CN114177744A - Trapezoidal polymer with micropores for gas separation, membrane and application - Google Patents
Trapezoidal polymer with micropores for gas separation, membrane and application Download PDFInfo
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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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
Abstract
The invention relates to a trapezoidal polymer with micropores for gas separation, a membrane and application. The self-microporous ladder polymer for gas separation has a structure of formula (I): in the formula (I), R1Is selected from Ra、Rb、Rc、RdAny one of the groups or a combination of at least two of the groups; r2Is selected from Re、Rf、Rg、RhAny one of the groups or a combination of at least two of the groups; n is a positive integer not less than 20. Self-microporous ladder polymer for gas separation provided by the application to CO2The gas permeability is good, and the selectivity is high; meanwhile, the ladder-shaped material with micropores for gas separation provided by the application has good solubility in an organic solvent, so that the processability is good, and a film forming process is realizedSimple and easy to use.
Description
Technical Field
The invention belongs to the field of gas separation membranes, and particularly relates to a trapezoidal polymer with micropores for gas separation, a membrane and application, in particular to a trapezoidal polymer with micropores for gas separation, a flat membrane for gas separation, a hollow fiber membrane for gas separation and application.
Background
Carbon dioxide is the major anthropogenic greenhouse gas, accounting for 77% of anthropogenic greenhouse gas emissions (accounting for 26% to 30% of all carbon dioxide emissions) over the last decade. The main artificial emission of carbon dioxide comes from the combustion of fossil fuels, the concentration of carbon dioxide in flue gases depends on the fuel, such as coal (12-15 mol% CO)2) And natural gas (3-4 mol% CO)2) (ii) a In petroleum and other industrial plants, the concentration of carbon dioxide in the exhaust gas is determined by the refinery (8-9 mol% CO)2) And cement production (14-33 mol% CO)2) And iron and steel production (20-44 mol% CO)2) And the like. Scientists generally believe that to control the global average air temperature to within 1.5 c of the pre-industrial baseline, i.e., a "safe" level of warming, humans must stabilize the atmospheric carbon dioxide concentration to around 350 ppm. However, as of 2019, the level of carbon dioxide in the atmosphere has reached about 410 ppm, and in order to improve the current situation, new materials and new technologies must be developed to remove carbon dioxide from the atmosphere in addition to reducing the amount of fossil fuel combustion and reducing carbon dioxide emission.
The gas separation membrane technology is a pressure-driven phase-change-free gas separation process, and has the advantages of high energy efficiency, small occupied area, simple and convenient equipment, easy regulation and control, greenness, no pollution and the like. The core of the gas separation membrane technology is a membrane material, a high-performance membrane material is a key for realizing high-efficiency and low-cost gas separation, and an ideal gas separation membrane material generally needs to have high gas permeability and separation selectivity at the same time, and also needs to have excellent mechanical strength, good processability and membrane stability. Although the gas separation membrane has a wide application prospect, the gas permeability of the current commercialized membrane materials, such as polyimide, polyethersulfone, acetate fiber and the like, is often very low, and the requirement of low-cost gas separation is difficult to meet, so that the development of novel high-performance membrane materials is the key point of research in the field of the current gas separation membranes.
Self-microporous Polymers (PIMs) are a class of microporous polymers with high specific surface area, and polymer chain segments cannot be effectively stacked due to the existence of rigid and twisted structures in the molecules, so that a large number of micropores (the vast majority of pore channel sizes are below 2 nm) are generated, and a very good channel is provided for gas transmission. Since the 2004 PIM-1 was made available and used for gas separation, more and more PIMs were developed and used in gas separation membranes.
Chinese patent CN105413412A prepares a self-crosslinkable self-microporous polymer gas separation membrane by introducing bromine substituent and azide substituent, and the crosslinking is carried out after the self-crosslinkable self-microporous polymer gas separation membrane is subjected to high-pressure CO2The mixed gas has better plasticizing resistance, but the preparation process is complex and the raw materials are expensive. Chinese patent CN109311899A prepared a polymer membrane based on a terogel base and used for gas separation, and the series of polymer membranes have excellent gas separation performance, but poor solubility and poor processability. Chinese patent CN112646170A discloses a chiral self-microporous polymer and a preparation method thereof, and the chiral self-microporous polymer is applied to gas separation, and the material has good gas separation performance after methanol is aged, but has low gas permeability before treatment. The existing reported self-microporous polymer is usually complicated in synthesis steps, the gas separation performance needs to be further improved, and no patent report of preparing a self-microporous polymer gas separation membrane through a superacid catalysis friedel-crafts reaction is found.
