CN104829853B - A kind of polyimide gas separating film and preparation method and application - Google Patents

A kind of polyimide gas separating film and preparation method and application Download PDF

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CN104829853B
CN104829853B CN201510249582.1A CN201510249582A CN104829853B CN 104829853 B CN104829853 B CN 104829853B CN 201510249582 A CN201510249582 A CN 201510249582A CN 104829853 B CN104829853 B CN 104829853B
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amino
polyimide
gas
dimethylphenyls
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CN104829853A (en
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范琳
佟辉
杨士勇
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Institute of Chemistry CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The invention discloses a kind of polyimide gas separating film and preparation method and application, the seperation film is made using the polyimide resin with fluorine-containing benzene lateral group structure shown in formula I.The polyimide gas separating film has the characteristics of high osmosis and high selectivity concurrently, to CO2Infiltration coefficient >=180barrer, to CO2/CH4Selection coefficient more than 30, while seperation film shows excellent heat resistance and mechanical property.Recovery of carbon dioxide etc. is many in the removal of the sour gas such as the separation of carbon dioxide and methane, carbon dioxide in natural, tertiary oil production in oil field in including biogas is related to CO for this kind of gas separation membrane2Separation in recovery with having important application value.

Description

A kind of polyimide gas separating film and preparation method and application
Technical field
The present invention relates to technical field of membrane, is specifically related to a kind of high osmosis, the separation of high selectivity copolyimide gas Film and preparation method and application.
Background technology
Gas is separated using membrane separation process due to separative efficiency is high, energy loss is low, green, operation Simply, it is safe and reliable and be easily installed the advantages such as debugging, separated in recent years in industrial gasses with having been obtained increasingly in purifying It is widely applied.Membrane material is the core of gas separation membrane technology, and current commercialized gas separation membrane material is mainly fiber The polymer film such as plain (CA), polysulfones (PSF), dimethyl silicone polymer (PDMS), polyphenylene oxide (PPO).But these gases separate The heat resistance of film is not ideal enough, and glass transition temperature is no more than 200 DEG C, therefore has the application of particular/special requirement to temperature at some In be limited.
Polyimides (PI) material is due to prominent heat resistance, mechanical property and good chemical stability, simultaneously Have excellent gas-selectively concurrently, be related to the acidic corrosive gas such as HTHP and carbon dioxide at some in recent years Separation application in receive much attention.But because polyimides is present than stronger intermolecular force, strand arrangement compared with Densification, fractional free volume is relatively low, although causing polyimide separation membrane with excellent gas-selectively, gas infiltration Property is not ideal enough, and commercialized polyimide separation membrane is to CO2Infiltration coefficient be only 10barrer.Researcher passes through poly- The group of large volume is introduced in acid imide molecular structure to improve fractional free volume, so as to improve the gas of polyimide separation membrane Body permeability.Ayala et al. is by using double (3,4- dicarboxyls benzoyl) the tertiary fourths of 5- of the dianhydride 1,3- containing large volume side base Base benzene and double (the 3,4- dicarboxyls benzoyl) biphenyl of 1,3- polymerize with double (4- aminophenyls) HFC-236fas of aromatic diamines 2,2- To polyimides, its glass transition temperature is 265 DEG C, and polyimide separation membrane prepared therefrom has excellent gas-selectively, To CO2Infiltration coefficient bring up to 15.6barrer (Ayala D, Lozano AE, de Abajo J, Garcia-Perez C, de la Campa JG,Peinemann KV,Freeman BD,Prabhakar R,Gas separation properties of aromatic polyimides.J Membr Sci,2003,215,61-73).The A of CN 101733027 disclose a kind of base In the double-end amino polyethers with backbone and 1,3- phenylenediamines and fluorine-containing aromatic dianhydride 4,4 '-(2,2- hexafluoro isopropyls) two Polyimide separation membrane prepared by phthalic anhydride (6FDA) copolymerization, because polymer has been broken in the introducing of long-chain copolymeric structure The original regular arrangement of strand, therefore make the gas separation membrane to CO2Infiltration coefficient bring up to 77.89barrer, to CO2/ CH4Selection coefficient be up to 20.03.The artificial gas permeability for further improving polyimide separation membrane such as Calle, Employ the 3,3,3 of massive structure ", 4 "-(5 '-tert-butyl group-trimethylbenzene) tetracarboxylic acid dianhydride and 2,4,6- trimethyl isophthalic Diamines prepares polyimide separation membrane, and the seperation film shows excellent gas permeability, to CO2Infiltration coefficient be up to 465barrer, but at the same time gas-selectively is remarkably decreased, to CO2/CH4Selection coefficient as little as 11.7 (Calle M, Garcia C,Lozano AE,de la Campa JG,de Abajo J,Alvarez C,Local chain mobility dependence on molecular structure in polyimides with bulky side groups: Correlation with gas separation properties,J Membr Sci,2013,434,121-129)。
The content of the invention
It is an object of the invention to overcome deficiency of the prior art, there is provided a kind of by poly- with fluorine-containing benzene lateral group structure High osmosis that imide resin is prepared, the polyimide gas separating film of high selectivity.
It is another object of the present invention to provide the preparation method and application of above-mentioned resin and gas separation membrane.
To achieve the above object, the present invention provides following technical scheme：
A kind of polyimide gas separating film, the seperation film is by the polyimide resin system with fluorine-containing benzene lateral group structure , the polyimide resin has the general structure shown in following formula I：
Wherein, any one of Ar in following radicals：
X is CH3Or F,
Y is H or CH3,
L, M, N are identical or different, are independently from each other H, F or CF3, also, at least one in L, M, N be F or Person CF3,
N is 50~300 integer.
According to the present invention, the number-average molecular weight (M of the polyimide resinn) between 50000~200000g/mol.
According to the present invention, the thickness of the seperation film is 25~75 μm.The gas separation membrane has high gas permeability concurrently With high gas-selectively, specifically, to CO2Infiltration coefficient PCO2>=180barrer, reaches as high as 280barrer；It is right CO2/CH4Selection coefficient more than 30, reach as high as 40.Meanwhile the gas separation membrane shows excellent heat resistance (its Glass transition temperature TgBetween 340~380 DEG C) and mechanical property (its tensile strength TsBetween 90~120MPa).
