CN115055066A

CN115055066A - Microporous polymer particle/polymer mixed matrix membrane and preparation method and application thereof

Info

Publication number: CN115055066A
Application number: CN202210512246.1A
Authority: CN
Inventors: 周浩力; 赵帅; 金万勤
Original assignee: Nanjing Tech University
Current assignee: Nanjing Tech University
Priority date: 2022-05-12
Filing date: 2022-05-12
Publication date: 2022-09-16
Anticipated expiration: 2042-05-12
Also published as: CN115055066B

Abstract

The invention discloses a preparation method of a microporous polymer particle/polymer mixed matrix membrane, which takes aniline compounds as monomers to prepare microporous polymer particles with high porosity and high specific surface area through the synergistic regulation and control effect of reaction conditions; by optimizing the doping ratio between the microporous polymer particles and the polymer, the microporous polymer particle/polymer mixed matrix membrane with high separation performance is prepared. The mixed matrix membrane prepared by the invention has outstanding separation performance on VOCs in enriched VOCs/inert gas, solves the characteristic that the permeability and the selectivity of the traditional polymer membrane are mutually restricted, and breaks through 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, a preparation method and application thereof, belongs to the polymer membrane preparation technology and the environmental protection field technology, belongs to the high polymer membrane field, and particularly belongs to the steam permeation field.

Background

Volatile Organic Compounds (VOCs) are a general term for organic compounds having a saturated vapor pressure of more than 133.32Pa at normal temperature, a boiling point of 50-260 ℃ at standard atmospheric pressure, or a 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 as well as on the environment. The comprehensive VOCs treatment strategy has three treatment strategies, namely source reduction, process control and terminal treatment. The tail end processing technology only needs to collect and process at the tail end, is various and can well control the discharge of VOCs, so the tail end processing technology 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 to be an effective separation technology for treating organic pollutants at present.

The advent of microporous organic polymers has contributed greatly to the application of gas storage and separation. Because of their remarkable physicochemical stability, microporous organic polymer particles are well suited for high temperature, moisture and acid gas capture and separation applications. Microporous organic polymers with polar groups have higher CO ₂ Binding energy. Due to the presence of hydrogen bonds and dipoles, there will be stronger CO ₂ The frames interact. The larger specific surface area, small pore size and polar functional groups facilitate the separation of gases. And it has high gas absorption capacity and chemical propertyUniformity and higher physicochemical stability, showing good prospects in separation applications. The microporous polymer also has strong adsorption capacity to VOCs due to the controllable pore structure. The inevitable presence of water in many sources of VOCs, the competitive adsorption of VOCs molecules and water molecules severely affects the adsorption capacity. The microporous organic polymer is an excellent moisture-resistant VOCs adsorbing material and shows good adsorbing capacity under high humidity.

The synthesis method is the key to the separation performance of the polymer. In 2013, Petal et al (Undredged high-temperature CO) ₂ selectivity in N ₂ -photo nanoporous evaluation organic polymers. Nature communications.2013,4(1): 1357. sup. Astro 1357) studies indicate 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 azo-polymer to CO ₂ Use in capture and separation. The conventional method for preparing azo polymers is to synthesize azo monomers in advance, and then react the azo monomers with certain groups to form azo polymers (CN111303411A, CN 106188387B). However, the method has the disadvantages of complicated reaction process, more reaction components and serious resource waste. At present, methods for in-situ synthesis of azo polymers (CN103936982A and CN108807939A) are mostly used, but the methods require synthesis of metal ion photocatalysts in advance, and have harsh reaction conditions and low conversion rate. This study reports another method of constructing azo polymers with high porosity and significant CO ₂ The absorption capacity.

Disclosure of Invention

The invention aims to provide a preparation method and application of a microporous polymer particle/polymer mixed matrix membrane, which solves the limitation of the existing method for removing organic matters in organic vapor by steam permeation, and increases the flux of VOCs while the prepared separation membrane has better stability.

The object of the invention can be achieved by the following measures:

a method of making a microporous polymer particle/polymer mixed matrix membrane, the method comprising the steps of:

(1) adding an organic solvent into aniline compounds serving as monomers, uniformly mixing for 20-24 hours, and then continuously carrying out polymerization reaction in the organic solvent; filtering the obtained polymer solution, taking precipitate, washing and drying to obtain microporous polymer particles;

(2) and carrying out ultrasonic dispersion on the microporous polymer particles, adding a polymer, dissolving the polymer in an organic solvent, heating to crosslink the polymer to prepare a membrane casting solution, coating the membrane casting solution on a support body after defoaming treatment, and drying to obtain the microporous polymer particle/polymer mixed matrix membrane.

