KR102548515B1 - Gas separation membrane using crosslinked carboxylate functionalized polymers of intrinsic microporosity and preparation method thereof - Google Patents

Abstract

The present invention relates to a cross-linked polymeric membrane for a gas separation membrane based on a carboxylated intrinsic microporous polymer and a method for preparing the same, and more specifically, to a film-forming composition by mixing a carboxylated intrinsic microporous polymer with a crosslinking agent and a solvent. It relates to an intrinsic microporous polymer-based cross-linked polymeric membrane prepared by preparing a membrane, forming it into a membrane, and then cross-linking the membrane, and a method for preparing the same and its use as a gas separation membrane. In the case of the cross-polymerized membrane according to the present invention, it was confirmed that a membrane having excellent gas permeability can be prepared by imparting functionality by adding a cross-linking agent and changing the spacing of existing polymer chains. In particular, in the case of separating hydrogen from a mixed gas of hydrogen and nitrogen and the case of separating oxygen from a mixed gas of oxygen and nitrogen, excellent performance exceeded the Robson's upper limit, which is the limiting index of gas separation performance.

Description

Gas separation membrane using crosslinked carboxylate functionalized polymers of intrinsic microporosity and preparation method thereof}

The present invention relates to a cross-polymerization membrane for a gas separation membrane based on a carboxylated intrinsic microporous polymer and a method for preparing the same.

More specifically, a cross-linked polymeric film based on intrinsic micro-porous polymer prepared by preparing a film-forming composition by mixing a carboxylated intrinsic micro-porous polymer with a cross-linking agent and a solvent, forming the film into a film, and cross-linking the film, and a method for preparing the same and its use as a gas separation membrane.

After industrialization, the increase in the use of fossil fuels has increased the concentration of carbon dioxide in the atmosphere, and the global warming effect has become a task to be solved by mankind, and research has been actively conducted to lower the carbon dioxide in the atmosphere. Among them, the membrane separation method is considered a high energy efficiency and environment-friendly process because it does not accompany phase change unlike conventional absorption or adsorption methods that have been used for capturing and storing carbon dioxide.

Demand for such high energy efficiency and environmentally friendly separation membranes is not limited to the separation of carbon dioxide in the atmosphere, but also for oxygen enrichment membranes that effectively separate oxygen in the atmosphere, separation of carbon dioxide from natural gas, and separation of hydrogen from syngas. Its application fields are wide, such as separation membranes. The most important material in the membrane method that can be used in various fields like this can be said to be the polymer material constituting the membrane. Until now, various materials such as siloxane-based polymers, substituted polyacetylene-based polymers, fluorine-based polymers, polysulfone-based polymers, cellulose acetate, polycarbonates, polyimides, and polyphenylene oxides have been widely used as materials for gas separation membranes. has been utilized

Recently, trapezoidal polymers with a twisted structure, called Polymers of Intrinsic Microporosity (PIMs), are in the limelight as a gas separation membrane material. This is because it has the advantage of being able to introduce the following permanent pores into the polymer main chain, and thus has a high specific surface area and free volume. When the material is used as a material for a gas separation membrane, it is expected to exhibit excellent performance exceeding the Robeson upper bound, which is the performance limit of a gas separation membrane material.

In order to prepare intrinsically porous polymers with better performance, various studies are being conducted ranging from polymerization and modification of new polymers to complexation with porous particles. In this regard, the inventors of the present invention, in the case of an intrinsic microporous polymer carboxylated by Macromolecules 2017, 50, 8019-8027, base hydrolysis of the parent polymer PIM-1 to carboxyl to the twisted trapezoidal main chain. It was announced that the introduction of an acid functional group and a reduced spacing between polymer chains due to the introduction of a carboxylic acid functional group and an increased affinity for carbon dioxide show that the carboxylated intrinsically porous polymer exhibits separation efficiency for hydrogen and carbon dioxide. there is.

