CN112275147B - Self-polymerization microporous polyimide gas separation membrane and preparation method and application thereof - Google Patents
Self-polymerization microporous polyimide gas separation membrane and preparation method and application thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
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- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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Abstract
The invention relates to a self-polymerization microporous polyimide gas separation membrane and a preparation method and application thereof, belonging to the technical field of membrane-process gas separation, aiming at preparing a synthetic high-molecular gas separation membrane with high selectivity and high permeability and meeting the requirements of industrial practical application. The invention synthesizes two trapezoidal diamine monomers containing the oxa-naphthalene structure for the first time, and the trapezoidal self-polymerization microporous polyimide polymer containing the oxa-naphthalene structure is synthesized through polycondensation, has good thermal stability and mechanical property, has high selectivity on oxygen/nitrogen, and can meet the practical application of gas separation.
Description
Technical Field
The invention belongs to the technical field of membrane method gas separation, and particularly relates to a self-polymerization microporous polyimide gas separation membrane, and a preparation method and application thereof.
Background
Energy shortage and environmental protection are major problems to be solved urgently in the world at present and are also problems to be solved urgently in socialist production and economic development of China. The gas separation membrane technology is a new green technology, and has been widely paid attention to due to the advantages of low energy consumption, simple equipment, convenient and flexible operation and the like. However, the gas separation performance of conventional membrane materials is not sufficient to meet the industrial requirements, and therefore more and more researchers are beginning to pay attention to novel polymer membrane materials with high separation performance.
The self-polymerization microporous polymer has good thermal stability and film forming property due to the special structural characteristics of the self-polymerization microporous polymer. The twisted molecular structure in the self-polymerized microporous polymer limits the free movement of the main chain and thus prevents the effective accumulation between the polymer chains, resulting in uniform micropores inside the polymer membrane, which has excellent gas permeability.
Polyimides have excellent thermal, chemical and mechanical properties and are one of the important high performance glassy polymers. Can be widely applied to the aerospace industry, the electronic industry, high-temperature adhesives, separation membranes, composite materials and the like. Has good thermal stability and film forming property and is widely favored by researchers. And polyimide has excellent gas selectivity as a gas separation membrane, but the gas flux is low.
Disclosure of Invention
In order to overcome the defects of the prior art, meet the requirements of industrial practical application and synthesize a high-molecular gas separation membrane with high selectivity and high permeability, the invention provides a self-polymerization microporous polyimide gas separation membrane, a preparation method and application thereof.
The design concept of the invention is as follows: the self-polymerization microporous polyimide main chain contains a trapezoidal structure, the distance between high molecular chains is increased, the separation and diffusion of gas are facilitated, the hydrogen bond effect between polymer molecules is reduced, and the solubility of the polymer is improved.
The invention is realized by the following technical scheme.
A self-polymerization microporous polyimide gas separation membrane, wherein the polymer of the self-polymerization microporous polyimide gas separation membrane is a homopolymer or a random copolymer, and the structural general formula of the self-polymerization microporous polyimide gas separation membrane is as follows:
wherein n represents the degree of polymerization, and n is a positive integer of 10-200; the polymer has a weight average molecular weight of 5000-; r1Is a diamine monomer with an oxa-bridged naphthalene ring structure, has the same structure as
Ladder structures of Base or Kanger's ether, R1Represents one or more of the following structures:
R2represents one or more of the following structures:
further, the diamine monomer of the oxa-bridged naphthalene ring structure is one or more of the following structures:
a preparation method of a self-polymerization microporous polyimide gas separation membrane comprises the following steps:
(1) under the nitrogen atmosphere, adding m-cresol solution into a three-mouth round-bottom bottle filled with an oxa-bridged naphthalene cyclic diamine monomer, and adding R after the oxa-bridged naphthalene cyclic diamine monomer is completely dissolved2One or two dianhydrides of structure (I) to have R2Adding isoquinoline into the solution after the dianhydride with the structure is completely dissolved, and adding oxa-bridged naphthalene ring diamine monomer and R in the reaction system2The dianhydride with the structure has the concentration of 15-20 wt% in the m-cresol solution, and the monomer of oxa-bridged naphthalene ring diamine has R2The molar ratio of dianhydride to isoquinoline is 1:1: 2; heating the reaction system to 80 ℃ for reaction for 4 hours, and then heating to 180 ℃ for reaction for 12 hours to obtain viscous reaction liquid;
(2) after the viscous reaction liquid prepared in the step (1) is cooled to room temperature, precipitating in a methanol solution to prepare a fibrous polymer, washing for a plurality of times, and then drying the obtained polymer at 100 ℃ for 12 hours in vacuum to prepare the polyimide polymer with micropores;
(3) dissolving the polyimide polymer with micropores prepared in the step (2) in a polar solvent to obtain a casting solution with the concentration of 5-10 wt%; and (3) after filtering the casting solution, pouring the casting solution on a clean horizontal glass plate, and drying for 6-20 hours in vacuum at the temperature of 60-100 ℃ to obtain the polyimide polymer film with the micropores.