A microporous polymer particle/polymer mixed matrix membrane, the separation membrane being prepared by:

In the separation membrane and the preparation method thereof, 3',5,5' -tetramethyl benzidine, 3 '-diaminobenzidine, 4' -diaminobiphenyl and 4, 4-diaminodiphenyl ether are used as monomers to carry out polymerization reaction under the catalysis condition of cuprous bromide and pyridine. After the reaction, the polymer particles are separated out, further washed and dried, then doped with the polymer which preferentially permeates VOCs, and 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 show that the microporous organic polymer particles have expected hypercrosslinked networks, and the separation membrane prepared by the microporous organic polymer particles has better separation performance and higher flux.

In some specific embodiments: in the step (1), the aniline compound is selected from the group consisting of 3,3',5,5' -tetramethylbenzidine, 3 '-diaminobenzidine, 4' -diaminodiphenyl ether, o-phenylenediamine, 2, 5-dimethyl-p-phenylenediamine, 1, 4-phenylenediamine, m-phenylenediamine, 2-aminobenzonitrile, 3-aminophenol, dichlorobis [ di-t-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-methylcyclohexyl) methyl-4-aminophenyl ether, (3-aminophenoxy) -acetonitrile, 3-aminophenylbenzophenone, 4, 8-dioxadodecane-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' -diaminodiphenylsulfone, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 5-amino-4-imidazolecarboxamide, methyl-ethyl-amide, methyl-4-aminobenzophenone, methyl-ethyl-amide, ethyl-4-amino-phenyl ether, ethyl-4-5-imidazole-amide, ethyl-4-amide, ethyl-4-amide, ethyl-4-amide, ethyl-4-methyl-amide, ethyl-methyl-4-methyl-ethyl-4-ethyl-4-methyl-phenyl ether, ethyl-methyl-4-amino-phenyl ether, 2, 4-diaminodiphenylether, 4-phenyl ether, 2, 4-phenyl ether, 4-bis (3-4-bis (4-diaminodiphenylether, 4-benz-4-benz, 2, and ethyl-benz, 2, 4-bis (4-benz-4-benz-4-benz-4-one, 2,4, 4' -diaminobenzanilide, 2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3, 3-hexafluoropropane, 2' -diaminoethanedioldiphenyl ether, bis (4-amino-2, 3-dichlorophenyl) methane, 1, 8-diamino-3, 6-dioxaoctane, 2, 6-diaminopurine, 1, 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-aminocrotonate), 4' -diaminop-terphenyl, N- (2-ethylamino) -1, 3-propanediamine, bis (3-amino-4-hydroxyphenyl) sulfone, 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane, 2,3,5, 6-tetrafluorop-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, 4-triaminodiphenyl ether, 2 '-diaminoethanediol diphenyl ether, 2-aminodiphenyl ether, neopentyl glycol bis (4-aminophenyl) ether, bis (3-aminopropyl) ether, bis (2-formylphenyl) ether, resorcin diglycidyl ether, 2' -bis (trifluoromethyl) -4,4 '-diaminophenyl ether, 5' - (hexafluoroisopropylidene) diorthotoluidine, di-tert-butyl-phenyl ether, di-n-butyl-ethyl ether, di-n-butyl-ethyl ether, di-n-butyl-ethyl ether, di-amino-phenyl ether, 3, 3-oxybis [5- (trifluoromethyl) aniline ], 2 '-bis (trifluoromethyl) diaminobiphenyl, 2-bis (3-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-methylphenyl) 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, diaminoglyoxaloxime, 3' -diaminodiphenylsulfone, and mixtures thereof, 2, 4-diaminoanisole, 2, 6-diaminopimelic acid, 4' -diaminobenzanilide, 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, 3, 5-diamino-1, 2, 4-triazole, 2, 4-diazepane, 2, 6-diamino-1, 5-triazine, 2, 6-diamino-1, 2, 6-triazoxide, 2, 4-triazoxide, and the like, Any one of 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 '-dimethylaminostyryl, 4' -diamino-2, 2 '-dimethyl-1, 1' -biphenyl, and 2, 4-diaminophenoxy ethanol hydrochloride;

preferably, the following components: the aniline compound is selected from 3,3',5,5' -tetramethyl benzidine, 3' -diaminobenzidine, 4' -diaminobenzidine and 4,4' -diaminodiphenyl ether.

In the step (1), a catalyst is added in the polymerization reaction and uniformly mixed for 20-30 h, wherein the catalyst is any one or two of sodium nitrite, potassium carbonate, gold nanoparticles, 4-dimethylamino pyridine, 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 preferably: the catalyst is cuprous bromide and pyridine in a mass ratio of 1: 3-6.

In a preferable scheme, the mass ratio of the catalyst to the monomer in the step (1) is 1: 0.6-2.0, and the catalyst is cuprous bromide and pyridine and the mass ratio is 1: 3.0-6.0.

The separation membrane and the preparation method of the separation membrane are as follows: 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 one or two of tetrahydrofuran, toluene, chloroform, methanol and acetone; further preferably: the organic solvent is tetrahydrofuran and toluene with the volume ratio of 1-3: 1-3.