The present invention also provides the preparation method of the polyimide resin in above-mentioned gas seperation film, it is characterised in that described Method comprises the following steps：Under inert gas shielding, the aromatic diamines shown in Formula II with fluorine-containing benzene lateral group structure are dissolved In organic solvent, aromatic dianhydride shown in formula III is then added, obtains polyimide resin of the present invention,
Wherein,
X, the same Formulas I of Y, L, M, N and Ar definition.
Preferably, Formula II and formula III are stirred to after all dissolving obtains homogeneous phase solution, adds catalyst and dehydrating agent Heating is reacted, and reaction finishes removing dehydrating agent, and precipitating reagent is poured into after cooling and obtains described polyimide resin：
In the above method, aromatic dianhydride shown in formula III is specially 4,4 '-(hexafluoro isopropyl) double phthalic anhydrides (6FDA), 4,4 '-(2,2,2- Trifluoromethyl-1s-phenyl-ethylidene) two phthalic anhydrides (3FDA), 4,4 '-[2,2,2- trifluoromethyls- 1- (3- trifluoromethyls)-ethylidene] two phthalic anhydrides (HFDA), 4,4 '-[2,2,2- Trifluoromethyl-1s-(3,5- bis trifluoromethyls Phenyl)-ethylidene] two phthalic anhydrides (9FDA), triptycene -2,3,6,7- tetracarboxylic dianhydrides (TDA), double (3 ', the 4 '-dicarboxyl benzene of 1,4- Epoxide) triptycene dianhydride (TODA), double (the 3,4- dianhydride phenoxyls phenyl) fluorenes (BAOFL) of 9,9-.
In the above method, the aromatic diamines with fluorine-containing benzene lateral group structure shown in Formula II are specially α, α-bis- (4- amino -3, 5- 3,5-dimethylphenyls) -1- (4 '-trifluoromethyl) methane, α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (3 ', 5 ' - Bis trifluoromethyl phenyl) methane, α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (4 '-fluorophenyl) methane, α, α-bis- (4- Amino -3,5- 3,5-dimethylphenyls) -1- (3 ', 5 '-difluorophenyl) methane, α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (3 ', 4 ', 5 '-trifluorophenyl) methane, α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (4 '-trifluoromethyl) second Alkane, α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (3 ', 5 '-bis trifluoromethyl phenyl) ethane, α, α-bis- (4- amino - 3,5- 3,5-dimethylphenyls) -1- (4 '-fluorophenyl) ethane, α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (3 ', 5 '-difluoros Phenyl) ethane, α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (3 ', 4 ', 5 '-trifluorophenyl) ethane, α, α-bis- (4- ammonia Base -3,5- difluorophenyls) -1- (4 '-trifluoromethyl) methane, α, α-bis- (4- amino -3,5- difluorophenyls) -1- (4 '-fluorine Phenyl) methane, α, α-bis- (4- amino -3,5- difluorophenyls) -1- (4 '-trifluoromethyl) ethane, α, α-bis- (4- amino - 3,5- difluorophenyls) -1- (4 '-fluorophenyl) ethane.
The organic solvent is selected from 1-METHYLPYRROLIDONE (NMP), gamma-butyrolacton, dimethyl sulfoxide (DMSO) (DMSO), N, N- bis- At least one of methylacetamide (DMAc) and N,N-dimethylformamide (DMF).
The one kind of the catalyst in isoquinolin, quinoline, triethylamine or pyridine.
The dehydrating agent is toluene or dimethylbenzene.
The precipitating reagent is selected from least one of water, methanol, ethanol, propyl alcohol, butanol or isopropanol.
The molar ratio example of the aromatic diamines and aromatic dianhydride with fluorine-containing benzene lateral group structure is 0.95~1.05： 1.0。
The homogeneous phase solution solid content is 25~40wt.%.
The catalyst and the molar ratio of aromatic dianhydride are 0.05~0.1：1.0.
The temperature that above-mentioned heating is reacted is 140~180 DEG C；Time is 8~12 hours.
The present invention also provides the preparation method of above-mentioned polyimide gas separating film, comprises the following steps：
The above-mentioned polyimide resin with fluorine-containing benzene lateral group structure is dissolved in organic solvent, it is molten to obtain the resin Liquid, then the resin solution after drying, is immersed in deionized water and peeled off, obtain the polyimides gas coated in substrate Body seperation film.
In above-mentioned gas separation membrane preparation method, the organic solvent is selected from 1-METHYLPYRROLIDONE (NMP), γ-Ding Nei At least one in ester, dimethyl sulfoxide (DMSO) (DMSO), DMAC N,N' dimethyl acetamide (DMAc) and N,N-dimethylformamide (DMF) Kind.
The base material is glass plate or stainless steel plate.
The solid content of the resin solution is 25~45wt.%.
In the baking step, temperature is 80~200 DEG C, and the time is 3~5 hours.
The present invention also provides the purposes of above-mentioned polyimide gas separating film, and it is used for the separation of carbon dioxide with returning Receive.
The separation includes the acidity such as the separation of carbon dioxide and methane, carbon dioxide in natural in biogas with recovery Recovery of carbon dioxide etc. in the removal of gas or tertiary oil production in oil field.
The beneficial effects of the invention are as follows：
Polyimide gas separating film provided by the invention, have high osmosis and high selectivity concurrently, while be also equipped with excellent Heat resistance and mechanical property, be more suitable for the separation and recovery for carbon dioxide.Specifically, the present invention is used and contained The aromatic dianhydride of massive structure prepares polyimides with the aromatic diamines with fluorine-containing benzene lateral group structure.Contain massive structure Dianhydride combine the diamines with big side base and can effectively suppress the tightly packed of strand, increase strand spacing, improve polymerization The fractional free volume of thing, so as to provide more micropores for being advantageous to gas transport, to improve the gas permeability of seperation film；With This simultaneously, by introducing fluoro-containing group in polymer architecture, using the interaction between fluorine atom and carbon dioxide molecule, Accelerate the course of dissolution of carbon dioxide, so as to further improve permeability of the seperation film to carbon dioxide；It is in addition, rigid Polymer backbone conformation can not only obtain the polyimides of Good Heat-resistance, and be advantageous to keep polyimide separation membrane Distinctive high gas-selectively.
