken and stirred at room temperature for 0.5h, followed by stirring at 80℃for 2h to give a casting solution. The obtained casting solution is coated on a polytetrafluoroethylene support, kept stand for 3 hours at room temperature, and then baked for 12 hours in a blast drying oven at 80 ℃ to obtain the PDMS film.
Test of the composite film obtained in this example for C 2 H 5 OH/CO 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa.After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 15314ppm on the permeate side, with a permeability of 20124barrer and a selectivity of 7.76.
Example 33
PDMS 1g and n-heptane 50g were taken and stirred at room temperature for 0.5h, followed by stirring at 80℃for 2h to give a casting solution. The obtained casting solution is coated on a polytetrafluoroethylene support, kept stand for 3 hours at room temperature, and then baked for 12 hours in a blast drying oven at 80 ℃ to obtain the PDMS film.
Test of the composite film obtained in this example for C 2 H 5 OH/N 2 Separation performance of the system, effective area of the polymer film was 10cm 2 The raw material concentration was 2000ppm, the temperature was 30 ℃, the pressure was supplied by a vacuum pump in the osmometry, and the pressure (gauge pressure) in the osmometry was always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 61084ppm on the permeate side, with a permeability of 13734barrer and a selectivity of 32.

Claims (20)

1. Use of microporous polymer particles/polymer blend matrix membranes for VOCs/inert gas separation, characterized in that: the preparation method of the microporous polymer particle/polymer mixed matrix membrane comprises the following steps:
(1) Aniline compounds are taken as monomers, organic solvents are added and uniformly mixed for 20-24 hours, and then polymerization reaction is carried out in the organic solvents continuously; filtering the obtained polymer solution, taking a precipitate, washing and drying to obtain microporous polymer particles, adding a catalyst into the polymerization reaction, and uniformly mixing for 20-30 hours, wherein the catalyst is any one or two of sodium nitrite, potassium carbonate, nano gold particles, 4-dimethylaminopyridine, sodium cyanide, potassium cyanide, dibutyl tin dilaurate, cuprous chloride, cuprous bromide and pyridine; the mass ratio of the catalyst to the monomer is 1:0.2-6.0;
(2) Carrying out ultrasonic dispersion on microporous polymer particles, adding a polymer, dissolving in an organic solvent, heating to crosslink the polymer to prepare a casting solution, coating the casting solution on a support after defoaming treatment, and drying to obtain a microporous polymer particle/polymer mixed matrix membrane; the mixed matrix membrane preferentially permeates VOCs, and the VOCs are at least one of alkanes, aromatic hydrocarbons, esters, aldehydes, alcohols and benzenes; the feeding concentration of the raw material side is 200-500000 ppm, the temperature is-30-120 ℃, and the pressure measured by permeation is 100-30000 Pa.
2. The use according to claim 1, characterized in that: in step (1), the aniline compound is selected from 3,3',5,5' -tetramethylbenzidine, 3 '-diaminobenzidine, 4' -diaminodiphenyl ether, o-phenylenediamine, 2, 5-dimethylphosphine, 1, 4-phenylenediamine, m-phenylenediamine, 2-aminobenzonitrile, 3-aminophenol, dichlorobis [ di-tert-butyl- (4-dimethylaminophenyl) phosphine ] palladium (II), 3-nitro-4-hydroxypropylaminophenol, 3-N-boc-amino-1- [ 2-amino-1- (2-aminophenyl) -ethyl ] -pyrrolidine, 3-N-boc-amino-1- [ 2-amino-1- (3-aminophenyl) -ethyl ] -pyrrolidine (1-methylcyclohexane) methyl-4-aminophenylether, (3-aminophenoxy) -acetonitrile, 3-aminophenylbenzophenone, 4, 8-dioxo-dodecane-1, 12-diamine, 3,4 '-diaminodiphenyl ether, 1, 3-bis (4-aminophenoxy) benzene, N-methyl-N- (4-aminophenoxyethyl) -4-aminophenylethylamine, 2, 4-diamino-6-butylamino-1, 3, 5-triazine, 4' -diaminodiphenyl sulfone, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 5-amino-4-imidazole carboxamide, 4' -diaminobenzidine, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane 2,2' -diaminoethylene glycol diphenyl ether, bis (4-amino-2, 3-dichlorophenyl) methane, 1, 8-diamino-3, 6-dioxaoctane 2, 6-diaminopurine, 1-bis (4-aminophenyl) cyclohexane, 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 3' -diaminodipropylamine, 2, 4-diamino-6-methyl-1, 3, 5-triazine bis [4- (3-aminophenoxy) phenyl ] sulfone, 4' -bis (4-aminophenoxy) biphenyl, neopentyl glycol bis (4-aminophenyl) ether, 2, 4-diamino-6-dimethylamine-1, 3, 5-triazine, 1, 4-butanediol bis (3-aminobutyrate), 4' -diamino-p-terphenyl, N- (2-ethylamino) -1, 3-propanediamine, bis (3-amino-4-hydroxyphenyl) sulfone, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 2,3,5, 6-tetrafluoro-p-xylylenediamine, 2,4,5, 6-tetrafluoro-1, 3-phenylenediamine, 3, 9-bis (3-aminopropyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane, 2-aminophenyl ether, 3,4' -diaminodiphenyl ether, 3, 4-diaminodiphenyl ether, 4-amino-4 ' -tert-butyldiphenyl ether, 3, 4-triaminopolyl ether, 2' -diaminoethylene glycol diphenyl ether, neopentyl ethylene glycol bis (4-aminophenyl) ether, bis (3-aminopropyl) ether, bis (2-formylphenyl) ether, resorcinol diglycidyl ether, 2' -bis (trifluoromethyl) -4,4' -diaminophenyl ether, 5' - (hexafluoroisomethylene) diphthaline, 3-oxybis [5- (trifluoromethyl) aniline ]: 2,2' -bis (trifluoromethyl) diaminobiphenyl, 2-bis (3-aminophenyl) hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane, 3-bis (trifluoromethyl) - [1, 1-biphenyl ] -4, 4-diamine, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, diaminodiphenylmethane dibromo-1, 5-diamino-4, 8-dihydroxy-9, 10-anthracenedione, diaminoglyoxime, 3' -diaminodiphenyl sulfone, 2, 4-diaminoanisole, 2, 6-diaminopimelic acid, 4' -diaminoanilide, 1, 8-diamino-3, 6-dioxaoctane, any of 2,4, 6-triaminopyrimidine, 2,4, 6-triamino-5-pyrimidine carbonitrile, 2, 4-diamino-6-diallylamino-1, 3, 5-triazine, (S) -2, 6-diamino-4, 5,6, 7-tetrahydrobenzothiazole, 1, 4-diamino-2, 3-dicyano-9, 10-anthraquinone, 2-chloro-4, 6-diamino-1, 3, 5-triazine, 1, 2-diamino-2-methylpropane, 3-aminopropionamide, malonamide, 4-diamino-1, 1-biphenyl-3, 3-dicarboxylic acid, 4-diaminobiphenyl-2, 2-dicarboxylic acid, 4-fluoro-1, 3-diaminobenzene, 2, 5-diamino-4 ' -nitro-4 ' -dimethylaminostilbene, 4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl and 2, 4-diaminophenethyl alkoxide.