The application needs to provide a simple preparation process and CO2High selectivity and strong permeability.
Disclosure of Invention
In view of the deficiencies of the prior art, the present invention discloses a self-microporous ladder polymer for gas separation, which has a structure of formula (I):
In the formula (I), R1Is selected from Ra、Rb、Rc、RdAny one of the groups or a combination of at least two of the groups; r2Is selected from Re、Rf、Rg、RhAny one of the groups or a combination of at least two of the groups; n is a positive integer ≧ 20 (e.g., 21, 22, 24, 26, 28, 30, 35, 40, 45, 50, 56, 60, 67, 75, 78, 80, 85, 88, 90, 95, 98, etc.).
The polymer provided by the application utilizes a pterene or spiroaromatic compound as a polymerization monomer to polymerize with another polymerization monomer trifluoromethyl compound to obtain a self-micropore ladder-shaped polymer for gas separation, and the material has high free volume content and can simultaneously carry out CO separation2Has high solubility, and thus exhibits high CO content2Permeability; and for other gases (e.g. N)2、CH4Etc.) due to poor solubility, inappropriate pore size, and low permeability, the self-supporting microporous ladder polymer provided by the present application is directed to CO2The gas and other gases have obvious permeability difference, and good CO can be obtained2The separation effect of (1).
In addition, the material that this application provided is trapezoidal polymer (the banded macromolecular chain that is produced by two above single chains are continuous, and the structure is similar to the polymer of trapezoidal), compares in single chain structure, and trapezoidal structure rigidity is better, and the polymer chain segment can not effectively pile up to produce a large amount of micropores, provide a very good passageway for gas transmission.
Especially for RaAnd RcThe structure of the pterenes is more suitable for the accumulation pore channel, and CO is2Higher permeability of gas and better selectivity for RbSpiro aromatic structure of (i), then CO2The selectivity of the gas is higher.
Preferably, n in the formula (I) is an integer between 20 and 100.
The n value is too low (lower than 20), the molecular weight of the self-micropore ladder-shaped polymer is low, and the film forming property is poor; too high n (above 100) may affect the solubility of the polymer with micropores, and the film-forming process is more complicated.
It is another object of the present invention to provide a process for the preparation of the inventive ladder-shaped microporous polymer for gas separation, comprising the steps of:
(1) dissolving a monomer A containing dihydroxy function and a monomer B containing trifluoromethyl ketone in a solvent C, adding a superacid catalyst after the monomers A and B are completely dissolved, and reacting to obtain a viscous polymer solution;
wherein the functional monomer A containing the dihydroxy comprises Ma、Mb、Mc、MdAny one or a combination of at least two of the above, wherein the trifluoromethyl ketone-containing monomer B is Me、Mf、Mg、MhAny one or a combination of at least two of;
(2) and (2) adding an excessive precipitator D into the polymer solution obtained in the step (1), then washing and filtering, refluxing in the precipitator for 3 times, filtering, and drying a solid sample to obtain the trapezoidal polymer with micropores for gas separation.
Preferably, the super acid catalyst comprises trifluoromethanesulfonic acid and/or methanesulfonic acid.
Preferably, the solvent C comprises a chlorinated organic solvent, preferably comprising dichloromethane and/or trichloromethane.
Preferably, the reaction temperature in the step (1) is 0-50 ℃, the reaction time is 6-72 h (for example, 7 h, 8h, 12 h, 15 h, 18 h, 22 h, 26 h, 30 h, 35 h, 38 h, 40 h, 44 h, 46 h, 48h, 52 h, 56 h, 58 h, 65 h, 68 h, 70 h, etc.), the reaction temperature is 0-50 ℃, and the reaction time is 45-60 h.
Preferably, the ratio of the dihydroxy functional monomer A and the trifluoromethyl ketone monomer B added in step (1) is 0.65-0.8 (e.g., 0.66, 0.67, 0.69, 0.72, 0.75, 0.78, etc.), preferably 0.7-0.75.