In addition, when using a polymer material having such excellent properties as a separator material, mechanical strength and chemical resistance are essential requirements for forming and reforming the separator and manufacturing modules and systems thereafter. In order to impart mechanical strength, dimensional stability and chemical resistance to the separator material, research on heat treatment and crosslinking reaction is being conducted, and Korean Patent Registration No. 10-0655674 is a prior art related thereto.

Therefore, the present inventors prepared a crosslinked polymeric membrane by adding a crosslinking agent to a carboxylated intrinsically porous polymer, which can be usefully used as a separator material having excellent mechanical strength, dimensional stability and chemical resistance, and excellent gas separation membrane properties. found out that there is, and completed the present invention.

Korean Patent Registration No. 10-0655674.

Macromolecules 2017, 50, 8019-8027.

The present invention was developed to solve the above problems, and an object of the present invention is to provide a cross-polymerized membrane for a gas separation membrane based on a carboxylated intrinsic microporous polymer.

In addition, the present invention is intended to provide a method for preparing a cross-polymerization membrane for a gas separation membrane based on the carboxylated intrinsic microporous polymer.

In the present invention, a polymer providing step of providing a homopolymer, copolymer or a mixture containing one or more of the compounds represented by Formula 1 in order to solve the above problems; Film-forming composition preparation step of mixing the polymer, crosslinking agent and solvent; It provides a method for preparing an intrinsic microporous polymer-based crosslinked polymeric membrane, comprising a membrane forming step of forming a membrane with the membrane forming composition and a crosslinking polymeric membrane manufacturing step of crosslinking the membrane.

<Formula 1>

In Formula 1, X is any one selected from the group consisting of X1 to X17, and n is an integer of 10 to 500 as a repeating unit.

In the manufacturing method according to the present invention, the crosslinking agent may have a chemical structure represented by Formula 2 below.

<Formula 2>

In Formula 2, R is any one of a straight-chain or branched-chain alkylene group, a straight-chain or branched-chain alkylene group containing an oxygen atom, or an arylene group.

In addition, the present invention provides the use of the cross-linked polymeric membrane as an effective gas separation membrane, and the gas separation membrane can be a very effective gas separation membrane for separating hydrogen from a mixed gas of hydrogen and nitrogen or separating oxygen from a mixed gas of oxygen and nitrogen. there is.

The present invention has the advantage of preparing a crosslinked reinforcement film having excellent mechanical strength and chemical resistance by mixing a carboxylated intrinsic microporous polymer with a crosslinking agent and a solvent and proceeding with a crosslinking reaction during film formation through a solution process. there is

In addition, in the case of the prepared cross-polymerization membrane, it was confirmed that a membrane having excellent gas permeability could be prepared by imparting functionality due to the addition of a cross-linking agent and changing the spacing of existing polymer chains.

1 is a graph showing experimental results for hydrogen permeability and hydrogen and nitrogen selectivity of a cross-linked polymeric membrane according to an embodiment of the present invention.
2 is a graph showing experimental results for oxygen permeability and oxygen and nitrogen selectivity of a cross-linked polymeric film according to an embodiment of the present invention.
3 is a graph showing experimental results for carbon dioxide permeability and carbon dioxide and methane selectivity of a cross-linked polymeric membrane according to an embodiment of the present invention.
4 is a graph showing experimental results for carbon dioxide permeability and carbon dioxide and nitrogen selectivity of a cross-linked polymeric membrane according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail. The terms or words used in this specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventors may appropriately define the concept of terms in order to explain their invention in the best way. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

“Polymers of Intrinsic Microporosity (PIM)” according to the present invention have a twisted backbone, resulting in a large amount of microporosity (microporosity) that occurs when the polymer structure is not densely stacked is the resulting polymer. In addition, according to the definition of IUPAC (International Union of Pure and Applied Chemistry), porous materials are micropores (pore size < 2 nm), mesopores (2 nm < pore size < 50 nm), depending on the pore size. ), macropores (pore size > 50 nm), the porous material including the intrinsically porous polymer according to the present invention may coexist with micropores and mesopores, but mainly micropores of less than 2 nm Qigong dominates.