The separation membrane and the preparation method of the separation membrane of the invention are as follows: the polymerization reaction temperature is 30-120 ℃, and the reaction time is 20-144 h; preferably, the following components: the polymerization reaction temperature is 60-100 ℃, and the reaction time is 20-84 h; further preferably: the polymerization condition is that the reaction is carried out for 10-14 h under the condition that the temperature is 55-65 ℃, and then the reaction is carried out for 10-14 h under the condition that the temperature is 75-85 ℃; or firstly reacting for 10-14 h at the temperature of 55-65 ℃, and then reacting for 36-72 h at the temperature of 75-85 ℃; or firstly reacting for 10-14 h under the condition of the temperature of 80-100 ℃, and then reacting for 10-14 h under the condition of 100-120 ℃.

The separation membrane and the preparation method of the separation membrane are as follows: the polymer in the step (2) is any one of Polydimethylsiloxane (PDMS), Poly Octyl Methyl Siloxane (POMS), poly trifluoropropyl methyl siloxane (PTFPMS), polyether copolyamide (PEBA), fluorine-containing polymer, polymer with micropores (PIMs) and hyperbranched polymer;

the separation membrane and the preparation method of the separation membrane are as follows: the mass ratio of the microporous polymer particles to the polymer in the step (2) is 1: 0.4-1000.0.

In a preferred embodiment, in the step (2), the mass ratio between the microporous polymer particles and the polymer is 1:0.4 to 1000.0; preferably: the mass ratio between the microporous polymer particles and the polymer is 1: 4.0 to 250; further preferably: the mass ratio between the microporous polymer particles and the polymer is 1: 25 to 110.

The separation membrane and the preparation method of the separation membrane are as follows: carrying out ultrasonic treatment on the microporous polymer particles in the step (2), wherein the treatment time is 0.1-1 h; preferably: the ultrasonic treatment time is 0.3-0.5 h.

The separation membrane and the preparation method of the separation membrane are as follows: 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 following components: 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 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 range is 75-85 ℃, and the heating time is 1-3 h.

The separation membrane and the preparation method of the separation membrane are as follows: the support in the step (2) is selected from an organic material bottom film or an inorganic material bottom 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 embodiments: in the step (2), coating the casting solution on a support, and then drying in an oven to obtain the microporous polymer particle/polymer mixed matrix membrane; wherein the oven is a forced air drying oven.

In the technical scheme of the invention, the drying and solvent removal are carried out by heating to volatilize, the heating temperature is 20-200 ℃, and the following steps are preferred: the heating temperature is 50-80 ℃ below the boiling point temperature of the solvent.

In the technical scheme of the invention, the drying and solvent removal are controlled to be finished within 0.3-48 h, and the preferred volatilization time is 10-15 h.

The separation membrane and the preparation method of the separation membrane are as follows: the microporous polymer particle/polymer mixed matrix membrane is used for separating VOCs (volatile organic compounds)/inert gases, and preferentially permeates VOCs, wherein the VOCs are at least one of alkanes, aromatic hydrocarbons, esters, aldehydes, alcohols and benzene; the feed 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 gauge pressure

Further preferably: the feeding concentration of the raw material side is 2000-30000 ppm, the temperature is 20-80 ℃, and the pressure measured by permeation is 200-1000 Pa gauge pressure.

The beneficial effects of the invention are: the separation membrane prepared by the invention is used for separating C ₂ H ₅ OH/CO ₂ The system has high permeability coefficient and selectivity. The polymer film material has better stability, ductility, thermal stability, chemical stability and excellent solvent resistance. However, the polymer membrane material has certain problems, such as general swelling resistance, general gas separation selectivity and the phenomenon of mutual balance between gas permeability coefficient and selectivity. The invention introduces microporous polymer particles, meets the requirement of the polymer membrane on the separation of VOCs, improves the flux and the selectivity of the VOCs, can achieve the treatment effect by less membrane area under the condition of the same unit treatment capacity, improves the efficiency and reduces the investment cost.

Drawings

FIG. 1 is a FT-IR diagram of a polymer powder in example 1 of the present invention;

FIG. 2 is an electron micrograph of a polymer powder in example 1 of the present invention;

FIG. 3 is a surface view of a microporous polymer particle/PDMS mixed matrix membrane in example 1 of the present invention;

FIG. 4 is a cross-sectional view of a microporous polymer particle/PDMS mixed matrix membrane in example 1 of the present invention.

Detailed Description

The invention is further illustrated by the following examples, without limiting the scope of the invention:

the flux (J) calculation for the microporous polymer particle/polymer mixed matrix membrane is as follows:

wherein W is the mass (g) of the permeating component, A is the effective area (m) of the membrane ² ) And t is the time interval(s) of the permeation process.

The permeability coefficient of the microporous polymer particle/polymer mixed matrix membrane is calculated as follows:

wherein: l is the thickness (cm) of the film, X _feed And X _perm The molar fractions of the i components, J, measured by raw material and by permeation, respectively _i Is the permeation flux of the i component, P _feed And P _perm The pressure (cmHg) measured for the feed and for the permeate, respectively.