3. The use according to claim 2, characterized in that: the aniline compound is selected from 3,3', 5' -tetramethyl benzidine, 3 '-diamino benzidine and 4,4' -diamino diphenyl ether.
4. The use according to claim 1, characterized in that: the mass ratio of the catalyst to the monomer is 1:0.5 to 2.
5. The use according to claim 4, characterized in that: the catalyst is cuprous bromide and pyridine with the mass ratio of 1:3-6.
6. The use according to claim 1, characterized in that: in the step (1), the organic solvent is any two of tetrahydrofuran, toluene, chloroform, methanol, acetone, methyl pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, m-cresol, acetonitrile, dioxane, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether, triethanolamine, carbon tetrachloride, trichloroethylene, tetrachloroethylene, trichloropropane and dichloroethane.
7. The use according to claim 6, characterized in that: in the step (1), the organic solvent is selected from any one or two of tetrahydrofuran, toluene, chloroform, methanol and acetone.
8. The use according to claim 7, characterized in that: the organic solvent is tetrahydrofuran and toluene with the volume ratio of 1-3:1-3.
9. The use according to claim 1, characterized in that: in the step (1), the polymerization reaction temperature is 30-120 ℃ and the reaction time is 20-144 h.
10. The use according to claim 9, characterized in that: in the step (1), the polymerization reaction temperature is 60-100 ℃ and the reaction time is 20-84 h.
11. The use according to claim 10, characterized in that: in the step (1), the polymerization condition is that the reaction is firstly carried out for 10-14 hours under the condition that the temperature is 55-65 ℃, and then the reaction is carried out for 10-14 hours under the condition that the temperature is 75-85 ℃; or firstly reacting for 10-14 h at 55-65 ℃, and then reacting for 36-72 h at 75-85 ℃; or firstly reacting for 10-14 hours at the temperature of 80-100 ℃, and then reacting for 10-14 hours at the temperature of 100-120 ℃.
12. The use according to claim 1, characterized in that: in the step (2), the polymer is any one of polydimethylsiloxane PDMS, polyoctylmethylsiloxane POMS, polytrifluoropropyl methylsiloxane PTFPMS, polyether copolyamide PEBA, fluorine-containing polymer, self-microporous polymer PIMs and hyperbranched polymer.
13. The use according to claim 1, characterized in that: in the step (2), the mass ratio between the microporous polymer particles and the polymer is 1:0.4 to 1000.
14. The use according to claim 13, characterized in that: in the step (2), the mass ratio between the microporous polymer particles and the polymer is 1:4.0 to 250.
15. The use according to claim 14, characterized in that: in the step (2), the mass ratio between the microporous polymer particles and the polymer is 1:25 to 110.
16. The use according to claim 1, characterized in that: in the step (2), the organic solvent is any one of n-hexane, n-heptane, toluene, tetrahydrofuran, chloroform, methanol, acetone, methyl pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, m-cresol, acetonitrile, dioxane, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether, triethanolamine, carbon tetrachloride, trichloroethylene, tetrachloroethylene, n-butanol, trichloropropane and dichloroethane.
17. The use according to claim 16, characterized in that: in the step (2), the organic solvent is selected from any one of n-butanol, methyl pyrrolidone, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide and n-heptane.
18. The use according to claim 1, characterized in that: in the step (2), the concentration of the casting solution is 0.5-80 wt%, the heating temperature is 20-180 ℃, and the support is selected from an organic material base film or an inorganic material base film.
19. The use according to claim 18, characterized in that: in the step (2), the concentration of the casting solution is 1-15 wt%, the heating temperature is 75-85 ℃ and the heating time is 1-3 h; the support is selected from any one of polytetrafluoroethylene, polyamide, cellulose acetate, ceramic, silicon carbide, alumina, polyvinylidene fluoride and polyacrylonitrile.
20. The use according to claim 1, characterized in that: the feeding concentration of the raw material side is 2000-30000 ppm, the temperature is 20-80 ℃, and the osmotic pressure is 200-1000 Pa.
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