In the present invention, a polymer providing step of providing a homopolymer, copolymer or a mixture containing one or more of the compounds represented by Formula 1 in order to solve the above problems; Film-forming composition preparation step of mixing the polymer, crosslinking agent and solvent; It provides a method for preparing an intrinsic microporous polymer-based crosslinked polymeric membrane, comprising a membrane forming step of forming a membrane with the membrane forming composition and a crosslinking polymeric membrane manufacturing step of crosslinking the membrane.

<Formula 1>

In Formula 1, X is any one selected from the group consisting of X1 to X17, and n is an integer of 10 to 500 as a repeating unit.

In the method for preparing an intrinsic microporous polymer-based crosslinking polymeric membrane according to an embodiment of the present invention, the crosslinking agent may have a chemical structure represented by Chemical Formula 2 below.

<Formula 2>

In Formula 2, R is any one of a linear or branched alkylene group, a linear or branched alkylene group containing an oxygen atom, or an arylene group.

More preferably, R in Formula 2 may be any one of the following Formulas.

-(CH ₂ ) _m -,

-(CH ₂ ) _m -O-(CH ₂ ) _l -,

delete

-CH ₂ -O-(CH ₂ ) ₄ -O-CH ₂ -

Here, m and l are the same or different and are each an integer from 1 to 6, and n is an integer from 1 to 10000.

In the method for preparing an intrinsic microporous polymer-based cross-linking polymeric membrane according to an embodiment of the present invention, the solvent is tetrahydrofuran (THF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), It may be at least one selected from the group consisting of dimethylformamide (DMF) and dimethylacetamide (DMAc), and tetrahydrofuran is more preferably used.

In the step of preparing the film-forming composition in which the polymer, crosslinking agent and solvent are mixed according to an embodiment of the present invention, the mixing ratio of the polymer, crosslinking agent and solvent is as follows. The crosslinking agent is preferably 0.1 to 50% by weight relative to the polymer. And it is preferable to prepare a solution containing 1 to 40% by weight of solids including a polymer and a crosslinking agent.

In the method for preparing an intrinsic microporous polymer-based crosslinked polymeric membrane according to an embodiment of the present invention, the step of preparing the crosslinked polymeric membrane for crosslinking the membrane may be performed through the reaction shown in Scheme 1 below.

<Scheme 1>

In Scheme 1, n is a repeating unit and an integer of 10 to 500, and R is any one of a straight-chain or branched-chain alkylene group, a straight-chain or branched-chain alkylene group containing an oxygen atom, or an arylene group. In particular, the arylene group may include a phenylene group, a naphthalenylene group, and an indenylene group. The crosslinking reaction is performed in a heating and drying step after evaporation of the solvent, and the heating and drying temperature range is preferably from room temperature to 250 °C.

In addition, the present invention provides an intrinsic microporous polymer-based crosslinked polymeric film characterized in that a homopolymer, a copolymer, or a mixture containing one or more of the compounds represented by Formula 1 is crosslinked through a reaction with a crosslinking agent.

<Formula 1>

In Formula 1, X is any one selected from the group consisting of X1 to X17 below.

In the intrinsic microporous polymer-based crosslinking polymeric membrane according to one embodiment of the present invention, the crosslinking agent may have a chemical structure represented by Chemical Formula 2 below.

<Formula 2>

In Formula 2, R is any one of a straight-chain or branched-chain alkylene group, a straight-chain or branched-chain alkylene group containing an oxygen atom, or an arylene group.

More preferably, R in Formula 2 may be any one of the following Formulas.

-(CH ₂ ) _m -,

-(CH ₂ ) _m -O-(CH ₂ ) _l -,

delete

-CH ₂ -O-(CH ₂ ) ₄ -O-CH ₂ -

Here, m and l are the same or different and are each an integer from 1 to 6, and n is an integer from 1 to 10000.