The selectivity calculation for the microporous polymer particle/polymer mixed matrix membrane is as follows:

wherein: p _voc And P _CO2 Respectively corresponding to VOC and CO ₂ Permeability coefficient of (a).

The separation factor calculation formula for the microporous polymer particle/polymer mixed matrix membrane is as follows:

wherein: x _feed And X _perm The molar fractions of the i components are measured for the feed and for the permeate, respectively.

Example 1

1g of 3,3',5,5' -tetramethylbenzidine was added to 220mL of a tetrahydrofuran/toluene (v/v ═ 1:1) solvent mixture. Cuprous bromide (0.235 g) and pyridine (0.94 g) were added. The resulting mixture was stirred at room temperature under an air atmosphere for 24h, at 60 ℃ for 12h and then at 80 ℃ for 12 h. 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 further washed with water and ethanol. Drying in a vacuum drying oven at 110 deg.C for 12h to obtain polymer powder, as shown in FIG. 1 and FIG. 2.

Taking 0.005g of polymer powder, dispersing in 20g of n-heptane, carrying out ultrasonic treatment for 0.5h, adding 0.995g of PDMSand 29g of n-heptane, stirring for 0.5h at room temperature, and then stirring for 2h at 80 ℃ to obtain a casting solution. The obtained casting solution was coated on a teflon support, left to stand at room temperature for 3 hours, and then dried in a forced air drying oven at 80 ℃ for 12 hours to obtain a microporous polymer particle/PDMS mixed matrix membrane, as shown in fig. 3 and 4.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is always maintained at about 200 pa. After membrane separation, the ethanol concentration 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',5,5' -tetramethylbenzidine was added to 220mL of a tetrahydrofuran/toluene (v/v ═ 1:1) solvent mixture. Cuprous bromide (0.235 g) and pyridine (0.94 g) were added. The resulting mixture was stirred at room temperature under an air atmosphere for 24h, at 60 ℃ for 12h and then at 80 ℃ for 12 h. 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 further washed with water and ethanol. Drying in a vacuum drying oven at 110 deg.C for 12 h.

Taking 0.01g of polymer powder, dispersing in 20g of n-heptane, carrying out ultrasonic treatment for 0.5h, adding 0.99g of PDMSand 29g of n-heptane, stirring at room temperature for 0.5h, and then stirring at 80 ℃ for 2h to obtain a casting solution. And coating the obtained casting solution on a polytetrafluoroethylene support, standing for 3h at room temperature, and then drying for 12h in a forced air drying oven at the temperature of 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix membrane.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is 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 permeability of 30074barrer and a selectivity of 15.93 for ethanol.

Example 3

Taking 0.015g of polymer powder, dispersing the polymer powder in 20g of n-heptane, carrying out ultrasonic treatment for 0.5h, adding 0.985g of PDMS and 29g of n-heptane, stirring for 0.5h at room temperature, and then stirring for 2h at 80 ℃ to obtain a casting solution. And coating the obtained casting solution on a polytetrafluoroethylene support, standing for 3h at room temperature, and then drying for 12h in a forced air drying oven at the temperature of 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix membrane.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ Separation Performance of the SystemThe effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 27889ppm on the permeate side, the permeability of ethanol was 29323barrer, and the selectivity was 15.05.

Example 4

Taking 0.02g of polymer powder, dispersing in 20g of n-heptane, carrying out ultrasonic treatment for 0.5h, adding 0.98g of PDMSs and 29g of n-heptane, stirring for 0.5h at room temperature, and then stirring for 2h at 80 ℃ to obtain a casting solution. And coating the obtained casting solution on a polytetrafluoroethylene support, standing for 3h at room temperature, and then drying for 12h in a forced air drying oven at the temperature of 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix membrane.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 26849ppm on the permeate side, the permeability of ethanol was 31184barrer, and the selectivity was 14.44.

Example 5

Taking 0.03g of polymer powder, dispersing the polymer powder in 20g of n-heptane, carrying out ultrasonic treatment for 0.5h, adding 0.97g of PDMSand 29g of n-heptane, stirring at room temperature for 0.5h, and then stirring at 80 ℃ for 2h to obtain a casting solution. And coating the obtained casting solution on a polytetrafluoroethylene support, standing for 3h at room temperature, and then drying for 12h in a forced air drying oven at the temperature of 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix membrane.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 27033ppm on the permeate side, the permeability of ethanol was 28380barrer, and the selectivity was 14.55.

Example 6

1g of 3,3' -diaminobenzidine was 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 at room temperature under an air atmosphere for 24h, at 60 ℃ for 12h and then at 80 ℃ for 12 h. 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 further washed with water and ethanol. Drying in a vacuum drying oven at 110 deg.C for 12 h.

Test the present exampleTo the composite film of C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 13270ppm on the permeate side, the ethanol permeability was 22694barrer, and the selectivity was 6.8.