Further, the thickness of the polyimide polymer film with micropores prepared in the step (3) is 30-70 μm.
Further, the preparation method of the diamine monomer with an oxabridged naphthalene ring structure in the step (1) comprises the following steps:
(1) firstly, adding a mixed solvent of tetrahydrofuran and trifluoroacetic acid into a flask filled with 2-naphthol in a nitrogen atmosphere, wherein the volume ratio of the tetrahydrofuran to the trifluoroacetic acid in the mixed solvent is 1: 2; next, to the mixed solvent was dropwise added malonic acetal with stirring, and the resulting mixture was reacted at room temperature for 3 hours, and then saturated NaHCO was added thereto3Adjusting the pH value of the aqueous solution to 7, and carrying out quenching reaction; extracting with dichloromethane for three times, separating the organic phase, drying with anhydrous sodium sulfate, and removing the solvent by rotary evaporation to obtain a crude product; finally, column chromatography is carried out [ SiO ]2V (petroleum ether) to V (dichloromethane) is 6: 1]Separating to obtain pure white solid monomer with oxa-bridged naphthalene ring structure;
(2) firstly, suspending and dissolving the white solid prepared in the step (1) in a glacial acetic acid solution, uniformly stirring, then heating to 50-60 ℃, and slowly dropwise adding a mixed solution of concentrated nitric acid and glacial acetic acid into the glacial acetic acid solution; secondly, continuously stirring for reaction for 3 hours, pouring into ice water while the mixture is hot, and quenching the reaction; washing with deionized water, 10 wt% concentration sodium hydroxide solution and ethanol to obtain yellow solid dinitro small molecule coarse product; finally, separating by column chromatography [ SiO2, V (petroleum ether): (6: 1) V (dichloromethane) ] to obtain pure oxa-bridged naphthalene ring dinitro monomer;
(3) dissolving the oxa-bridged naphthalene ring dinitro monomer prepared in the step (2) and a palladium-carbon catalyst with the concentration of 10 wt% in a 1, 4-dioxane solution in a nitrogen atmosphere, reacting, mixing and heating to reflux, dropwise adding hydrazine hydrate into the reaction solution by using a dropping funnel, and carrying out reflux reaction for 12 hours; the reaction product is filtered while hot and then is subjected to vacuum rotary evaporation to prepare the white oxabridged naphthalene cyclic diamine monomer.
The application of a self-polymerized microporous polyimide gas separation membrane comprises the following steps:
(1) soaking the self-polymerization microporous polyimide gas separation membrane in methanol for 10-20 hours, and then carrying out vacuum drying at 80-120 ℃ for 12-24 hours;
(2) and (2) placing the dried gas separation membrane obtained in the step (1) in a gas separation device for testing gas separation performance.
Further, a gas separation device is fixed on a test cell, the separation performance of the self-polymerization microporous polyimide gas separation membrane is tested by adopting a constant volume pressure changing method, and the test area is 0.3cm2The upstream pressure was 0.6MPa, the test temperature was 35 ℃ and the downstream pressure was monitored.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention synthesizes two trapezoidal diamine monomers containing an oxa-naphthalene structure for the first time;
2. synthesizing a trapezoidal self-polymerization microporous polyimide polymer containing an oxa-naphthalene structure through a polycondensation reaction;
3. the obtained polyimide polymer with micropores can be well dissolved in a polar solvent, the gas separation membrane has good thermal stability and mechanical property, the decomposition temperature of the polymer can reach 400-600 ℃, and the tensile strength can reach 80-120 MPa;
4. the obtained polyimide polymer with micropores has high selectivity to oxygen/nitrogen, and can meet the practical application of gas separation.