Preferably, the amount of the superacid catalyst added in the step (1) is 4 to 10 times (e.g., 5 times, 7 times, 9 times, etc.) of the dihydroxy functional monomer a.
Preferably, in the polymer solution in the step (1), the sum of the masses of the dihydroxy functional monomer A and the trifluoromethyl ketone monomer B added per 100mL of the solvent C is 25-50 g (for example, 26 g, 28 g, 30 g, 32 g, 35 g, 38 g, 40 g, 44 g, 48 g, etc.).
Preferably, the precipitating agent D comprises methanol and/or ethanol.
The addition amount of the precipitant D in the step (2) is 5-20 g of the polymer solution obtained in the step (1) per 100mL of the precipitant D.
Preferably, the temperature of the washing and filtering in the step (2) is 45-55 ℃.
Preferably, the drying in the step (2) is carried out at 100-150 ℃ in vacuum.
The reaction conditions in the step (1) can improve the speed of the main reaction and reduce the occurrence of side reactions; the treatment conditions of step (2) can improve the purity of the polymer.
It is another object of the present invention to provide a flat membrane for gas separation, which is prepared by a method comprising the steps of:
(a) dispersing the ladder-shaped polymer with the micropores for gas separation in a dispersing solvent to obtain a coating solution;
(b) and coating the coating liquid on a substrate, and drying to obtain the flat membrane.
Preferably, the dispersing solvent comprises a chlorinated organic solvent, preferably comprising dichloromethane and/or trichloromethane.
Preferably, in the coating solution, the dispersion concentration of the self-microporous trapezoidal polymer for gas separation is 3-6 wt%.
Preferably, the substrate is any one of a quartz plate, a glass plate, a metal plate, or a combination of at least two of them.
Preferably, the amount of coating is per 100 cm2Coating 0.6-0.8 g of polymer material.
The fourth object of the present invention is to provide a hollow fiber membrane for gas separation, which is prepared by a method comprising the steps of:
(A) dispersing the self-micropore ladder-shaped polymer for gas separation in a dispersion solvent to obtain spinning solution;
(B) spinning the spinning solution to obtain a hollow fiber membrane;
preferably, the dispersing solvent comprises an organic solvent, preferably comprising tetrahydrofuran,N,N-dimethylacetamide and ethanol.
Preferably, the dispersion concentration of the self-contained micro-porous ladder-shaped polymer for gas separation in the spinning solution is 15-30 wt%.
The fifth object of the present invention is to provide a flat membrane for gas separation of the third object or a hollow fiber membrane for gas separation of the fourth object, the flat membrane and/or the hollow fiber membrane being used for CO2Trapping and separating;
preferably, the polymer film and/or the hollow fiber membrane are used for removing CO from air2CO in flue gas2Any one of trapping, natural gas purification, air separation, hydrogen separation, and natural gas stripping of helium.
Compared with the prior art, the method has the following beneficial effects:
self-microporous ladder polymer for gas separation provided by the application to CO2The gas permeability is good, and the selectivity is high; meanwhile, the self-micropore ladder-shaped polymer for gas separation has good solubility in an organic solvent, so that the processability is good, the film forming process is simple, and the use is easier.
Drawings
FIG. 1 shows nuclear magnetic hydrogen spectrum of polymer I with micropores and trapezoids;
FIG. 2 shows the IR spectrum of polymer I with micropores.
Detailed Description
The technical solution of the present invention is further explained with reference to the following embodiments, but it should be noted that the embodiments are only an embodiment and explanation of the technical solution of the present invention, and should not be construed as a limitation to the scope of the present invention.
The reagents and instruments used in the examples are commercially available and the detection methods are conventional methods well known in the art.
Example 1
A self-contained microporous ladder polymer for gas separation is prepared by the following steps:
(1) adding 4.87 g of 2, 6-dihydroxytriptycene (17 mmol) and 4.18 g of trifluoro acetophenone (24 mmol) into a 250 mL single-neck flask with a magnetic stirrer, adding 32 mL of anhydrous dichloromethane, adding 8.18 mL of trifluoromethanesulfonic acid (92.4 mmol) after the monomers are dissolved by stirring in an ice water bath, removing the ice water bath, and stirring at room temperature for 48 hours until viscous colloid is precipitated out from the solution;
(2) slowly pouring the viscous liquid obtained in the step (1) into stirred 100mL of methanol, washing and filtering for three times at the temperature of 50 ℃, and drying the solid sample in vacuum at the temperature of 100-150 ℃ to obtain the self-micropore ladder-shaped polymer I for gas separation.