Brief description of the drawings
Fig. 1 is the infrared spectrum of polyimide separation membrane prepared by embodiment 1.
Embodiment
With reference to specific embodiment, the present invention is further elaborated, but the invention is not restricted to following examples.It is described Method is conventional method unless otherwise instructed.The raw material can obtain from the open approach of business unless otherwise instructed.This Degree and percent concentration are mass percentage content and mass percent concentration unless otherwise instructed in invention.
The preparation of embodiment 1, polyimide gas separating film
In the three-necked flask equipped with mechanical agitation, water knockout drum, nitrogen inlet-outlet and thermometer, 39.85 gram (0.1 is added Mole) α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (4 '-trifluoromethyl) methane and 1-METHYLPYRROLIDONE (NMP) 126 grams, stir under nitrogen protection to after being completely dissolved, add 44.42 grams of (0.1 mole) 4,4 '-(hexafluoro isopropyls) Double phthalic anhydrides (6FDA), obtain the homogeneous phase solution that solid content is 40wt.%.By 0.65 gram of (0.005 mole) isoquinolin Be added to 21 grams of toluene in above-mentioned homogeneous phase solution, reaction system be warming up to 180 DEG C reaction 12 hours after, steam toluene, stop Heating.Reaction solution is cooled to pour into after 80~120 DEG C fibrous crude product is obtained in methanol, collect the crude product of precipitation, used Filtering, crushing, drying, obtain polyimide resin, yield 97%, number-average molecular weight (M after first alcohol and water washs repeatedlyn) be 1.69×105g/mol。
Above-mentioned polyimide resin is dissolved in the tree for obtaining that solid content is 40wt.% in 1-METHYLPYRROLIDONE (NMP) Lipoprotein solution, after filtered, vacuum defoamation, it is coated on surface smooth glass plate or stainless steel plate, passes through under air atmosphere 80 DEG C/1 hour, 120 DEG C/1 hour, 160 DEG C/1 hour, 180 DEG C/1 hour, after ladder-elevating temperature heat is dried within 200 DEG C/1 hour, by glass Glass plate or stainless steel plate, which are immersed in deionized water, makes separation film automatic stripping, is obtained through 120 DEG C of vacuum drying certain thickness poly- Acid imide seperation film.
FT-IR(film,cm-1)：2925,1787,1733,1622,1527,1487,1440,1369,1298,1257, 1209,1145,1110,1045,723。
The thickness of seperation film can be controlled by adjusting the model of painting deflector roll.The main performance of the polyimide separation membrane It is shown in Table 1.
The preparation of embodiment 2, polyimide gas separating film
In the three-necked flask equipped with mechanical agitation, water knockout drum, nitrogen inlet-outlet and thermometer, 34.85 gram (0.1 is added Mole) α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (4 '-fluorophenyl) methane and DMAC N,N' dimethyl acetamide (DMAc) 147 grams, stir under nitrogen protection to after being completely dissolved, add 44.42 grams of double neighbours of (0.1 mole) 4,4 '-(hexafluoro isopropyl) Phthalate anhydride (6FDA), obtain the homogeneous phase solution that solid content is 35wt.%.By 1.29 grams of (0.01 mole) quinoline and 25 gram two Toluene is added in above-mentioned homogeneous phase solution, after reaction system is warming up to 140 DEG C of reactions 12 hours, is steamed dimethylbenzene, is stopped heating. Reaction solution is cooled to pour into after 80~120 DEG C fibrous crude product is obtained in ethanol, collect the crude product of precipitation, with ethanol and Filtering, crushing, drying, obtain polyimide resin, yield 98%, number-average molecular weight (M after water washs repeatedlyn) for 1.99 × 105g/mol。
Above-mentioned polyimide resin is dissolved in the tree for obtaining that solid content is 40wt.% in 1-METHYLPYRROLIDONE (NMP) Lipoprotein solution, after filtered, vacuum defoamation, it is coated on surface smooth glass plate or stainless steel plate, passes through under air atmosphere 80 DEG C/1 hour, 120 DEG C/1 hour, 160 DEG C/1 hour, 180 DEG C/1 hour, after ladder-elevating temperature heat is dried within 200 DEG C/1 hour, by glass Glass plate or stainless steel plate, which are immersed in deionized water, makes separation film automatic stripping, is obtained through 120 DEG C of vacuum drying certain thickness poly- Acid imide seperation film.The thickness of seperation film can be controlled by adjusting the model of painting deflector roll.The master of the polyimide separation membrane Performance is wanted to be shown in Table 1.
The preparation of embodiment 3, polyimide gas separating film
In the three-necked flask equipped with mechanical agitation, water knockout drum, nitrogen inlet-outlet and thermometer, 38.44 gram (0.1 is added Mole) α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (3 ', 4 ', 5 '-trifluorophenyl) methane and 1-METHYLPYRROLIDONE (NMP) 154 grams, stir under nitrogen protection to after being completely dissolved, add 44.42 grams of (0.1 mole) 4,4 '-(hexafluoro isopropyls) Double phthalic anhydrides (6FDA), obtain the homogeneous phase solution that solid content is 35wt.%.By 1.29 grams of (0.01 mole) quinoline and 26 Gram toluene is added in above-mentioned homogeneous phase solution, after reaction system is warming up to 180 DEG C of reactions 10 hours, is steamed toluene, is stopped heating. Reaction solution is cooled to pour into after 80~120 DEG C fibrous crude product is obtained in ethanol, collect the crude product of precipitation, with ethanol and Filtering, crushing, drying, obtain polyimide resin, yield 99%, number-average molecular weight (M after water washs repeatedlyn) for 1.86 × 105g/mol。
Above-mentioned polyimide resin is dissolved in the tree for obtaining that solid content is 40wt.% in 1-METHYLPYRROLIDONE (NMP) Lipoprotein solution, after filtered, vacuum defoamation, it is coated on surface smooth glass plate or stainless steel plate, passes through under air atmosphere 80 DEG C/1 hour, 120 DEG C/1 hour, 160 DEG C/1 hour, 180 DEG C/1 hour, after ladder-elevating temperature heat is dried within 200 DEG C/1 hour, by glass Glass plate or stainless steel plate, which are immersed in deionized water, makes separation film automatic stripping, is obtained through 120 DEG C of vacuum drying certain thickness poly- Acid imide seperation film.The thickness of seperation film can be controlled by adjusting the model of painting deflector roll.The master of the polyimide separation membrane Performance is wanted to be shown in Table 1.