Drawings
FIG. 1 is a nuclear magnetic spectrum of a five-membered oxabridged naphthalene ring diamine monomer (A) prepared in example 1;
FIG. 2 is a nuclear magnetic spectrum of a six-membered oxabridged naphthalene ring dinitro monomer prepared in example 2;
FIG. 3 is a thermogravimetric analysis curve of the polymer prepared in example 4.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. Unless otherwise specified, the examples follow conventional experimental conditions. In addition, it will be apparent to those skilled in the art that various modifications or improvements can be made to the material components and amounts in these embodiments without departing from the spirit and scope of the invention as defined in the appended claims.
Synthesis of oxabridged naphthalene ring structural monomer.
Example 1
(1) To a round bottom flask containing 1.5282 g of 2-naphthol was added a 9 ml mixed solvent of tetrahydrofuran/trifluoroacetic acid (V: V ═ 1:2) under a nitrogen atmosphere. 0.3076 g of glyoxal were added dropwise with stirring, and after the resulting mixture had reacted at room temperature for 3 hours, saturated NaHCO was added thereto3The reaction was quenched with aqueous solution, pH adjusted to 7. After that, extraction with dichloromethane was carried out three times (30 mL. times.3), the organic phase was separated and dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation to obtain a crude product. Finally, column chromatography is carried out on the product [ SiO ]2V (petroleum ether) to V (dichloromethane) is 6: 1]Separating to obtain white cotton wool needle-like five-membered ring oxa-bridged naphthalene ring structural monomer (7a,14 c-dihydronaphtho [2, 1-b)]Naphtho [1',2':4,5 ]]Furo [3,2-d ] s]Furan) in 70% yield;
(2) suspending and dissolving 2 g of the white monomer obtained in the step (1) in 80 ml of glacial acetic acid solution, uniformly stirring, heating to 50-60 ℃, and slowly dropwise adding a mixed solution of 4 ml of concentrated nitric acid and 20 ml of acetic acid. Then, the reaction was stirred for 3 hours and poured into ice water while the mixture was still hot to quench the reaction. Washing with deionized water, 10 wt% sodium hydroxide solution and ethanol to obtain yellow solid dinitro small molecule crude product. By column chromatography [ SiO ]2V (petroleum ether) to V (dichloro)Methane) ═ 1:1]Separating to obtain a light yellow five-membered oxa-bridged naphthalene ring dinitro monomer with the yield of 83 percent;
(3) dissolving the five-membered ring oxa-bridged naphthalene ring dinitro monomer obtained in the step (2) and 10 wt% palladium carbon catalyst in 150 ml of 1, 4-dioxane, mixing and heating the reaction until reflux, dropwise adding hydrazine hydrate into the reaction solution by using a dropping funnel, and then carrying out reflux reaction for 12 hours. Filtering while the mixture is hot, and then carrying out vacuum rotary evaporation to obtain a white five-membered oxabridged naphthalene ring diamine monomer A with the yield of 95 percent.
Example 2
(1) To a round bottom flask containing 0.995 g of 2-naphthol was added 9 ml of a mixed solvent of tetrahydrofuran/trifluoroacetic acid (V: V ═ 1:2) under a nitrogen atmosphere. 0.576 g of 1,1,3, 3-tetramethoxypropane was added dropwise under stirring, and after the resulting mixture was reacted at room temperature for 3 hours, saturated NaHCO was added thereto3The reaction was quenched with aqueous solution, pH adjusted to 7. After that, extraction with dichloromethane was carried out three times (30 mL. times.3), the organic phase was separated and dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation to obtain a crude product. Finally, column chromatography is carried out on the product [ SiO ]2V (petroleum ether) to V (dichloromethane) is 6: 1]Separating to obtain white six-membered ring oxabridged naphthalene ring structural monomer (16H-8, 16-methyl dinaphtho [2,1-d:1',2' -g)][1,3]Dioxane) with a yield of 87%;
(2) suspending and dissolving 2 g of the white monomer obtained in the step (1) in 80 ml of glacial acetic acid solution, uniformly stirring, heating to 50-60 ℃, and slowly dropwise adding a mixed solution of 4.5 ml of concentrated nitric acid and 20 ml of acetic acid. Then, the reaction was stirred for 4 hours and poured into ice water while the mixture was still hot to quench the reaction. Washing with deionized water, 10 wt% sodium hydroxide solution and ethanol to obtain yellow solid dinitro small molecule crude product. By column chromatography [ SiO ]2V (petroleum ether) to V (dichloromethane) 2: 1]Separating to obtain a brown yellow six-membered oxa-bridged naphthalene dinitro monomer with a yield of 88 percent;
(3) dissolving 1.0 g of the hexatomic ring oxabridged naphthalene ring dinitro monomer obtained in the step (2) and 0.01 g of 10 wt% palladium carbon catalyst in 50 ml of 1, 4-dioxane under a nitrogen atmosphere, reacting, mixing and heating to reflux, dropwise adding hydrazine hydrate into the reaction solution by using a dropping funnel, and then refluxing for reaction for 12 hours. The mixture was filtered while hot and then rotary evaporated in vacuo to give white hexatomic oxabridged naphthalene ring diamine monomer B in 95% yield.