FIG. 1 shows nuclear magnetic hydrogen spectra (Brooks AVANCE III 500 MHz) of a self-supported microporous ladder polymer I for gas separation; FIG. 2 shows the IR spectrum (Thermo NICOLET iS 50) of a ladder-shaped polymer I with micropores for gas separation. As can be seen from FIGS. 1 and 2, the present application has been prepared
The polymer of structure has an n value of 55.2 as determined by gel permeation chromatography (Agilent PL-GPC 220).
Example 2
A self-contained microporous ladder polymer for gas separation is prepared by the following steps:
(1) adding 4.87 g of 2, 6-dihydroxytriptycene (17 mmol) and 3.95 g of trifluoro acetophenone (22.7 mmol) into a 250 mL single-neck flask with a magnetic stirrer, adding 19 mL of anhydrous dichloromethane, adding an ice water bath, stirring until the monomers are dissolved, adding 8.18 mL of trifluoromethanesulfonic acid (92.4 mmol), removing the ice water bath, and stirring at room temperature for 48 hours until the solution precipitates out a viscous colloid;
(2) slowly pouring the viscous liquid obtained in the step (1) into stirred 100mL ethanol, washing and filtering for three times at the temperature of 50 ℃, and drying the solid sample at the temperature of 100-150 ℃ in vacuum to obtain the self-micropore ladder-shaped polymer II for gas separation, wherein the n value is 55.3 measured by gel permeation chromatography (Agilent PL-GPC 220).
Example 3
A self-contained microporous ladder polymer for gas separation is prepared by the following steps:
(1) adding 4.01 g of 2, 6-dihydroxytriptycene (14 mmol) and 3.31 g of trifluoroacetophenone (19 mmol) into a 250 mL single-neck flask with a magnetic stirrer, adding 24 mL of chloroform, adding an ice water bath, stirring until the monomers are dissolved, adding 140 mmol of methanesulfonic acid, removing the ice water bath, and stirring at room temperature for 48 hours until the solution precipitates out a viscous colloid;
(2) slowly pouring the viscous liquid obtained in the step (1) into a stirred mixed solvent (volume ratio is 1: 1) of 100mL of methanol and ethanol, washing and filtering at 50 ℃ for three times, drying the solid sample at 100-150 ℃ in vacuum to obtain the self-contained microporous ladder-shaped polymer III for gas separation, wherein the n value is 48.2 measured by gel permeation chromatography (Agilent PL-GPC 220).
Example 4
A self-contained microporous ladder polymer for gas separation is prepared by the following steps:
(1) in a 250 mL single-neck flask with a magnetic stirrer, 5.9 g of
(17 mmol) and 2.59 g of trifluoroacetone (23 mmol), 18 mL of anhydrous dichloromethane are added, the mixture is stirred in an ice-water bath until the monomers are dissolved, 13.25 mL of trifluoromethanesulfonic acid (149.1 mmol) are added, the ice-water bath is removed, and the mixture is stirred at room temperature for 48h until the solution is viscousA colloid;
(2) slowly pouring the viscous liquid obtained in the step (1) into stirred 100mL of methanol, washing and filtering for three times at the temperature of 50 ℃, and drying the solid sample at the temperature of 100-150 ℃ in vacuum to obtain the self-micropore ladder-shaped polymer IV for gas separation, wherein the n value is 60.1 measured by gel permeation chromatography (Agilent PL-GPC 220).