In the intrinsic microporous polymer-based crosslinking polymeric membrane according to an embodiment of the present invention, the crosslinking polymeric membrane may be a gas separation membrane, more preferably, the gas separation membrane separates hydrogen from a mixed gas of hydrogen and nitrogen or oxygen and nitrogen. It may be a gas separation membrane that separates oxygen from a mixed gas of

The carboxylated intrinsically porous polymer crosslinked polymeric film according to the present invention is a crosslinking reaction product based on a crosslinking reaction between the intrinsically porous polymer represented by Chemical Formula 1 and the crosslinking agent compound represented by Chemical Formula 2.

The intrinsically porous polymer into which the carboxylic acid functional group represented by Formula 1 according to the present invention is introduced can be used as a gas separation membrane. This is because, in the case of the intrinsic microporous polymer according to the present invention, it is easy to move gas through a high free volume and specific surface area. The specific surface area of the intrinsic microporous polymer is not limited, but may have a surface area of about 200 m ² /g or more. It may preferably have a surface area of 200 m ² /g or more and 2000 m ² /g or less, more preferably 200 m ² /g or more and 1500 m ² /g or less.

In addition, the intrinsic microporous polymer having a carboxylic acid functional group introduced according to the present invention represented by Formula 1 is a polymer having a carboxylic acid functional group having a high affinity for carbon dioxide, and is a carboxylated intrinsic micro-porous polymer. is an intrinsic microporous polymer in which a carboxylic acid functional group having a high affinity for carbon dioxide is introduced into a twisted backbone.

Therefore, the intrinsically porous polymer introduced with a carboxylic acid functional group according to the present invention has a higher specific surface area and a functional functional group than other polymers, and is relatively free from relatively large gas molecules such as methane and nitrogen. A separation membrane that is easy to separate small gases such as small carbon dioxide and hydrogen can be manufactured.

Hereinafter, implementation examples and embodiments of the present invention will be described in detail so that those with general knowledge in the technical field to which the present application pertains can easily practice, as shown in the accompanying drawings, preferred embodiments of the present invention. In particular, the technical idea of the present invention and its core configuration and operation are not limited by this. In addition, the contents of the present invention can be implemented in various types of equipment, and is not limited to the implementation examples and examples described herein.

<Preparation Example 1> Preparation of Polymers of Intrinsic Microporosity (PIM)

After removing the water inside the two-necked round flask (250 ml), 5.5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1 was added to the flask under a nitrogen atmosphere. '-spirobiindan (TTSBI, 5.5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindan) (10.21 g, 30 mmol), K ₂ CO ₃ ( 8.29 g, 60 mmol), tetrafluorophthalonitrile (TFTPN, tetrafluorophthalonitrile) (6.00 g, 30 mmol) and dimethylformamide (DMF) (210 ml) were added, followed by polymerization at 55 °C for 72 hours. After completion of the reaction, 350 ml of tetrahydrofuran (THF) was added to the reactor cooled to room temperature to precipitate high molecular weight PIM-1, and the supernatant containing low molecular weight and oligomers was removed. The polymer was re-dissolved in tetrahydrofuran (THF) and reprecipitation was repeated twice using methanol. The final product was vacuum dried to obtain a yellow intrinsic microporous polymer represented by Chemical Formula 3 (PIM-1) (10.3 g). As a result of GPC (Gel permeation chromatography) measurement, M _n = 60,900 and PDI (Polydispersity index) showed a value of 1.58.

<Formula 3>

<Preparation Example 2> Preparation of carboxylated intrinsic microporous polymer (PIM-COOH)

480 ml distilled water, 600 ml ethanol, and 240 g NaOH were put in a three-necked round flask (2000 ml) to prepare a 20% by weight NaOH solution, and then the intrinsic microporous polymer (PIM-1) obtained in Preparation Example 1 was added. and modified at 125 ° C. for 360 hours. After completion of the reaction, the aqueous layer and the organic layer were allowed to separate in a liquid-liquid separator, and then the organic layer containing the modified intrinsic microporous polymer was separated, slowly precipitated in about 5 wt% HCl solution, and filtered. After washing with distilled water several times, the filtrate was dried for 24 hours in a vacuum dryer with a temperature controlled at 60 ° C., and then dissolved in tetrahydrofuran (THF) and reprecipitated using water and methanol was repeated twice. . The final product was vacuum-dried to obtain a carboxylated intrinsic microporous polymer (PIM-1) (7.0 g) represented by Chemical Formula 4 below. As a result of GPC measurement, M _n =25,700 and PDI of 1.07 were shown.