The synthesis of (di) oxabridged naphthalene ring structure from microporous polyimide polymer.
Example 3
(1) Under the atmosphere of nitrogen, 12 ml of m-cresol is added into a three-mouth round-bottom bottle containing 0.85 g of monomer A, 1.11 g of 6FDA is added after complete dissolution, 0.7 ml of isoquinoline is added after complete dissolution, the temperature is increased to 80 ℃ for reaction for 4 hours, and then the temperature is increased to 180 ℃ for reaction for 12 hours. After the viscous reaction liquid is cooled to room temperature, fibrous polymer is obtained by precipitation in methanol solution, and the obtained polymer is dried for 12 hours in vacuum at 100 ℃ after 4 times of washing. The A-6FDA polymer was obtained in a yield of 94%; the A-6FDA polymer structure is shown below:
(2) 0.5 g of A-6FDA polymer is dissolved in 6.25 ml of N-methylpyrrolidone (NMP) to obtain 8% of casting solution, and after filtration, the casting solution is poured on a clean horizontal glass plate and dried for 12 hours at 80 ℃ to obtain a polymer film with the thickness of about 45 microns. At 35 ℃, the gas separation membrane pair is O2And CO2Respectively, are 7.5Barrer and 34.3Barrer, O2/N2And CO2/CH4Has a permselectivity of 5.6 and 47.4.
Example 4
(1) Under the nitrogen atmosphere, 13 ml of m-cresol is added into a three-mouth round-bottom bottle containing 0.89 g of B monomer, 1.11 g of 6FDA is added after complete dissolution, 0.7 ml of isoquinoline is added after complete dissolution, the temperature is increased to 80 ℃ for reaction for 4 hours, and then the temperature is increased to 180 ℃ for reaction for 12 hours. After the viscous reaction liquid is cooled to room temperature, fibrous polymer is obtained by precipitation in methanol solution, and the obtained polymer is dried for 12 hours in vacuum at 100 ℃ after 4 times of washing. B-6FDA polymer was obtained in about 95% yield;
the B-6FDA polymer has the following structural formula:
(2) dissolving 0.5 g of B-6FDA polymer in 5 ml of NMP to obtain 10% of casting solution, filtering, pouring the casting solution on a clean horizontal glass plate, and drying at 80 ℃ for 12 hours to obtain a polymer film with the thickness of about 50 microns. At 35 ℃, the gas separation membrane pair is O2And CO2Respectively 6.0Barrer and 30.3Barrer, O2/N2And CO2/CH4Has a permselectivity of 5.5 and 43.2.
Example 5
(1) Under the atmosphere of nitrogen, 10 ml of m-cresol is added into a three-mouth round-bottom bottle containing 0.85 g of A monomer, 0.555 g of 6FDA and 0.368 g of BPDA are added after complete dissolution, 0.7 ml of isoquinoline is added after complete dissolution, the temperature is increased to 80 ℃ for reaction for 4 hours, and the temperature is increased to 180 ℃ for reaction for 12 hours. After the viscous reaction liquid is cooled to room temperature, fibrous polymer is obtained by precipitation in methanol solution, and the obtained polymer is dried for 12 hours in vacuum at 100 ℃ after 4 times of washing. A-6FDA/BPDA polymer is obtained with a yield of about 95%;
the A-6FDA/BPDA polymer has the following structural formula:
wherein m is n-1;
(2) 0.5 g of A-6FDA/BPDA polymer is dissolved in 5 ml of NMP to obtain 10% of casting solution, and after filtration, the casting solution is poured on a clean horizontal glass plate and dried at 80 ℃ for 12 hours to obtain a polymer film with the thickness of about 48 microns. At 35 ℃, the gas separation membrane pair is O2And CO2Respectively, are 20.0Barrer and 103.5Barrer, O2/N2And CO2/CH4The permselectivity of (a) was 5.0 and 45.0.