The preparation of embodiment 4, polyimide gas separating film
In the three-necked flask equipped with mechanical agitation, water knockout drum, nitrogen inlet-outlet and thermometer, 48.05 gram (0.1 is added Mole) α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (3 ', 5 '-bis trifluoromethyl phenyl) ethane and gamma-butyrolacton 218 Gram, stir under nitrogen protection to after being completely dissolved, add 45.23 grams of (0.1 mole) 4,4 '-(2,2,2- Trifluoromethyl-1s-benzene Base-ethylidene) two phthalic anhydrides (3FDA), obtain the homogeneous phase solution that solid content is 30wt.%.By 1.03 grams of (0.008 mole) isoquinolines Quinoline and 36 grams of toluene are added in above-mentioned homogeneous phase solution, reaction system be warming up to 180 DEG C reaction 8 hours after, steam toluene, stop Heating.Reaction solution is cooled to after 80~120 DEG C and pours into ethanol/water mixed liquor (ethanol/water volume ratio=3:1) fiber is obtained in Shape crude product, the crude product of precipitation is collected, filter, crush after being washed repeatedly with second alcohol and water, drying, obtaining polyimides tree Fat, yield 96%, number-average molecular weight (Mn) it is 1.47 × 105g/mol。
Above-mentioned polyimide resin is dissolved in the resin solution for obtaining that solid content is 30wt.% in gamma-butyrolacton, passed through After filter, vacuum defoamation, it is coated on surface smooth glass plate or stainless steel plate, passes through 80 DEG C/1 hour under air atmosphere, 120 DEG C/1 hour, 160 DEG C/1 hour, 180 DEG C/1 hour, after ladder-elevating temperature heat is dried within 200 DEG C/1 hour, by glass plate or stainless Steel plate, which is immersed in deionized water, makes separation film automatic stripping, and obtaining certain thickness polyimides through 120 DEG C of vacuum drying separates Film.The thickness of seperation film can be controlled by adjusting the model of painting deflector roll.The main performance of the polyimide separation membrane is shown in Table 1。
The preparation of embodiment 5, polyimide gas separating film
In the three-necked flask equipped with mechanical agitation, water knockout drum, nitrogen inlet-outlet and thermometer, 38.25 grams are added (0.105 mole) α, α-bis- (4- amino -3,5- difluorophenyls) -1- (4 '-fluorophenyl) methane and DMAC N,N' dimethyl acetamide (DMAc) 195 grams, stir under nitrogen protection to after being completely dissolved, add 45.23 grams of (0.1 mole) 4,4 '-(2,2,2- trifluoros Methyl isophthalic acid-phenyl-ethylidene) two phthalic anhydrides (3FDA), obtain the homogeneous phase solution that solid content is 30wt.%.By 1.01 grams, (0.01 rubs You) triethylamine and 32 grams of dimethylbenzene are added in above-mentioned homogeneous phase solution, after reaction system is warming up to 140 DEG C of reactions 12 hours, steam Go out dimethylbenzene, stop heating.Reaction solution is cooled to after 80~120 DEG C to pour into fibrous crude product is obtained in propyl alcohol, collect analysis The crude product gone out, filter, crush after being washed repeatedly with the third alcohol and water, drying, obtaining polyimide resin, yield 97%, number Average molecular weight (Mn) it is 6.4 × 104g/mol。
It is 35wt.%'s above-mentioned polyimide resin to be dissolved in solid content is obtained in DMAC N,N' dimethyl acetamide (DMAc) Resin solution, after filtered, vacuum defoamation, it is coated on surface smooth glass plate or stainless steel plate, is passed through under air atmosphere 80 DEG C/1 hour is spent, 120 DEG C/1 hour, 160 DEG C/1 hour, after ladder-elevating temperature heat is dried within 180 DEG C/1 hour, by glass plate or stainless Steel plate, which is immersed in deionized water, makes separation film automatic stripping, and obtaining certain thickness polyimides through 120 DEG C of vacuum drying separates Film.The thickness of seperation film can be controlled by adjusting the model of painting deflector roll.The main performance of the polyimide separation membrane is shown in Table 1。
The preparation of embodiment 6, polyimide gas separating film
In the three-necked flask equipped with mechanical agitation, water knockout drum, nitrogen inlet-outlet and thermometer, 36.64 gram (0.1 is added Mole) α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (3 ', 5 '-difluorophenyl) methane and N,N-dimethylformamide (DMF) 133 grams, stir under nitrogen protection to after being completely dissolved, add 52.03 grams of (0.1 mole) 4,4 '-[2,2,2- trifluoros Methyl isophthalic acid-(3- trifluoromethyls)-ethylidene] two phthalic anhydrides (HFDA), obtain the homogeneous phase solution that solid content is 40wt.%.Will 0.63 gram of (0.008 mole) triethylamine and 22 grams of dimethylbenzene are added in above-mentioned homogeneous phase solution, and reaction system is warming up to 140 DEG C instead After answering 10 hours, dimethylbenzene is steamed, stops heating.Reaction solution is cooled to pour into after 80~120 DEG C threadiness is obtained in methanol Crude product, the crude product of precipitation is collected, filters, crushes after being washed repeatedly with first alcohol and water, drying, obtaining polyimide resin, Yield is 98%, number-average molecular weight (Mn) it is 1.74 × 105g/mol。
It is 45wt.%'s above-mentioned polyimide resin to be dissolved in solid content is obtained in DMAC N,N' dimethyl acetamide (DMAc) Resin solution, after filtered, vacuum defoamation, it is coated on surface smooth glass plate or stainless steel plate, is passed through under air atmosphere 80 DEG C/1 hour is spent, 120 DEG C/1 hour, 160 DEG C/1 hour, after ladder-elevating temperature heat is dried within 180 DEG C/1 hour, by glass plate or stainless Steel plate, which is immersed in deionized water, makes separation film automatic stripping, and obtaining certain thickness polyimides through 120 DEG C of vacuum drying separates Film.The thickness of seperation film can be controlled by adjusting the model of painting deflector roll.The main performance of the polyimide separation membrane is shown in Table 1。
The preparation of embodiment 7, polyimide gas separating film