Example 7

1g of 3,3' -diaminobenzidine was added to 220mL of a tetrahydrofuran/toluene (v/v ═ 1:1) solvent mixture. Cuprous bromide (0.235 g) and pyridine (0.94 g) were added. The resulting mixture was stirred at room temperature under an air atmosphere for 24h, at 60 ℃ for 12h and then at 80 ℃ for 12 h. 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 further washed with water and ethanol. Drying in a vacuum drying oven at 110 deg.C for 12 h.

Test 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 is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 17587ppm on the permeate side, the permeability of ethanol was 35388barrer, and the selectivity was 9.2.

Example 8

1g of 4,4' -diaminobenzidine was 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 at room temperature under an air atmosphere for 24h, at 60 ℃ for 12h and then at 80 ℃ for 12 h. 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 further washed with water and ethanol. Drying in a vacuum drying oven at 110 deg.C for 12 h.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 17971ppm on the permeate side, with a permeability of 50419barrer and a selectivity of 9.41.

Example 9

1g of 4,4' -diaminodiphenyl ether was 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 at room temperature under an air atmosphere for 24h, at 60 ℃ for 12h and then at 80 ℃ for 12 h. 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 further washed with water and ethanol. Drying in a vacuum drying oven at 110 deg.C for 12 h.

Taking 0.01g of polymer powder, dispersing in 20g of n-heptane, carrying out ultrasonic treatment for 0.5h, adding 0.99g of PDMSand 29g of n-heptane, stirring at room temperature for 0.5h, and then stirring at 80 ℃ for 2h to obtain a casting solution. And coating the obtained membrane casting solution on a polytetrafluoroethylene support, standing for 3h at room temperature, and then drying for 12h in a forced air drying oven at the temperature of 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix membrane.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is always maintained at about 200 pa. After membrane separation, the ethanol concentration 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',5,5' -tetramethylbenzidine was added to 220mL of a toluene solvent. Cuprous bromide (0.235 g) and pyridine (0.94 g) were added. The resulting mixture was stirred at room temperature under an air atmosphere for 24h, at 60 ℃ for 12h and then at 80 ℃ for 12 h. 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 further washed with water and ethanol. Drying in a vacuum drying oven at 110 deg.C for 12 h.

Taking 0.01g of polymer powder, dispersing the polymer powder in 20g of n-heptane, carrying out ultrasonic treatment for 0.5h, adding 0.99g of PDMSand 29g of n-heptane, stirring for 0.5h at room temperature, and then stirring for 2h at 80 ℃ to obtain a casting solution. And coating the obtained casting solution on a polytetrafluoroethylene support, standing for 3h at room temperature, and then drying for 12h in a forced air drying oven at the temperature of 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix membrane.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 27033ppm on the permeate side, with a permeability of 50434barrer and a selectivity of 11.87 for ethanol.

Example 11

1g of 3,3',5,5' -tetramethylbenzidine was added to 220mL of a tetrahydrofuran/toluene (v/v ═ 1:1) solvent mixture. Cuprous bromide (0.235 g) and pyridine (1.2 g) were added. The resulting mixture was stirred at room temperature under an air atmosphere for 24h, at 60 ℃ for 12h and then at 80 ℃ for 12 h. 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 further washed with water and ethanol. Drying in a vacuum drying oven at 110 deg.C for 12 h.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 27033ppm on the permeate side, the permeability of ethanol was 30433barrer, and the selectivity was 15.36.

Example 12

1g of 3,3',5,5' -tetramethylbenzidine was added to 220mL of a tetrahydrofuran/toluene (v/v ═ 1:1) solvent mixture. Cuprous bromide (0.235 g) and pyridine (0.94 g) were added. The resulting mixture was stirred at room temperature under an air atmosphere for 24h, at 60 ℃ for 12h and then at 80 ℃ for 36 h. 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 further washed with water and ethanol. Drying in a vacuum drying oven at 110 deg.C for 12 h.

Taking 0.01g of polymer powder, dispersing the polymer powder in 20g of n-heptane, carrying out ultrasonic treatment for 0.5h, adding 0.99g of PDMSand 29g of n-heptane, stirring for 0.5h at room temperature, and then stirring for 2h at 80 ℃ to obtain a casting solution. And coating the obtained membrane casting solution on a polytetrafluoroethylene support, standing for 3h at room temperature, and then drying for 12h in a forced air drying oven at the temperature of 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix membrane.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 27033ppm on the permeate side, the permeability of the ethanol was 29987barrer, and the selectivity was 15.88.

Example 13

1g of 3,3',5,5' -tetramethylbenzidine was added to 220mL of a tetrahydrofuran/toluene (v/v ═ 1:1) solvent mixture. Cuprous bromide (0.235 g) and pyridine (0.94 g) were added. The resulting mixture was stirred at room temperature under an air atmosphere for 24h, at 60 ℃ for 12h and then at 80 ℃ for 72 h. 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 further washed with water and ethanol. Drying in a vacuum drying oven at 110 deg.C for 12 h.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ Separation performance of the system, effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 27033ppm on the permeate side, the permeability of ethanol was 30104barrer, and the selectivity was 16.