Example 6
(1) Under the atmosphere of nitrogen, 12 ml of m-cresol is added into a three-mouth round-bottom bottle containing 0.85 g of A monomer, 0.555 g of 6FDA and 0.4028 g of BTDA are added after complete dissolution, 0.7 ml of isoquinoline is added after complete dissolution, the temperature is increased to 80 ℃ for reaction for 4 hours, and the temperature is increased to 180 ℃ for reaction for 12 hours. After the viscous reaction liquid is cooled to room temperature, fibrous polymer is obtained by precipitation in methanol solution, and the obtained polymer is dried for 12 hours in vacuum at 100 ℃ after 4 times of washing. The A-6FDA/BTDA polymer is obtained, and the yield is about 95%;
the structural formula is as follows:
wherein m is n-1;
(2) 0.5 g of A-6FDA/BTDA polymer is dissolved in 5 ml of NMP to obtain 10% of casting solution, and after filtration, the casting solution is poured on a clean horizontal glass plate and dried for 12 hours at 80 ℃ to obtain a polymer film with the thickness of about 58 microns. At 35 ℃, the gas separation membrane pair is O2And CO2Respectively has a permeability coefficient of 18.7Barrer and 83.34Barrer, O2/N2And CO2/CH4Has a permselectivity of 5.2 and 46.3.
Example 7
(1) Under the atmosphere of nitrogen, 12 ml of m-cresol is added into a three-mouth round-bottom bottle containing 0.89 g of B monomer, 0.555 g of 6FDA and 0.368 g of BPDA are added after complete dissolution, 0.7 ml of isoquinoline is added after complete dissolution, the temperature is increased to 80 ℃ for reaction for 4 hours, and the temperature is increased to 180 ℃ for reaction for 12 hours. After the viscous reaction liquid is cooled to room temperature, fibrous polymer is obtained by precipitation in methanol solution, and the obtained polymer is dried for 12 hours in vacuum at 100 ℃ after 4 times of washing. B-6FDA/BPDA polymer is obtained with a yield of about 95%;
the structural formula of the B-6FDA/BPDA polymer is shown as follows:
wherein m is n-1;
(2) 0.5 g of B-6FDA/BPDA polymer is dissolved in 5 ml of NMP to obtain 10% of casting solution, and after filtration, the casting solution is poured on a clean horizontal glass plate and dried for 12 hours at 80 ℃ to obtain a polymer film with the thickness of about 55 microns. At 35 ℃, the gas separation membrane pair is O2And CO2Respectively has a permeability coefficient of 20.5Barrer and 99.7Barrer, O2/N2And CO2/CH4The permselectivity of (a) was 5.0 and 41.5.
Example 8
(1) Under the atmosphere of nitrogen, 12 ml of m-cresol is added into a three-mouth round-bottom bottle containing 0.89 g of B monomer, 0.555 g of 6FDA and 0.4028 g of BTDA are added after complete dissolution, 0.7 ml of isoquinoline is added after complete dissolution, the temperature is increased to 80 ℃ for reaction for 4 hours, and the temperature is increased to 180 ℃ for reaction for 12 hours. After the viscous reaction liquid is cooled to room temperature, fibrous polymer is obtained by precipitation in methanol solution, and the obtained polymer is dried for 12 hours in vacuum at 100 ℃ after 4 times of washing. B-6FDA/BTDA polymer was obtained with a yield of about 95%;
the structural formula of the B-6FDA/BTDA polymer is shown as follows:
(2) 0.5 g of B-6FDA/BTDA polymer was dissolved in 5 ml of NMP to obtain a 10% casting solution, which was filtered and poured onto a clean horizontal glass plate and dried at 80 ℃ for 12 hours to obtain a polymer film having a thickness of about 61 μm. At 35 ℃, the gas separation membrane pair is O2And CO2Respectively, are 17.7Barrer and 72.8Barrer, O2/N2And CO2/CH4Has a permselectivity of 5.7 and 48.5.