Example 5
A self-contained microporous ladder polymer for gas separation is prepared by the following steps:
(1) in a 250 mL single-neck flask with a magnetic stir bar, 7.8 g of pentapterene was added
(17 mmol) and 3.93 g of trifluorpyrazoletoethanone (24 mmol), adding 32 mL of anhydrous dichloromethane, adding ice water bath, stirring until the monomers are dissolved, adding 15.0 mL of trifluoromethanesulfonic acid (169.4 mmol), removing the ice water bath, and stirring at room temperature for 55 hours until the solution precipitates out of a viscous colloid;
(2) slowly pouring the viscous liquid obtained in the step (1) into stirred 100mL of methanol, washing and filtering for three times at the temperature of 50 ℃, and drying the solid sample at the temperature of 100-150 ℃ in vacuum to obtain the self-micropore ladder-shaped polymer V for gas separation, wherein the n value is 39.7 measured by gel permeation chromatography (Agilent PL-GPC 220).
Example 6
A self-contained microporous ladder polymer for gas separation is prepared by the following steps:
(1) in a 250 mL single-neck flask with a magnetic stirrer, 4.87 g of 2, 6-dihydroxytriptycene (17 mmol) and 6.34 g of perfluoroacetophenone (24 mmol) are added, 32 mL of anhydrous dichloromethane are added, an ice water bath is added for stirring until the monomers are dissolved, 8.18 mL of trifluoromethanesulfonic acid (92.4 mmol) is added, the ice water bath is removed, and the mixture is stirred at room temperature for 48h until a viscous colloid precipitates;
(2) slowly pouring the viscous liquid obtained in the step (1) into stirred 100mL of methanol, washing and filtering for three times at the temperature of 50 ℃, and drying the solid sample at the temperature of 100-150 ℃ in vacuum to obtain the self-micropore ladder-shaped polymer VI for gas separation, wherein the n value is 58.8 measured by gel permeation chromatography (Agilent PL-GPC 220).
Example 7
A self-micropore ladder-shaped material for gas separation is prepared by the following method:
(1) adding 4.87 g of 2, 6-dihydroxytriptycene (17 mmol) and 4.53 g of trifluoroacetophenone (26 mmol) into a 250 mL single-neck flask with a magnetic stirrer, adding 32 mL of anhydrous dichloromethane, adding an ice water bath, stirring until the monomers are dissolved, adding 8.18 mL of trifluoromethanesulfonic acid (92.4 mmol), removing the ice water bath, and stirring at room temperature for 48 hours until viscous substances are precipitated out of the solution;
(2) slowly pouring the polymer solution obtained in the step (1) into 100mL of methanol under stirring, washing and filtering for three times at the temperature of 50 ℃, and drying the solid sample at the temperature of 100-150 ℃ in vacuum to obtain the self-micropore ladder-shaped polymer VII for gas separation, wherein the average n value is 22 as determined by Gel Permeation Chromatography (GPC).
Example 8
A self-micropore ladder-shaped material for gas separation is prepared by the following method:
(1) adding 4.87 g of 2, 6-dihydroxytriptycene (17 mmol) and 3.66 g of trifluoro acetophenone (21 mmol) into a 250 mL single-neck flask with a magnetic stirrer, adding 32 mL of anhydrous dichloromethane, adding 8.18 mL of trifluoromethanesulfonic acid (92.4 mmol) after the monomers are dissolved by stirring in an ice water bath, removing the ice water bath, and stirring at room temperature for 48 hours until viscous substances are precipitated out of the solution;
(2) slowly pouring the polymer solution obtained in the step (1) into 100mL of methanol under stirring, washing and filtering for three times at the temperature of 50 ℃, and drying the solid sample at the temperature of 100-150 ℃ in vacuum to obtain the self-micropore ladder-shaped polymer VIII for gas separation, wherein the average n value is 91 as determined by Gel Permeation Chromatography (GPC).
Comparative example 1
A self-micropore ladder-shaped material for gas separation is prepared by the following method:
(1) adding 4.87 g of 2, 6-dihydroxytriptycene (17 mmol) and 5.92 g of trifluoro acetophenone (34 mmol) into a 250 mL single-neck flask with a magnetic stirrer, adding 32 mL of anhydrous dichloromethane, adding 8.18 mL of trifluoromethanesulfonic acid (92.4 mmol) after the monomers are dissolved by stirring in an ice water bath, removing the ice water bath, and stirring at room temperature for 48 hours until viscous substances are precipitated out of the solution;
(2) slowly pouring the polymer solution obtained in the step (1) into 100mL of methanol under stirring, washing and filtering for three times at the temperature of 50 ℃, and drying the solid sample at the temperature of 100-150 ℃ in vacuum to obtain the self-micropore ladder-shaped polymer IX for gas separation, wherein the average n value is 11 as determined by Gel Permeation Chromatography (GPC).