Example 14

1g of 3,3',5,5' -tetramethylbenzidine was added to 220mL of a tetrahydrofuran/toluene (v/v ═ 1:1) solvent mixture. Cuprous bromide (0.235 g) and pyridine (0.94 g) were added. The resulting mixture was stirred at room temperature under an air atmosphere for 24h, at 80 ℃ for 12h and then at 100 ℃ for 12 h. 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 further washed with water and ethanol. Drying in a vacuum drying oven at 110 deg.C for 12 h.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 26849ppm on the permeate side, the permeability of ethanol was 30184barrer, and the selectivity was 15.79.

Example 15

1g of 3,3',5,5' -tetramethylbenzidine was added to 220mL of a tetrahydrofuran/toluene (v/v ═ 1:1) solvent mixture. Cuprous bromide (0.235 g) and pyridine (0.94 g) were added. The resulting mixture was stirred at room temperature under an air atmosphere for 24h, at 100 ℃ for 12h and then at 120 ℃ for 12 h. 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 further washed with water and ethanol. Drying in a vacuum drying oven at 110 deg.C for 12 h.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 26849ppm on the permeate side, with a permeability of 30786barrer and a selectivity of 15.9 for ethanol.

Example 16

1g of 3,3',5,5' -tetramethylbenzidine was 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 at room temperature under an air atmosphere for 24h, at 60 ℃ for 12h and then at 80 ℃ for 12 h. 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 further washed with water and ethanol. Drying in a vacuum drying oven at 110 deg.C for 12 h.

Test the composite film obtained in this example for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 5000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is 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, the ethanol permeability was 18242barrer, and the selectivity was 9.77.

Example 17

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The measured concentration of the raw material is 8000ppm, the temperature is 30 ℃, the permeation measurement provides pressure through a vacuum pump, and the pressure (gauge pressure) of the permeation measurement is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 8000ppm on the feed side to 56208ppm on the permeate side, the ethanol permeability was 13702barrer, and the selectivity was 7.36.

Example 18

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The measured concentration of the raw material is 12000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation measurement, and the pressure (gauge pressure) in the permeation measurement is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 12000ppm on the feed side to 93727ppm on the permeate side, the permeability of ethanol was 15815barrer, and the selectivity was 8.74.

Example 19

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of raw material is 17000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in permeation measurement, and the pressure (gauge pressure) in permeation measurement is always maintained at about 200 pa. After membrane separation, the ethanol concentration is from the raw material side17000ppm rose to 80808ppm on the permeate side, the permeability of ethanol was 9784barrer, and the selectivity was 5.15.

Example 20

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ Separation performance of the system, effective area of the polymer film is 10cm ² The measured concentration of the raw material is 21000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation measurement, and the pressure (gauge pressure) in the permeation measurement is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 21000ppm on the feed side to 10060ppm on the permeate side, the permeability of ethanol was 9663barrer, and the selectivity was 5.29.

Example 21

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ Separation performance of the system, effective area of the polymer film is 10cm ² The measured concentration of the raw material is 24000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation measurement, and the pressure (gauge pressure) in the permeation measurement is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 24000ppm on the feed side to 11589ppm on the permeate side, the permeability of ethanol was 9981barrer, and the selectivity was 5.41.

Example 22

1g of 3,3',5,5' -tetramethylbenzidine was 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 at room temperature under an air atmosphere for 24h, at 60 ℃ for 12h, and then at 80 ℃ for 12 h. 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 further washed with water and ethanol. Drying in a vacuum drying oven at 110 deg.C for 12 h.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The raw material concentration is 2000ppm, the temperature is 20 ℃, the infiltration measurement provides pressure through a vacuum pump, and the infiltration measurementThe pressure (gauge pressure) of (2) is 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, the permeability of ethanol was 40670barrer, and the selectivity was 19.81.

Example 23

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 40 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is 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 permeability of 26678barrer and a selectivity of 15.13 for ethanol.

Example 24

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 50 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is 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, the permeability of ethanol was 25347barrer, and the selectivity was 14.13.

Example 25

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² Original sourceThe concentration measured by material is 2000ppm, the temperature is 60 ℃, the pressure is provided by a vacuum pump in the permeation measurement, and the pressure (gauge pressure) in the permeation measurement is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 18000ppm on the permeate side, the permeability of the ethanol was 21928barrer, and the selectivity was 11.92.

Example 26

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The measured concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation measurement, and the pressure (gauge pressure) in the permeation measurement is always maintained at about 600 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 25919ppm on the permeate side, the permeability of the ethanol was 26776barrer, and the selectivity was 14.2.

Example 27

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is always maintained at about 800 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 21327ppm on the permeate side, the permeability of ethanol was 21714barrer, and the selectivity was 11.79.