Example 9
(1) Under the nitrogen atmosphere, 26 ml of m-cresol is added into a three-mouth round-bottom bottle containing 0.85 g of A monomer and 0.89 g of B monomer, 2.22 g of 6FDA is added after complete dissolution, 1.4 ml of isoquinoline is added after complete dissolution, the temperature is increased to 80 ℃ for reaction for 4 hours, and the temperature is increased to 180 ℃ for reaction for 12 hours. After the viscous reaction liquid is cooled to room temperature, fibrous polymer is obtained by precipitation in methanol solution, and the obtained polymer is dried for 12 hours in vacuum at 100 ℃ after 4 times of washing. The A/B-6FDA polymer is obtained, and the yield is about 97 percent;
the structural formula of the A/B-6FDA polymer is shown as follows:
wherein: m: n is 1: 1;
(2) 0.5 g of A/B-6FDA polymer is dissolved in 5 ml of NMP to obtain 10% of casting solution, the casting solution is poured on a clean horizontal glass plate after filtration, and the casting solution is dried for 12 hours at 80 ℃ to obtain a polymer film with the thickness of about 53 microns. At 35 ℃, the gas separation membrane pair is O2And CO2Respectively 5.8Barrer and 32.0Barrer, O2/N2And CO2/CH4Has a permselectivity of 5.3 and 45.7.
Example 10
(1) Under the atmosphere of nitrogen, 25 ml of m-cresol is added into a three-mouth round-bottom bottle containing 0.68 g of A monomer and 1.06 g of B monomer, 1.11 g of 6FDA and 0.545 g of PMDA are added after complete dissolution, 1.4 ml of isoquinoline is added after complete dissolution, the temperature is increased to 80 ℃ for reaction for 4 hours, and then the temperature is increased to 180 ℃ for reaction for 12 hours. After the viscous reaction liquid is cooled to room temperature, fibrous polymer is obtained by precipitation in methanol solution, and the obtained polymer is dried for 12 hours in vacuum at 100 ℃ after 4 times of washing. The A/B-6FDA/PMDA polymer is obtained, and the yield is about 97%;
the structural formula is as follows:
wherein (m + X) is (n + Y) 1: 1; (m + n): 2:3 (X + Y);
(2) 0.5 g of A/B-6FDA/PMDA polymer is dissolved in 5 ml of NMP to obtain 10 percent of casting solution, and after filtration, the casting solution is poured on a clean horizontal glass plate and dried for 12 hours at 80 ℃ to obtain a polymer film with the thickness of about 61 microns. At 35 ℃, the gas separation membrane pair is O2And CO2Respectively has a permeability coefficient of 99.4Barrer and 408.9Barrer, O2/N2And CO2/CH4Has a permselectivity of 6.1 and 48.1.
Example 11
(1) Under the nitrogen atmosphere, 11 ml of m-cresol is added into a three-mouth round-bottom bottle filled with 0.89 g of E monomer, 1.11 g of 6FDA is added after complete dissolution, 0.7 ml of isoquinoline is added after complete dissolution, the temperature is increased to 80 ℃ for reaction for 4 hours, and then the temperature is increased to 180 ℃ for reaction for 12 hours. After the viscous reaction liquid is cooled to room temperature, fibrous polymer is obtained by precipitation in methanol solution, and the obtained polymer is dried for 12 hours in vacuum at 100 ℃ after 4 times of washing. E-6FDA polymer was obtained in about 97% yield.
The structural formula is as follows:
(2) dissolving 0.5 g of E-6FDA polymer in 5 ml of NMP to obtain 10% of casting solution, filtering, pouring the casting solution on a clean horizontal glass plate, and drying at 80 ℃ for 12 hours to obtain a polymer film with the thickness of about 47 microns. At 35 ℃, the gas separation membrane pair is O2And CO2Has a permeability coefficient of 98.0Barrer and 503.8Barrer, O2/N2And CO2/CH4Has a permselectivity of 4.6 and 40.3.
Example 12
(1) Under the nitrogen atmosphere, 27 ml of m-cresol is added into a three-mouth round-bottom bottle containing 0.89 g of B monomer and 0.89 g of C monomer, 2.22 g of 6FDA is added after complete dissolution, 1.4 ml of isoquinoline is added after complete dissolution, the temperature is increased to 80 ℃ for reaction for 4 hours, and the temperature is increased to 180 ℃ for reaction for 12 hours. After the viscous reaction liquid is cooled to room temperature, fibrous polymer is obtained by precipitation in methanol solution, and the obtained polymer is dried for 12 hours in vacuum at 100 ℃ after 4 times of washing. B/C-BTDA polymer is obtained with a yield of about 97%;
the structural formula of the B/C-BTDA polymer is shown as follows:
wherein: m: n is 1: 1;
(2) dissolving 0.5 g of B/C-BTDA polymer in 5 ml of NMP to obtain 10% of casting solution, filtering, pouring the casting solution on a clean horizontal glass plate, and drying at 80 ℃ for 12 hours to obtain a polymer film with the thickness of about 55 microns. At 35 ℃, the gas separation membrane pair is O2And CO2Respectively have permeability coefficients of 90.3Barrer and 418.1Barrer, O2/N2And CO2/CH4The permselectivity of (a) was 5.1 and 43.1.