Application example 1
A flat sheet membrane for gas separation, prepared by the method of:
(a) redissolving the self-microporous ladder-shaped polymer I for gas separation obtained in the example 1 in a chloroform solvent to prepare a coating solution with the concentration of 4 wt%;
(b) and (3) coating the coating liquid on a quartz substrate of 10 multiplied by 10cm, and drying in vacuum at 100-120 ℃ to obtain a flat membrane with the thickness of 50-53 mu m.
Application example 2
The difference from application example 1 is that: the self-microporous trapezoidal polymer I for gas separation obtained in the example 1 is replaced by the self-microporous trapezoidal polymer II for gas separation obtained in the example 2, and the thickness of the prepared flat membrane is 50-52 μm.
Application example 3
The difference from application example 1 is that: the self-microporous ladder-shaped polymer I for gas separation obtained in example 1 is replaced by the self-microporous ladder-shaped polymer III for gas separation obtained in example 3, and the thickness of the prepared flat membrane is 50-53 μm.
Application example 4
The difference from application example 1 is that: the self-microporous trapezoidal polymer I for gas separation obtained in example 1 is replaced by the self-microporous trapezoidal polymer IV for gas separation obtained in example 4, and the thickness of the prepared flat membrane is 48-50 μm.
Application example 5
The difference from application example 1 is that: the self-microporous trapezoidal polymer I for gas separation obtained in example 1 is replaced by the self-microporous trapezoidal polymer V for gas separation obtained in example 5, and the thickness of the prepared flat membrane is 52-56 μm.
Application example 6
The difference from application example 1 is that: the self-microporous trapezoidal polymer I for gas separation obtained in example 1 is replaced by the self-microporous trapezoidal polymer VI for gas separation obtained in example 6, and the thickness of the prepared flat membrane is 53-57 mu m.
Application example 7
A flat sheet membrane for gas separation, prepared by the method of:
(a) redissolving the self-microporous ladder-shaped polymer I for gas separation obtained in the example 1 in a chloroform solvent to prepare a coating solution with the concentration of 3 wt%;
(b) and (3) coating the film coating liquid on a quartz substrate of 10 multiplied by 10cm, and drying in vacuum at 100-120 ℃ to obtain a flat membrane with the thickness of 42-44 mu m.
Application example 8
A flat sheet membrane for gas separation, prepared by the method of:
(a) redissolving the self-microporous ladder-shaped polymer I for gas separation obtained in the example 1 in a chloroform solvent to prepare a coating solution with the concentration of 6 wt%;
(b) and (3) coating the film coating liquid on a quartz substrate of 10cm multiplied by 10cm, and drying in vacuum at 100-120 ℃ to obtain a flat membrane with the thickness of 50-53 mu m.
Application example 9
A hollow fiber membrane for gas separation, the preparation method of the hollow fiber membrane comprising the steps of:
(A) from example 1 for gas separationThe polymer I with micropores is in tetrahydrofuran,N,N-redissolving in a mixed solvent of dimethylacetamide and ethanol to obtain a spinning solution; the spinning solution consists of a trapezoidal polymer I/tetrahydrofuran with self-micropores for gas separationN,N-dimethylacetamide/ethanol mass ratio of 18.5:66:12.5: 3.0;
(B) spinning the spinning solution under the following spinning conditions: the spinning solution is as described in step (A); the core liquid is matched with the spinning solution (tetrahydrofuran-N,N-dimethylacetamide/ethanol mass ratio of 50:42.5: 7.5; the height of the air gap is 4 cm; the filament collecting speed is 16.5 m/min; the flow rate of the spinning solution is 180 mL/h; the flow rate of the core liquid was 60 mL/h, and a hollow fiber membrane (thickness of about 100 μm, thickness of the dense selective layer was about 200 nm) was obtained.
Application example 10
The difference from application example 1 is that: the self-microporous trapezoidal polymer I for gas separation obtained in example 1 is replaced by the self-microporous trapezoidal polymer VII for gas separation obtained in example 7, and the thickness of the prepared flat membrane is 45-48 μm.