Example 28

1g of 3,3',5,5' -tetramethylbenzidine was added to 220mL of a tetrahydrofuran/toluene (v/v ═ 1:1) solvent mixture. Cuprous bromide (0.235 g) and pyridine (0.94 g) were added. The resulting mixture was stirred at room temperature under an air atmosphere for 24h, at 60 ℃ for 12h, and then at 80 ℃ for 12 h. 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 further washed with water and ethanol. Drying in a vacuum drying oven at 110 deg.C for 12 h.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The measured concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation measurement, and the pressure (gauge pressure) in the permeation measurement is always maintained at about 1000 pa. After membrane separation, the ethanol concentration increased from 2000ppm on the feed side to 18747ppm on the permeate side, the permeability of ethanol was 20373barrer, and the selectivity was 10.39.

Example 29

Taking 0.01g of polymer powder, dispersing in 20g of n-butyl alcohol, carrying out ultrasonic treatment for 0.5h, adding PEBA25330.99g and 29g of n-butyl alcohol, stirring for 0.5h at room temperature, and then stirring for 2h at 80 ℃ to obtain a casting solution. And coating the obtained casting solution on a polytetrafluoroethylene support, standing for 3h at room temperature, and then drying for 12h in a forced air drying oven at the temperature of 80 ℃ to obtain the microporous polymer particle/PEBA mixed matrix membrane.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is 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, the permeability of ethanol was 6756.3barrer, and the selectivity was 10.89.

Example 30

Taking 0.01g of polymer powder, dispersing the polymer powder in 20g of n-heptane, carrying out ultrasonic treatment for 0.5h, adding 0.99g of PDMS and 29g of n-heptane, stirring the mixture at room temperature for 0.5h, and then stirring the mixture at 80 ℃ for 2h to obtain a casting solution. And coating the obtained casting solution on a polytetrafluoroethylene support, standing for 3h at room temperature, and then drying for 12h in a forced air drying oven at the temperature of 80 ℃ to obtain the microporous polymer particle/PDMS mixed matrix membrane.

The composite films obtained in this example were tested for C ₂ H ₅ OH/N ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is 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, the permeability of the ethanol was 9327.03barrer, and the selectivity was 38.8.

Example 31

The composite films obtained in this example were tested for C ₂ H ₅ OH/N ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The measured concentration of the raw material is 20000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation measurement, and the pressure (gauge pressure) in the permeation measurement is always maintained at about 200 pa. After membrane separation, the ethanol concentration increased from 20000ppm on the feed side to 47799ppm on the permeate side, the ethanol permeability was 12934barrer, and the selectivity was 49.9.

Example 32

1g of PDMS and 50g of n-heptane are taken and stirred for 0.5h at room temperature and then for 2h at 80 ℃ to obtain the membrane casting solution. And coating the obtained casting solution on a polytetrafluoroethylene support, standing at room temperature for 3h, and then drying in a forced air drying oven at 80 ℃ for 12h to obtain the PDMS membrane.

The composite films obtained in this example were tested for C ₂ H ₅ OH/CO ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is 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, the permeability of the ethanol was 20124barrer, and the selectivity was 7.76.

Example 33

Test the composite film obtained in this example for C ₂ H ₅ OH/N ₂ The separation performance of the system, the effective area of the polymer film is 10cm ² The concentration of the raw material is 2000ppm, the temperature is 30 ℃, the pressure is provided by a vacuum pump in the permeation test, and the pressure (gauge pressure) in the permeation test is 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, the ethanol permeability was 13734barrer, and the selectivity was32。

Claims

1. A method of making a microporous polymer particle/polymer mixed matrix membrane, comprising: the method comprises the following steps:

2. The method of claim 1, wherein: in the step (1), the aniline compound is selected from the group consisting of 3,3',5,5' -tetramethylbenzidine, 3 '-diaminobenzidine, 4' -diaminodiphenyl ether, o-phenylenediamine, 2, 5-dimethyl-p-phenylenediamine, 1, 4-phenylenediamine, m-phenylenediamine, 2-aminobenzonitrile, 3-aminophenol, dichlorobis [ di-t-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-methylcyclohexyl) methyl-4-aminophenyl ether, (3-aminophenoxy) -acetonitrile, 3-aminophenylbenzophenone, 4, 8-dioxadodecane-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' -diaminodiphenylsulfone, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 5-amino-4-imidazolecarboxamide, methyl-ethyl-amide, methyl-4-aminobenzophenone, methyl-ethyl-amide, ethyl-4-amino-phenyl ether, ethyl-4-5-imidazole-amide, ethyl-4-amide, ethyl-4-amide, ethyl-4-amide, ethyl-4-methyl-amide, ethyl-methyl-4-methyl-ethyl-4-ethyl-4-methyl-phenyl ether, ethyl-methyl-4-amino-phenyl ether, 2, 4-diaminodiphenylether, 4-phenyl ether, 2, 4-phenyl ether, 4-bis (3-4-bis (4-diaminodiphenylether, 4-benz-4-benz, 2, and ethyl-benz, 2, 4-bis (4-benz-4-benz-4-benz-4-one, 2,4, 4' -diaminobenzanilide, 2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3, 3-hexafluoropropane, 2' -diaminoethanediol diphenyl ether, bis (4-amino-2, 3-dichlorophenyl) methane, 1, 8-diamino-3, 6-dioxaoctane, 2, 6-diaminopurine, 1, 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-aminocrotonate), 4' -diaminop-terphenyl, N- (2-ethylamino) -1, 3-propanediamine, bis (3-amino-4-hydroxyphenyl) sulfone, 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane, 2,3,5, 6-tetrafluorop-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, 4-triaminodiphenyl ether, 2 '-diaminoethanediol diphenyl ether, 2-aminodiphenyl ether, neopentylglycol bis (4-aminophenyl) ether, bis (3-aminopropyl) ether, bis (2-formylphenyl) ether, resorcinoldiglycidyl ether, 2' -bis (trifluoromethyl) -4,4 '-diaminophenyl ether, 5' - (hexafluoroisopropylidene) diorthotoluidine, 3, 3-oxybis [5- (trifluoromethyl) aniline ], 2 '-bis (trifluoromethyl) diaminobiphenyl, 2-bis (3-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-methylphenyl) 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, diaminoglyoxaloxime, 3' -diaminodiphenylsulfone, 2, 4-diaminoanisole, 2, 6-diaminopimelic acid, 4' -diaminobenzanilide, 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, 3, 5-diamino-1, 2, 4-triazole, triazole, Any one of 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 '-dimethylaminostyryl, 4' -diamino-2, 2 '-dimethyl-1, 1' -biphenyl, and 2, 4-diaminophenoxy ethanol hydrochloride;

preferably: the aniline compound is selected from 3,3',5,5' -tetramethyl benzidine, 3' -diaminobenzidine, 4' -diaminobenzidine and 4,4' -diaminodiphenyl ether.

3. The method of claim 1, wherein: in the step (1), a catalyst is added in the polymerization reaction and uniformly mixed for 20-30 h, wherein the catalyst is any one or two of sodium nitrite, potassium carbonate, gold nanoparticles, 4-dimethylamino pyridine, 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;

4. The method of claim 1, 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 one or two of tetrahydrofuran, toluene, chloroform, methanol and acetone; further preferably: the organic solvent is tetrahydrofuran and toluene with the volume ratio of 1-3: 1-3.

5. The preparation method according to claim 1, wherein in the step (1), the polymerization reaction temperature is 30-120 ℃, and the reaction time is 20-144 h; preferably, the following components: the polymerization reaction temperature is 60-100 ℃, and the reaction time is 20-84 h; further preferably: the polymerization condition is that the reaction is carried out for 10-14 h under the condition that the temperature is 55-65 ℃, and then the reaction is carried out for 10-14 h under the condition that the temperature is 75-85 ℃; or firstly reacting for 10-14 h at the temperature of 55-65 ℃, and then reacting for 36-72 h at the temperature of 75-85 ℃; or firstly reacting for 10-14 h under the condition of the temperature of 80-100 ℃, and then reacting for 10-14 h under the condition of 100-120 ℃.

6. The method according to claim 1, wherein in the step (2), the polymer is any one of Polydimethylsiloxane (PDMS), Poly Octyl Methyl Siloxane (POMS), poly trifluoropropyl methyl siloxane (PTFPMS), polyether copolyamide (PEBA), fluoropolymer, polymers with micropores (PIMs) and hyperbranched polymers.

7. The method according to claim 1, wherein in the step (2), the mass ratio between the microporous polymer particles and the polymer is 1:0.4 to 1000.0; preferably: the mass ratio between the microporous polymer particles and the polymer is 1: 4.0 to 250; further preferably: the mass ratio of the microporous polymer particles to the polymer is 1: 25 to 110.

8. The method according to claim 1, wherein in the step (2), the organic solvent is any one of n-hexane, n-heptane, toluene, tetrahydrofuran, chloroform, methanol, acetone, methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, 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.

9. The method of claim 1, wherein: in the step (2), the concentration of the casting solution is 0.5-80 wt%, and the heating temperature is 20-180 ℃; the concentration of the casting solution is preferably 1-15 wt%, the heating temperature is 75-85 ℃, and the heating time is 1-3 h.

The support body is selected from an organic material bottom film or an inorganic material bottom film; preferably, the following components: the support is selected from any one of polytetrafluoroethylene, polyamide, cellulose acetate, ceramic, silicon carbide, alumina, polyvinylidene fluoride and polyacrylonitrile.

10. The method of claim 1, wherein: the microporous polymer particle/polymer mixed matrix membrane is used for separating VOCs/inert gases, and the VOCs preferentially permeate through the microporous polymer particle/polymer mixed matrix membrane, and the VOCs are at least one of alkanes, aromatics, esters, aldehydes, alcohols and benzene; the feed 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 gauge pressure

Further preferably: the feeding concentration of the raw material side is 2000-30000 ppm, the temperature is 20-80 ℃, and the pressure of permeation measurement is 200-1000 Pa.