Example 13
(1) Under the atmosphere of nitrogen, 11 ml of m-cresol is added into a three-mouth round-bottom bottle containing 0.89 g of C monomer, 0.776 g of ODPA is added after complete dissolution, 0.7 ml of isoquinoline is added after complete dissolution, the temperature is increased to 80 ℃ for reaction for 4 hours, and then the temperature is increased to 180 ℃ for reaction for 12 hours. After the viscous reaction liquid is cooled to room temperature, fibrous polymer is obtained by precipitation in methanol solution, and the obtained polymer is dried for 12 hours in vacuum at 100 ℃ after 4 times of washing. The C-ODPA polymer was obtained in a yield of about 97%.
The structural formula of the C-ODPA polymer is shown as follows:
(2) dissolving 0.5 g of C-ODPA polymer in 5 ml of NMP to obtain 10% of membrane casting solution, filtering, pouring the membrane casting solution into a clean containerThe glass plate was dried at 80 ℃ for 12 hours to obtain a polymer film having a thickness of about 45 μm. At 35 ℃, the gas separation membrane pair is O2And CO2Has a permeability coefficient of 73.0Barrer and 138.6Barrer, O2/N2And CO2/CH4Has a permselectivity of 4.8 and 38.5.
Example 14
(1) Under the atmosphere of nitrogen, 21.5 ml of m-cresol is added into a three-mouth round-bottom bottle containing 0.89G of F monomer and 0.89G of G monomer, 1.47G of BPDA is added after complete dissolution, 1.4 ml of isoquinoline is added after complete dissolution, the temperature is increased to 80 ℃ for reaction for 4 hours, and the temperature is increased to 180 ℃ for reaction for 12 hours. After the viscous reaction liquid is cooled to room temperature, fibrous polymer is obtained by precipitation in methanol solution, and the obtained polymer is dried for 12 hours in vacuum at 100 ℃ after 4 times of washing. The F/G-BPDA polymer is obtained with the yield of about 97 percent;
the structural formula of the F/G-BPDA polymer is shown as follows:
wherein: m: n is 1: 1;
dissolving 0.5G of F/G-BPDA polymer in 5 ml of NMP to obtain 10% of casting solution, filtering, pouring the casting solution on a clean horizontal glass plate, and drying at 80 ℃ for 12 hours to obtain a polymer film with the thickness of about 52 microns. At 35 ℃, the gas separation membrane pair is O2And CO2Has permeability coefficients of 87.3Barrer and 448.6Barrer, O2/N2And CO2/CH4Has a permselectivity of 4.3 and 39.7.
Example 15: gas separation test:
fixing the obtained separation membrane on a test cell, and testing the separation performance by adopting a constant-volume variable-pressure method, wherein the test area is about 0.3cm2The upstream pressure is controlled to be about 0.6MPa, the testing temperature is 35 ℃, and the downstream pressure is monitored.