<Formula 4>

<Example 1> Preparation of crosslinked polymer membrane (Crosslinked PIM-COOH) for gas separation membrane containing carboxylated intrinsic microporous polymer

To prepare a carboxylated intrinsic microporous polymer crosslinked membrane, 0.196 g PIM-COOH prepared in step 1, 0.004 g 1,4-butanediol diglycidyl ether (1,4-Butanediol diglycidyl ether) , 24 ml of tetrahydrofuran (THF) was added to prepare a polymer solution. The prepared polymer solution was injected into a glass Petri-dish while filtering out impurities with a 5 μm syringe filter. After slowly evaporating the solvent for two days under an air atmosphere, the film was separated from the glass petri dish using distilled water. It was dried for 24 hours in a vacuum dryer adjusted to 100 °C. The dried film was soaked in methanol for 2 hours, recovered, and dried again in a vacuum dryer adjusted to 100 °C for 24 hours. In the same manner as described above, a polymer crosslinked membrane containing a carboxylated polymer having intrinsic micropores having a thickness of 10 to 100 μm was prepared.

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<Example 2> Preparation of Crosslinked PIM-COOH for Gas Separation Membrane Containing Carboxylated Intrinsically Microporous Polymer (BD_5wt%)

To prepare a carboxylated intrinsic microporous polymer crosslinked membrane, 0.190 g PIM-COOH prepared in step 1, 0.010 g 1,4-butanediol diglycidyl ether (1,4-Butanediol diglycidyl ether) , 24 ml of tetrahydrofuran (THF) was added to prepare a polymer solution. The prepared polymer solution was injected into a glass Petri-dish while filtering out impurities with a 5 μm syringe filter. After slowly evaporating the solvent for two days under an air atmosphere, the film was separated from the glass petri dish using distilled water. It was dried for 24 hours in a vacuum dryer adjusted to 100 °C. The dried film was soaked in methanol for 2 hours, recovered, and dried again in a vacuum dryer adjusted to 100 °C for 24 hours. In the same manner as described above, a polymer crosslinked membrane containing a carboxylated polymer having intrinsic micropores having a thickness of 10 to 100 μm was prepared.

<Example 3> Preparation of Crosslinked PIM-COOH for Gas Separation Membrane Containing Carboxylated Intrinsically Microporous Polymer (PEO500_2wt%)

To prepare a carboxylated intrinsic microporous polymer crosslinked membrane, 0.196 g PIM-COOH prepared in step 1 above, 0.004 g polyethylene glycol diglycidyl ether (Poly(ethylene glycol) diglycidyl ether, Mn = 500 ), 24 ml of tetrahydrofuran (THF) was added to prepare a polymer solution. The prepared polymer solution was injected into a glass Petri-dish while filtering out impurities with a 5 μm syringe filter. After slowly evaporating the solvent for two days under an air atmosphere, the film was separated from the glass petri dish using distilled water. It was dried for 24 hours in a vacuum dryer adjusted to 100 °C. The dried film was soaked in methanol for 2 hours, recovered, and dried again in a vacuum dryer adjusted to 100 °C for 24 hours. In the same manner as described above, a polymer crosslinked membrane containing a carboxylated polymer having intrinsic micropores having a thickness of 10 to 100 μm was prepared.

<Example 4> Preparation of Crosslinked PIM-COOH for Gas Separation Membrane Containing Carboxylated Intrinsically Microporous Polymer (PEO500_5wt%)

To prepare a carboxylated intrinsic microporous polymer crosslinked membrane, 0.190 g PIM-COOH prepared in step 1 above, 0.010 g polyethylene glycol diglycidyl ether (Poly(ethylene glycol) diglycidyl ether, Mn = 500 ), 24 ml of tetrahydrofuran (THF) was added to prepare a polymer solution. The prepared polymer solution was injected into a glass Petri-dish while filtering out impurities with a 5 μm syringe filter. After slowly evaporating the solvent for two days under an air atmosphere, the film was separated from the glass petri dish using distilled water. It was dried for 24 hours in a vacuum dryer adjusted to 100 °C. The dried film was soaked in methanol for 2 hours, recovered, and dried again in a vacuum dryer adjusted to 100 °C for 24 hours. In the same manner as described above, a polymer crosslinked membrane containing a carboxylated polymer having intrinsic micropores having a thickness of 10 to 100 μm was prepared.