Application example 11
The difference from application example 1 is that: the self-microporous trapezoidal polymer I for gas separation obtained in example 1 is replaced by the self-microporous trapezoidal polymer VIII for gas separation obtained in example 8, and the thickness of the prepared flat membrane is 60-63 μm.
Comparative application example 1
The difference from application example 1 is that: when the self-supporting microporous ladder-shaped polymer I for gas separation obtained in example 1 was replaced with the self-supporting microporous ladder-shaped polymer IX for gas separation obtained in comparative example 1, a flat sheet membrane could not be obtained because the value of n was too small.
And (3) performance testing:
gas permeability: the measurement conditions were 0.5 MPa, 35 ℃ and He and H were measured2、CO2、O2、N2And CH4Permeability of six gases. The test results are shown in Table 1.
Table 1 gas permeability data for materials provided in the application examples
As can be seen from Table 1, the flat sheet membranes and hollow fiber membranes provided herein are directed to CO2Has high permeability and permselectivity, and is suitable for CO2Removal and filtration.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A self-supporting microporous ladder polymer for gas separation, the self-supporting microporous ladder polymer for gas separation having a structure according to formula (I):
In the formula (I), R1Is selected from Ra、Rb、Rc、RdAny one of the groups or a combination of at least two of the groups; r2Is selected from Re、Rf、Rg、RhAny one of the groups or a combination of at least two of the groups; n is a positive integer not less than 20;
2. the self-supported microporous ladder polymer for gas separation of claim 1, wherein n is an integer of 20 to 100.
3. A method for preparing the ladder-shaped polymer with micropores for gas separation according to claim 1 or 2, wherein the method comprises the following steps:
(1) dissolving a monomer A containing dihydroxy function and a monomer B containing trifluoromethyl ketone in a solvent C, adding a superacid catalyst after the monomers A and B are completely dissolved, and reacting to obtain a viscous polymer solution;
wherein the functional monomer A containing the dihydroxy comprises Ma、Mb、Mc、MdAny one or a combination of at least two of the above, wherein the trifluoromethyl ketone-containing monomer B is Me、Mf、Mg、MhAny one or a combination of at least two of;
(2) and (2) adding an excessive precipitator D into the polymer solution obtained in the step (1), then washing and filtering, refluxing in the precipitator for 3 times, filtering, and drying a solid sample to obtain the trapezoidal polymer with micropores for gas separation.
4. The method of claim 3, wherein the superacid catalyst comprises trifluoromethanesulfonic acid and/or methanesulfonic acid;
the reaction temperature in the step (1) is 0-50 ℃, and the reaction time is 6-72 h.
5. The preparation method according to claim 3, wherein the dihydroxy functional monomer A and the trifluoromethyl ketone monomer B in step (1) are added in a ratio of 0.65 to 0.8;
the adding amount of the superacid catalyst in the step (1) is 4-10 times of that of the functional monomer A containing dihydroxy.
6. The method according to claim 3, wherein the precipitant D comprises methanol and/or ethanol.
7. A flat membrane for gas separation, which is prepared by the following steps:
(a) dispersing the self-microporous ladder-shaped polymer for gas separation according to claim 1 or 2 in a dispersion solvent to obtain a coating solution;
(b) and coating the coating liquid on a substrate, and drying to obtain the flat membrane.
8. The flat sheet membrane according to claim 7, wherein the dispersion concentration of the self-microporous ladder-shaped polymer for gas separation in the coating solution is 3 to 6 wt%.
9. A hollow fiber membrane for gas separation, characterized in that the preparation method of the hollow fiber membrane comprises the following steps:
(A) dispersing the self-contained micro-porous ladder-shaped polymer for gas separation according to claim 1 or 2 in a dispersion solvent to obtain a spinning solution;
(B) and spinning the spinning solution to obtain the hollow fiber membrane.
10. Use of a flat sheet membrane for gas separation according to claim 7 or 8, or a hollow fiber membrane for gas separation according to claim 9, wherein the flat sheet membrane and/or the hollow fiber membrane is/are used for CO2Trapping and separation.
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| WO2024081279A1 (en) * | 2022-10-12 | 2024-04-18 | Osmoses Inc. | Ladder polymers and improved methods of making the same |
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