The following table shows the gas separation test results for each film formed and tested.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (7)
1. A self-polymerization microporous polyimide gas separation membrane is characterized in that: the polymer of the self-polymerization microporous polyimide gas separation membrane is a homopolymer, and the structural general formula of the polymer is as follows:
wherein n represents the degree of polymerization, and n is a positive integer of 10-200; the polymer has a weight average molecular weight of 5000-; r1Is a diamine monomer with an oxa-bridged naphthalene ring structure, has the same structure as
Ladder structures of Base or Kanger's ether, R1Represents one or more of the following structures:
R2represents one or more of the following structures:
2. the self-polymerizing microporous polyimide gas separation membrane of claim 1, wherein: the diamine monomer of the oxa-bridged naphthalene ring structure is one or more of the following structures:
3. the method of claim 1 for preparing a self-polymeric microporous polyimide gas separation membrane, comprising the steps of:
(1) under the nitrogen atmosphere, adding m-cresol solution into a three-mouth round-bottom bottle filled with an oxa-bridged naphthalene cyclic diamine monomer, and adding R after the oxa-bridged naphthalene cyclic diamine monomer is completely dissolved2One or two dianhydrides of structure (I) to have R2Adding isoquinoline into the solution after the dianhydride with the structure is completely dissolved, and adding oxa-bridged naphthalene ring diamine monomer and R in the reaction system2The dianhydride with the structure has the concentration of 15-20 wt% in the m-cresol solution, and the monomer of oxa-bridged naphthalene ring diamine has R2The molar ratio of dianhydride to isoquinoline is 1:1: 2; heating the reaction system to 80 ℃ for reaction for 4 hours, and then heating to 180 ℃ for reaction for 12 hours to obtain viscous reaction liquid;
(2) after the viscous reaction liquid prepared in the step (1) is cooled to room temperature, precipitating in a methanol solution to prepare a fibrous polymer, washing for a plurality of times, and then drying the obtained polymer at 100 ℃ for 12 hours in vacuum to prepare the polyimide polymer with micropores;
(3) dissolving the polyimide polymer with micropores prepared in the step (2) in a polar solvent to obtain a casting solution with the concentration of 5-10 wt%; and (3) after filtering the casting solution, pouring the casting solution on a clean horizontal glass plate, and drying for 6-20 hours in vacuum at the temperature of 60-100 ℃ to obtain the polyimide polymer film with the micropores.
4. The method of claim 3, wherein the method comprises the steps of: the thickness of the polyimide polymer film with the micropores prepared in the step (3) is 30-70 mu m.
5. The method of claim 3, wherein the method comprises the steps of: the preparation method of the diamine monomer with the oxabridged naphthalene ring structure in the step (1) comprises the following steps:
(1) firstly, adding a mixed solvent of tetrahydrofuran and trifluoroacetic acid into a flask filled with 2-naphthol in a nitrogen atmosphere, wherein the volume ratio of the tetrahydrofuran to the trifluoroacetic acid in the mixed solvent is 1: 2; next, to the mixed solvent was dropwise added malonic acetal with stirring, and the resulting mixture was reacted at room temperature for 3 hours, and then saturated NaHCO was added thereto3Adjusting the pH value of the aqueous solution to 7, and carrying out quenching reaction; extracting with dichloromethane for three times, separating the organic phase, drying with anhydrous sodium sulfate, and removing the solvent by rotary evaporation to obtain a crude product; finally, separating by column chromatography to prepare a pure white solid oxa-bridged naphthalene ring structural monomer;
(2) firstly, suspending and dissolving the white solid prepared in the step (1) in a glacial acetic acid solution, uniformly stirring, then heating to 50-60 ℃, and slowly dropwise adding a mixed solution of concentrated nitric acid and glacial acetic acid into the glacial acetic acid solution; secondly, continuously stirring for reaction for 3 hours, pouring into ice water while the mixture is hot, and quenching the reaction; washing with deionized water, 10 wt% concentration sodium hydroxide solution and ethanol to obtain yellow solid dinitro small molecule coarse product; finally, separating by column chromatography to obtain pure oxa-bridged naphthalene ring dinitro monomer;
(3) dissolving the oxa-bridged naphthalene ring dinitro monomer prepared in the step (2) and a palladium-carbon catalyst with the concentration of 10 wt% in a 1, 4-dioxane solution in a nitrogen atmosphere, reacting, mixing and heating to reflux, dropwise adding hydrazine hydrate into the reaction solution by using a dropping funnel, and carrying out reflux reaction for 12 hours; the reaction product is filtered while hot and then is subjected to vacuum rotary evaporation to prepare the white oxabridged naphthalene cyclic diamine monomer.
6. The use of a self-polymerizing microporous polyimide gas separation membrane according to claim 1, comprising the steps of:
(1) soaking the self-polymerization microporous polyimide gas separation membrane in methanol for 10-20 hours, and then carrying out vacuum drying at 80-120 ℃ for 12-24 hours;
(2) and (2) placing the dried gas separation membrane obtained in the step (1) in a gas separation device for testing gas separation performance.
7. Use according to claim 6, characterized in that: fixing a gas separation device on a test cell, and testing the separation performance of the self-polymerization microporous polyimide gas separation membrane by adopting a constant-volume pressure-changing method, wherein the test area is 0.3cm2The upstream pressure was 0.6MPa, the test temperature was 35 ℃ and the downstream pressure was monitored.
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