<Example 5> Preparation of Crosslinked PIM-COOH for Gas Separation Membrane Containing Carboxylated Intrinsically Microporous Polymer (BADGE_5wt%)

To prepare a carboxylated intrinsic microporous polymer crosslinked membrane, 0.190 g PIM-COOH prepared in step 1 above, 0.010 g bisphenol A diglycidyl ether, 24 ml tetrahydrofuran (THF) ) was added to prepare a polymer solution. The prepared polymer solution was injected into a glass Petri-dish while filtering out impurities with a 5 μm syringe filter. After slowly evaporating the solvent for two days under an air atmosphere, the film was separated from the glass petri dish using distilled water. It was dried for 24 hours in a vacuum dryer adjusted to 100 °C. The dried film was soaked in methanol for 2 hours, recovered, and dried again in a vacuum dryer adjusted to 100 °C for 24 hours. In the same manner as described above, a polymer crosslinked membrane containing a carboxylated polymer having intrinsic micropores having a thickness of 10 to 100 μm was prepared.

<Comparative Examples 1 and 2> Preparation of non-crosslinked intrinsic microporous polymer membrane

In order to prepare a non-crosslinked intrinsic microporous polymer membrane (PIM-1) and a carboxylated intrinsic microporous polymer membrane (PIM-COOH), 0.2 g PIM prepared in Preparation Examples 1 and 2 or 0.2 g PIM-COOH, 24 ml of tetrahydrofuran (THF) was added to prepare a polymer solution. The prepared polymer solution was injected into a glass Petri-dish while filtering out impurities with a 5 μm syringe filter. After slowly evaporating the solvent for two days under an air atmosphere, the dried film was separated from a glass Petri dish. It was dried for 24 hours in a vacuum dryer adjusted to 100 °C. In the same manner as described above, a non-crosslinked intrinsic microporous polymer membrane (PIM-1) and a carboxylated intrinsic microporous polymer membrane (PIM-COOH) having a thickness of 10 to 100 μm were prepared.

<Analysis Example> Evaluation of gas separation membrane characteristics

Oxygen, nitrogen, methane, carbon dioxide, hydrogen gas using the crosslinked polymer membrane for gas separation comprising the carboxylated intrinsic microporous polymer prepared in Examples 1-5 according to the present invention and the non-crosslinked membrane according to Comparative Example A gas permeability test was performed. The results are summarized in Tables 1 and 2, and are shown in Figures 1 to 4.

Sample Permeability (Barrer) ^a _{H2 CO2} O ₂ N _{2 CH4} PIM-1 3,511 3,934 1,049 269 366 PIM-COOH 90.53 96.43 9.8 1.8 3.82 BD_2wt% 1,326 811.35 196.84 37.82 45 BD_5wt% 375.01 280.42 55.35 12.47 14.36 PEO500_ 2wt% 332.77 263.23 50.48 11.37 13.75 PEO500_5wt% 239.21 188.48 34.64 7.70 8.72 BADGE_5wt% 348.98 266.55 46.09 9.80 10.10

^a : 1 barrer = 10 ^-10 cm ³ (STP) cm/ (s cm ² cmHg)

Sample Selectivity (α) ^b CO ₂ /CH ₄ CO ₂ /N ₂ O ₂ /N ₂ H ₂ /N ₂ PIM-1 11 14.6 3.9 13 PIM-COOH 25.2 53.6 5.4 50.3 BD_2wt% 18.2 21.5 5.2 35.1 BD_5wt% 19.5 22.5 4.4 30.1 PEO500_2wt% 19.1 23.1 4.4 29.3 PEO500_5wt% 21.6 24.5 4.5 31.1 BADGE_5wt% 26.4 27.2 4.7 35.6