In the three-necked flask equipped with mechanical agitation, water knockout drum, nitrogen inlet-outlet and thermometer, 41.25 gram (0.1 is added Mole) α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (4 '-trifluoromethyl) ethane and 1-METHYLPYRROLIDONE (NMP) 173 grams, stir under nitrogen protection to after being completely dissolved, add 52.03 grams of (0.1 mole) 4,4 '-[2,2,2- trifluoros Methyl isophthalic acid-(3- trifluoromethyls)-ethylidene] two phthalic anhydrides (HFDA), obtain the homogeneous phase solution that solid content is 35wt.%.Will 0.65 gram of (0.005 mole) isoquinolin and 29 grams of toluene are added in above-mentioned homogeneous phase solution, and reaction system is warming up to 180 DEG C of reactions After 8 hours, toluene is steamed, stops heating.Reaction solution is cooled to after 80~120 DEG C and pours into methanol/water mixed liquor (methanol/water Volume ratio=1:1) fibrous crude product is obtained in, collects the crude product of precipitation, filtering, powder after being washed repeatedly with first alcohol and water Broken, drying, obtains polyimide resin, yield 97%, number-average molecular weight (Mn) it is 1.27 × 105g/mol。
Above-mentioned polyimide resin is dissolved in the resin solution for obtaining that solid content is 35wt.% in gamma-butyrolacton, passed through After filter, vacuum defoamation, it is coated on surface smooth glass plate or stainless steel plate, passes through 80 DEG C/1 hour under air atmosphere, 120 DEG C/1 hour, 160 DEG C/1 hour, 180 DEG C/1 hour, after ladder-elevating temperature heat is dried within 200 DEG C/1 hour, by glass plate or stainless Steel plate, which is immersed in deionized water, makes separation film automatic stripping, and obtaining certain thickness polyimides through 120 DEG C of vacuum drying separates Film.The thickness of seperation film can be controlled by adjusting the model of painting deflector roll.The main performance of the polyimide separation membrane is shown in Table 1。
The preparation of embodiment 8, polyimide gas separating film
In the three-necked flask equipped with mechanical agitation, water knockout drum, nitrogen inlet-outlet and thermometer, 43.50 grams are added (0.105 mole) α, α-bis- (4- amino -3,5- difluorophenyls) -1- (4 '-trifluoromethyl) methane and dimethyl sulfoxide (DMSO) (DMSO) 287 grams, stir under nitrogen protection to after being completely dissolved, add 52.03 grams of (0.1 mole) 4,4 '-[2,2,2- trifluoros Methyl isophthalic acid-(3- trifluoromethyls)-ethylidene] two phthalic anhydrides (HFDA), obtain the homogeneous phase solution that solid content is 25wt.%.Will 0.79 gram of (0.01 mole) pyridine and 48 grams of toluene are added in above-mentioned homogeneous phase solution, and reaction system is warming up to 160 DEG C of reactions 12 After hour, toluene is steamed, stops heating.Reaction solution is cooled to pour into after 80~120 DEG C fibrous crude product is obtained in propyl alcohol, The crude product separated out is collected, filters, crush after being washed repeatedly with the third alcohol and water, drying, obtaining polyimide resin, yield is 96%, number-average molecular weight (Mn) it is 7.03 × 104g/mol。
Above-mentioned polyimide resin is dissolved in obtained in dimethyl sulfoxide (DMSO) (DMSO) solid content be 30wt.% resin it is molten Liquid, after filtered, vacuum defoamation, be coated on surface smooth glass plate or stainless steel plate, under air atmosphere by 80 DEG C/ 1 hour, 120 DEG C/1 hour, 160 DEG C/1 hour, 180 DEG C/1 hour, after ladder-elevating temperature heat is dried within 200 DEG C/1 hour, by glass plate Or make separation film automatic stripping in stainless steel plate immersion deionized water, it is sub- to obtain certain thickness polyamides through 120 DEG C of vacuum drying Amine seperation film.The thickness of seperation film can be controlled by adjusting the model of painting deflector roll.The main property of the polyimide separation membrane 1 can be shown in Table.
The preparation of embodiment 9, polyimide gas separating film
In the three-necked flask equipped with mechanical agitation, water knockout drum, nitrogen inlet-outlet and thermometer, 36.25 gram (0.1 is added Mole) α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (4 '-fluorophenyl) ethane and 1-METHYLPYRROLIDONE (NMP) 177 Gram, stir under nitrogen protection to after being completely dissolved, addition 58.83 grams (0.1 moles) 4,4 '-[2,2,2- Trifluoromethyl-1s- (3,5- bis trifluoromethyl phenyl)-ethylidene] two phthalic anhydrides (9FDA), obtain the homogeneous phase solution that solid content is 35wt.%.By 1.29 Gram (0.01 mole) quinoline and 29 grams of toluene are added in above-mentioned homogeneous phase solution, and reaction system is warming up to 180 DEG C and reacted 10 hours Afterwards, toluene is steamed, stops heating.Reaction solution is cooled to after 80~120 DEG C and pours into methanol/water mixed liquor (methanol/water volume ratio =3:1) fibrous crude product is obtained in, collects the crude product of precipitation, filters, crush after being washed repeatedly with first alcohol and water, drying, Obtain polyimide resin, yield 97%, number-average molecular weight (Mn) it is 1.51 × 105g/mol。
It is 35wt.%'s above-mentioned polyimide resin to be dissolved in solid content is obtained in DMAC N,N' dimethyl acetamide (DMAc) Resin solution, after filtered, vacuum defoamation, it is coated on surface smooth glass plate or stainless steel plate, is passed through under air atmosphere 80 DEG C/1 hour is spent, 120 DEG C/1 hour, 160 DEG C/1 hour, after ladder-elevating temperature heat is dried within 180 DEG C/1 hour, by glass plate or stainless Steel plate, which is immersed in deionized water, makes separation film automatic stripping, and obtaining certain thickness polyimides through 120 DEG C of vacuum drying separates Film.The thickness of seperation film can be controlled by adjusting the model of painting deflector roll.The main performance of the polyimide separation membrane is shown in Table 1。
The preparation of embodiment 10, polyimide gas separating film