^b : selectivity is the ratio of permeability of two gases

As can be seen in Tables 1 and 2, the crosslinked carboxylated intrinsic microporous polymer membrane (Crosslinked PIM-COOH) of the present invention has higher gas permeability than the conventional uncrosslinked carboxylated intrinsic microporous polymer. It can be seen that represents The polymer crosslinked membrane for gas separation membrane (Crosslinked PIM-COOH) comprising the carboxylated intrinsic microporous polymer prepared in Examples 1-5 of the present invention is the conventional carboxylated intrinsic microporous polymer prepared in Comparative Examples 1 and 2. It can be seen that the gas permeability is significantly higher than that of the microporous polymer (PIM-COOH).

In addition, Table 2 shows crosslinked polymer membranes for gas separation membranes (Crosslinked PIM-COOH) containing the carboxylated intrinsic microporous polymer prepared in Examples 1-5 of the present invention prepared in Comparative Examples 1 and 2. Methane for carbon dioxide (CO ₂ /CH ₄ ), nitrogen for carbon dioxide (CO ₂ /N ₂ ), nitrogen for hydrogen (H ₂ /N ₂ ) and oxygen compared to the conventional intrinsic microporous polymer (PIM-1) It can be seen that high selectivity for nitrogen (O ₂ /N ₂ ) gas pair is shown.

Sample CHCl ₃ DMSO THF PIM-1 soluble insoluble soluble PIM-COOH insoluble soluble soluble BD_2wt% insoluble swelling swelling BD_5wt% insoluble swelling swelling PEO500_ 2wt% insoluble swelling swelling PEO500_5wt% insoluble swelling swelling BADGE_5wt% insoluble swelling swelling

In addition, Table 3 summarizes the contents of the solubility test for PIM-1, PIM-COOH, and crosslinked polymer. In solubility experiments using chloroform (CHCl ₃ ), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF), which are good solvents for PIM-1 and PIM-COOH, the crosslinked membrane showed swelling or insolubility. The crosslinked membranes thus prepared showed excellent chemical resistance to the solvents.

1 is a graph showing experimental results for hydrogen permeability and hydrogen and nitrogen selectivity of a cross-linked polymeric membrane according to an embodiment of the present invention. The polymer crosslinked membrane (Crosslinked PIM-COOH) for gas separation membrane comprising the carboxylated intrinsic microporous polymer prepared in Examples 1-5 is more selective than the conventional carboxylated intrinsic porous polymer (PIM-COOH). It can be seen that the gas permeability to hydrogen is remarkably high even without a significant drop in the degree. In addition, the crosslinked membrane prepared from Example 1 exhibits excellent performance exceeding the Robeson upper bound, which is an important criterion for determining the economic feasibility of polymer membranes for hydrogen and nitrogen gas, and is expected to be commercially available.

2 is a graph showing experimental results for oxygen permeability and oxygen and nitrogen selectivity of a cross-linked polymeric film according to an embodiment of the present invention. The polymer crosslinked membrane for gas separation membrane (Crosslinked PIM-COOH) comprising the carboxylated intrinsic microporous polymer prepared in Example 1 has higher selectivity than the conventional carboxylated intrinsic microporous polymer (PIM-COOH). It can be seen that the gas permeability to oxygen is remarkably high without a significant drop. In addition, the crosslinked membrane prepared from Example 1 exhibits excellent performance exceeding the Robeson upper bound, which is an important criterion for determining the economic feasibility of polymer membranes for oxygen and nitrogen gas, and is expected to be commercially available.

3 is a graph showing experimental results for carbon dioxide permeability and carbon dioxide and methane selectivity of a cross-linked polymeric membrane according to an embodiment of the present invention. The polymer crosslinked membrane for gas separation membrane (Crosslinked PIM-COOH) comprising the carboxylated intrinsic microporous polymer prepared in Example 1 has higher selectivity than the conventional carboxylated intrinsic microporous polymer (PIM-COOH). It can be seen that the gas permeability to carbon dioxide is remarkably high without a significant drop.

4 is a graph showing experimental results for carbon dioxide permeability and carbon dioxide and nitrogen selectivity of a cross-linked polymeric membrane according to an embodiment of the present invention. The polymer crosslinked membrane for gas separation membrane (Crosslinked PIM-COOH) comprising the carboxylated intrinsic microporous polymer prepared in Example 1 has higher selectivity than the conventional carboxylated intrinsic microporous polymer (PIM-COOH). It can be seen that the gas permeability to carbon dioxide is remarkably high without a significant drop.

Claims (10)

A polymer providing step of providing a homopolymer, a copolymer or a mixture containing one or more of the compounds represented by Formula 1 below;
A film-forming composition preparation step of mixing the polymer, a crosslinking agent having a chemical structure of Formula 2, and a solvent;
A film forming step of forming a film with the film forming composition and
A method for preparing an intrinsic microporous polymer-based crosslinked polymeric film, comprising the step of preparing a crosslinked polymeric film for crosslinking the film:
<Formula 1>

In Formula 1, X is any one selected from the group consisting of X1 to X17, n is an integer of 10 to 500 as a repeating unit,

<Formula 2>

In Formula 2, R is any one of a straight-chain or branched-chain alkylene group, a straight-chain or branched-chain alkylene group containing an oxygen atom, or an arylene group. delete The method of claim 1,
Method for preparing an intrinsic microporous polymer-based cross-linked polymeric film, characterized in that R in Formula 2 is any one of the following formulas:
-(CH ₂ ) _m -,
-(CH ₂ ) _m -O-(CH ₂ ) _l -,
-CH ₂ -O-(CH ₂ ) ₄ -O-CH ₂ -

Here, m and l are the same or different and are each an integer from 1 to 6, and n is an integer from 1 to 10000. The method of claim 1,
The solvent is 1 selected from the group consisting of tetrahydrofuran (THF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and dimethylacetamide (DMAc). A method for producing an intrinsic microporous polymer-based cross-linked polymeric membrane, characterized in that it is more than species. The method of claim 1,
Method for preparing an intrinsic microporous polymer-based crosslinked polymeric film, characterized in that the step of preparing the crosslinked polymeric film for crosslinking the film is performed through the reaction of Scheme 1 below:
<Scheme 1>

In Scheme 1, n is a repeating unit and an integer of 10 to 500, and R is any one of a straight-chain or branched-chain alkylene group, a straight-chain or branched-chain alkylene group containing an oxygen atom, or an arylene group. Intrinsic microporous polymer-based cross-linking polymeric membrane, characterized in that a homopolymer, copolymer, or a mixture containing one or more of the compounds represented by Formula 1 is cross-linked through a reaction with a cross-linking agent having the chemical structure of Formula 2 below. :
<Formula 1>

In Formula 1, X is any one selected from the group consisting of the following X1 to X17,

<Formula 2>

In Formula 2, R is any one of a straight-chain or branched-chain alkylene group, a straight-chain or branched-chain alkylene group containing an oxygen atom, or an arylene group. delete The method of claim 6,
In Formula 2, R is an intrinsic microporous polymer-based cross-linked polymer film, characterized in that any one of the following formulas:
-(CH ₂ ) _m -,
-(CH ₂ ) _m -O-(CH ₂ ) _l -,
-CH ₂ -O-(CH ₂ ) ₄ -O-CH ₂ -

Here, m and l are the same or different and are each an integer from 1 to 6, and n is an integer from 1 to 10000. The method of claim 6,
The cross-linked polymeric membrane is an intrinsic microporous polymer-based cross-linked polymeric membrane, characterized in that the gas separation membrane. The method of claim 9,
The gas separation membrane is an intrinsic microporous polymer-based cross-linking polymeric membrane, characterized in that the gas separation membrane separates hydrogen from a mixed gas of hydrogen and nitrogen or separates oxygen from a mixed gas of oxygen and nitrogen.

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