In the three-necked flask equipped with mechanical agitation, water knockout drum, nitrogen inlet-outlet and thermometer, 39.85 gram (0.1 is added Mole) α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (3 ', 4 ', 5 '-trifluorophenyl) ethane and N, N- dimethyl formyl 148 grams of amine (DMF), is stirred to after being completely dissolved under nitrogen protection, adds 58.83 grams of (0.1 mole) 4,4 '-[2,2,2- tri- Methyl fluoride -1- (3,5- bis trifluoromethyl phenyl)-ethylidene] two phthalic anhydrides (9FDA), it is mixing for 40wt.% to obtain solid content Liquid.0.40 gram of (0.005 mole) pyridine and 25 grams of dimethylbenzene are added in above-mentioned homogeneous phase solution, reaction system is warming up to 140 After DEG C reaction 12 hours, steam dimethylbenzene, stop heating.Reaction solution is cooled to pour into isopropanol after 80~120 DEG C and obtained Fibrous crude product, the crude product of precipitation is collected, filter, crush after being washed repeatedly with isopropyl alcohol and water, drying, obtain polyamides Asia Polyimide resin, yield 97%, number-average molecular weight (Mn) it is 1.36 × 105g/mol。
Above-mentioned polyimide resin is dissolved in obtained in dimethyl sulfoxide (DMSO) (DMSO) solid content be 35wt.% resin it is molten Liquid, after filtered, vacuum defoamation, be coated on surface smooth glass plate or stainless steel plate, under air atmosphere by 80 DEG C/ 1 hour, 120 DEG C/1 hour, 160 DEG C/1 hour, 180 DEG C/1 hour, after ladder-elevating temperature heat is dried within 200 DEG C/1 hour, by glass plate Or make separation film automatic stripping in stainless steel plate immersion deionized water, it is sub- to obtain certain thickness polyamides through 120 DEG C of vacuum drying Amine seperation film.The thickness of seperation film can be controlled by adjusting the model of painting deflector roll.The main property of the polyimide separation membrane 1 can be shown in Table.
The preparation of embodiment 11, polyimide gas separating film
In the three-necked flask equipped with mechanical agitation, water knockout drum, nitrogen inlet-outlet and thermometer, 39.72 grams are added (0.105 mole) α, α-bis- (4- amino -3,5- difluorophenyls) -1- (4 '-fluorophenyl) ethane and N,N-dimethylformamide (DMF) 230 grams, stir under nitrogen protection to after being completely dissolved, add 58.83 grams of (0.1 mole) 4,4 '-[2,2,2- trifluoros Methyl isophthalic acid-(3,5- bis trifluoromethyl phenyl)-ethylidene] two phthalic anhydrides (9FDA), it is mixing for 30wt.% to obtain solid content Liquid.0.79 gram of (0.01 mole) pyridine and 38 grams of dimethylbenzene are added in above-mentioned homogeneous phase solution, reaction system is warming up to 140 DEG C After reaction 12 hours, dimethylbenzene is steamed, stops heating.Reaction solution is cooled to pour into after 80~120 DEG C fibre is obtained in isopropanol Shape crude product is tieed up, collects the crude product of precipitation, filters, crush after being washed repeatedly with isopropyl alcohol and water, drying, obtaining polyimides Resin, yield 96%, number-average molecular weight (Mn) it is 5.01 × 104g/mol。
It is 25wt.%'s above-mentioned polyimide resin to be dissolved in solid content is obtained in N,N-dimethylformamide (DMF) Resin solution, after filtered, vacuum defoamation, it is coated on surface smooth glass plate or stainless steel plate, is passed through under air atmosphere Spend 80 DEG C/1 hour, 120 DEG C/1 hour, after 160 DEG C/1 hour ladder-elevating temperature heat is dried, glass plate or stainless steel plate are immersed go from Make separation film automatic stripping in sub- water, certain thickness polyimide separation membrane is obtained through 120 DEG C of vacuum drying.The thickness of seperation film Degree can be controlled by adjusting the model of painting deflector roll.The main performance of the polyimide separation membrane is shown in Table 1.
The preparation of embodiment 12, polyimide gas separating film
In the three-necked flask equipped with mechanical agitation, water knockout drum, nitrogen inlet-outlet and thermometer, 44.31 grams are added (0.095 mole) α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (3 ', 5 '-bis trifluoromethyl phenyl) methane and γ-fourth 195 grams of lactone, is stirred to after being completely dissolved under nitrogen protection, 39.43 grams of (0.1 mole) triptycenes -2,3 of addition, and 6,7- tetra- Acid dianhydride (TDA), obtain the homogeneous phase solution that solid content is 30wt.%.By 0.65 gram of (0.005 mole) isoquinolin and 32 grams of diformazans Benzene is added in above-mentioned homogeneous phase solution, after reaction system is warming up to 180 DEG C of reactions 12 hours, is steamed dimethylbenzene, is stopped heating.Will Reaction solution, which is poured into after being cooled to 80~120 DEG C in butanol, obtains fibrous crude product, collects the crude product of precipitation, with fourth alcohol and water Filtering, crushing, drying, obtain polyimide resin, yield 97%, number-average molecular weight (M after washing repeatedlyn) for 8.15 × 104g/mol。
Above-mentioned polyimide resin is dissolved in the resin solution for obtaining that solid content is 30wt.% in gamma-butyrolacton, passed through After filter, vacuum defoamation, it is coated on surface smooth glass plate or stainless steel plate, passes through 80 DEG C/1 hour under air atmosphere, 120 DEG C/1 hour, 160 DEG C/1 hour, 180 DEG C/1 hour, after ladder-elevating temperature heat is dried within 200 DEG C/1 hour, by glass plate or stainless Steel plate, which is immersed in deionized water, makes separation film automatic stripping, and obtaining certain thickness polyimides through 120 DEG C of vacuum drying separates Film.The thickness of seperation film can be controlled by adjusting the model of painting deflector roll.The main performance of the polyimide separation membrane is shown in Table 1。
The preparation of embodiment 13, polyimide gas separating film
In the three-necked flask equipped with mechanical agitation, water knockout drum, nitrogen inlet-outlet and thermometer, 38.05 gram (0.1 is added Mole) α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (3 ', 5 '-difluorophenyl) ethane and dimethyl sulfoxide (DMSO) (DMSO) 178 grams, stir under nitrogen protection to after being completely dissolved, add 57.85 grams of (0.1 mole) Isosorbide-5-Nitrae-bis- (3 ', 4 '-dicarboxyl benzene Epoxide) triptycene dianhydride (TODA), obtain the homogeneous phase solution that solid content is 35wt.%.By 0.50 gram of (0.005 mole) triethylamine Be added to 30 grams of dimethylbenzene in above-mentioned homogeneous phase solution, reaction system be warming up to 160 DEG C reaction 12 hours after, steam dimethylbenzene, Stop heating.Reaction solution is cooled to pour into after 80~120 DEG C fibrous crude product is obtained in ethanol, collect the thick production of precipitation Thing, filter, crush after being washed repeatedly with second alcohol and water, drying, obtaining polyimide resin, yield 97%, number-average molecular weight (Mn) it is 9.24 × 104g/mol。
It is 40wt.%'s above-mentioned polyimide resin to be dissolved in solid content is obtained in DMAC N,N' dimethyl acetamide (DMAc) Resin solution, after filtered, vacuum defoamation, it is coated on surface smooth glass plate or stainless steel plate, is passed through under air atmosphere 80 DEG C/1 hour is spent, 120 DEG C/1 hour, 160 DEG C/1 hour, after ladder-elevating temperature heat is dried within 180 DEG C/1 hour, by glass plate or stainless Steel plate, which is immersed in deionized water, makes separation film automatic stripping, and obtaining certain thickness polyimides through 120 DEG C of vacuum drying separates Film.The thickness of seperation film can be controlled by adjusting the model of painting deflector roll.The main performance of the polyimide separation membrane is shown in Table 1。
The preparation of embodiment 14, polyimide gas separating film
In the three-necked flask equipped with mechanical agitation, water knockout drum, nitrogen inlet-outlet and thermometer, 44.98 grams are added (0.105 mole) α, α-bis- (4- amino -3,5- difluorophenyls) -1- (4 '-trifluoromethyl) ethane and N- crassitudes 203 grams of ketone (NMP), is stirred to after being completely dissolved under nitrogen protection, adds double (3, the 4- dianhydrides of 64.26 grams of (0.1 mole) 9,9- Phenoxyl phenyl) fluorenes (BAOFL), obtain the homogeneous phase solution that solid content is 35wt.%.By 0.65 gram of (0.005 mole) quinoline Be added to 34 grams of toluene in above-mentioned homogeneous phase solution, reaction system be warming up to 180 DEG C reaction 10 hours after, steam toluene, stop Heating.Reaction solution is cooled to after 80~120 DEG C and pours into ethanol/water mixed liquor (ethanol/water volume ratio=1:1) fiber is obtained in Shape crude product, the crude product of precipitation is collected, filter, crush after being washed repeatedly with second alcohol and water, drying, obtaining polyimides tree Fat, yield 96%, number-average molecular weight (Mn) it is 5.93 × 104g/mol。
It is 30wt.%'s above-mentioned polyimide resin to be dissolved in solid content is obtained in DMAC N,N' dimethyl acetamide (DMAc) Resin solution, after filtered, vacuum defoamation, it is coated on surface smooth glass plate or stainless steel plate, is passed through under air atmosphere 80 DEG C/1 hour is spent, 120 DEG C/1 hour, 160 DEG C/1 hour, after ladder-elevating temperature heat is dried within 180 DEG C/1 hour, by glass plate or stainless Steel plate, which is immersed in deionized water, makes separation film automatic stripping, and obtaining certain thickness polyimides through 120 DEG C of vacuum drying separates Film.The thickness of seperation film can be controlled by adjusting the model of painting deflector roll.The main performance of the polyimide separation membrane is shown in Table 1。
The main performance of table 1, polyimide gas separating film
aHeat resistance is determined using dynamic mechanical analysis, wherein TgFor glass transition temperature.
bMechanical property is determined using universal testing machine according to GB/T 1040.3-2006, TSFor tensile strength.
cGas separating property is determined using the test of VAC-V2 pressure differential gas permeameters according to ISO15105-1, test-strips Part is 1 atmospheric pressure/30 DEG C, and seperation film sample thickness is 50 μm.Gas permeability coefficient P units are barrer, 1barrer=1 ×10-10cm3(STP)cm/cm2S cmHg, select factor alpha=PA/PB。

Claims (12)

  1. A kind of 1. polyimide gas separating film of separation and recovery for carbon dioxide, it is characterised in that the seperation film It is made by the polyimide resin with fluorine-containing benzene lateral group structure, the polyimide resin has the structure shown in following formula I Formula：
    Wherein, any one of Ar in following radicals：
    X is CH3Or F,
    Y is H or CH3,
    L, M, N are identical or different, are independently from each other H, F or CF3, also, at least one in L, M, N is F or CF3,
    N is 50~300 integer.
  2. 2. gas separation membrane according to claim 1, it is characterised in that the number-average molecular weight of the polyimide resin (Mn) between 50000~200000g/mol.
  3. 3. gas separation membrane according to claim 1 or 2, it is characterised in that the thickness of the seperation film is 25~75 μm.
  4. 4. a kind of preparation method of the polyimide resin in gas separation membrane described in any one of claim 1-3, its feature It is, methods described comprises the following steps：
    Under inert gas shielding, the aromatic diamines for having fluorine-containing benzene lateral group structure shown in Formula II are dissolved in organic solvent, Then aromatic dianhydride shown in formula III is added, obtains the polyimide resin：
    Wherein,
    X, the same Formulas I of Y, L, M, N and Ar definition.
  5. 5. according to the method for claim 4, it is characterised in that by fragrance two shown in aromatic diamines shown in Formula II and formula III Acid anhydride is stirred to after all dissolving obtains homogeneous phase solution, adds catalyst and dehydrating agent heating is reacted, reaction finishes removing Dehydrating agent, precipitating reagent is poured into after cooling and obtains described polyimide resin.
  6. 6. the method according to claim 4 or 5, it is characterised in that aromatic dianhydride shown in formula III is 4,4 '-(hexafluoro isopropyl Base) double phthalic anhydrides (6FDA), 4,4 '-(2,2,2- Trifluoromethyl-1s-phenyl-ethylidene) two phthalic anhydrides (3FDA), 4,4 '- [2,2,2- Trifluoromethyl-1s-(3- trifluoromethyls)-ethylidene] two phthalic anhydrides (HFDA), 4,4 '-[2,2,2- trifluoromethyls- 1- (3,5- bis trifluoromethyl phenyls)-ethylidene] two phthalic anhydrides (9FDA), triptycene -2,3,6,7- tetracarboxylic dianhydrides (TDA), 1,4- Double (3 ', 4 '-di carboxyl phenyloxy) triptycene dianhydrides (TODA) or double (the 3,4- dianhydride phenoxyls phenyl) fluorenes of 9,9- (BAOFL)；
    The aromatic diamines with fluorine-containing benzene lateral group structure are α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- shown in Formula II (4 '-trifluoromethyl) methane, α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (3 ', 5 '-bis trifluoromethyl phenyl) Methane, α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (4 '-fluorophenyl) methane, α, α-bis- (4- amino -3,5- dimethyl Phenyl) -1- (3 ', 5 '-difluorophenyl) methane, α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (3 ', 4 ', 5 '-trifluoro-benzenes Base) methane, α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (4 '-trifluoromethyl) ethane, α, α-bis- (4- amino - 3,5- 3,5-dimethylphenyls) -1- (3 ', 5 '-bis trifluoromethyl phenyl) ethane, α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (4 '-fluorophenyl) ethane, α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (3 ', 5 '-difluorophenyl) ethane, α, α-bis- (4- amino -3,5- 3,5-dimethylphenyls) -1- (3 ', 4 ', 5 '-trifluorophenyl) ethane, α, α-bis- (4- amino -3,5- difluorobenzenes Base) -1- (4 '-trifluoromethyl) methane, α, α-bis- (4- amino -3,5- difluorophenyls) -1- (4 '-fluorophenyl) methane, α, α-bis- (4- amino -3,5- difluorophenyls) -1- (4 '-trifluoromethyl) ethane or α, α-bis- (4- amino -3,5- difluorobenzenes Base) -1- (4 '-fluorophenyl) ethane.
  7. 7. according to the method for claim 5, it is characterised in that the organic solvent be selected from 1-METHYLPYRROLIDONE (NMP), In gamma-butyrolacton, dimethyl sulfoxide (DMSO) (DMSO), DMAC N,N' dimethyl acetamide (DMAc) and N,N-dimethylformamide (DMF) It is at least one；
    The one kind of the catalyst in isoquinolin, quinoline, triethylamine or pyridine；
    The dehydrating agent is toluene or dimethylbenzene；
    The precipitating reagent is selected from least one of water, methanol, ethanol, propyl alcohol, butanol or isopropanol.
  8. 8. according to the method for claim 5, it is characterised in that the aromatic diamines with fluorine-containing benzene lateral group structure and virtue The molar ratio example of fragrant dianhydride is 0.95~1.05：1.0；
    The homogeneous phase solution solid content is 25~40wt.%；
    The catalyst and the molar ratio of aromatic dianhydride are 0.05~0.1：1.0；
    The temperature that above-mentioned heating is reacted is 140~180 DEG C；Time is 8~12 hours.
  9. A kind of 9. polyimide gas separating film of the separation and recovery that are used for carbon dioxide described in any one of claim 1-3 Preparation method, it is characterised in that methods described comprises the following steps：
    The above-mentioned polyimide resin with fluorine-containing benzene lateral group structure is dissolved in organic solvent, obtains the resin solution, The resin solution after drying, is immersed in deionized water and peeled off, obtain the copolyimide gas point coated in substrate again From film.
  10. 10. the preparation method described in claim 9, it is characterised in that the organic solvent is selected from 1-METHYLPYRROLIDONE (NMP), gamma-butyrolacton, dimethyl sulfoxide (DMSO) (DMSO), DMAC N,N' dimethyl acetamide (DMAc) and N,N-dimethylformamide At least one of (DMF)；
    The substrate is glass plate or stainless steel plate；
    The solid content of the resin solution is 25~45wt.%；
    In the baking step, temperature is 80~200 DEG C, and the time is 3~5 hours.
  11. 11. the purposes of the polyimide gas separating film described in claim any one of 1-3, its be used for the separation of carbon dioxide with Recovery.
  12. 12. purposes according to claim 11, it is characterised in that the separation includes carbon dioxide in biogas with recovery Separation, natural gas with methane include the sour gas of carbon dioxide removal or tertiary oil production in oil field in carbon dioxide Recovery.
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CN108440754A (en) * 2018-03-15 2018-08-24 常州大学 One kind is containing tertiary butyl substitution m-Terphenyl structure polyimide film material and preparation method thereof
WO2020018621A1 (en) * 2018-07-20 2020-01-23 Dupont Electronics, Inc. Polymers for use in electronic devices
CN110156990B (en) * 2019-05-30 2020-12-08 武汉华星光电半导体显示技术有限公司 Polyimide compound, preparation method and application thereof
CN111116912B (en) * 2019-12-31 2022-12-06 山东华夏神舟新材料有限公司 Polyimide resin, preparation method thereof and method for preparing polyimide film/cross-linked polyimide film by using polyimide resin
CN111019133B (en) * 2019-12-31 2022-06-07 山东华夏神舟新材料有限公司 Polyimide resin for gas separation membrane, preparation method thereof and method for preparing polyimide gas separation membrane by using polyimide resin
CN111229061B (en) * 2020-01-17 2021-11-19 西安交通大学 Porous graphene separation membrane and preparation method thereof
CN112480406A (en) * 2020-11-30 2021-03-12 山东华夏神舟新材料有限公司 High-permeability high-selectivity polyimide film and preparation method thereof
CN112574412A (en) * 2020-12-20 2021-03-30 天津工业大学 Polyimide prepared based on diamino triptycene and derivatives thereof and used for gas separation and preparation method thereof
CN113072703A (en) * 2021-04-19 2021-07-06 中国科学院化学研究所 Thermoplastic polyimide with excellent comprehensive performance and preparation method and application thereof
CN117024733A (en) * 2021-06-23 2023-11-10 中国石油化工股份有限公司 Polyimide copolymers and membranes, methods for their preparation and use, and systems and methods for purifying helium
CN116272441B (en) * 2022-04-24 2023-10-27 中国科学院过程工程研究所 Structure and preparation method of gas separation membrane for natural gas helium stripping and plasticizing resistance effect
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