CN107913580A - A kind of application of polyimides in gas separation - Google Patents

A kind of application of polyimides in gas separation Download PDF

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Publication number
CN107913580A
CN107913580A CN201711127968.0A CN201711127968A CN107913580A CN 107913580 A CN107913580 A CN 107913580A CN 201711127968 A CN201711127968 A CN 201711127968A CN 107913580 A CN107913580 A CN 107913580A
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diaminourea
polyimides
gas separation
formulas
glass plate
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阎敬灵
胡小凡
王震
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The present invention provides a kind of application of polyimides with structure shown in Formulas I in gas separation.The present invention has obtained the polyimides with good filming ability by introducing with what twist structured 2,2 ', 3,3 ' bibenzene tetracarboxylic dianhydride and diamine monomer polymerize.Synthesized polyimides cost is relatively low, while has higher specific surface area, heat endurance, gas-selectively and gas-premeable, has a good application prospect in gas separation.

Description

A kind of application of polyimides in gas separation
Technical field
The invention belongs to technical field of macromolecules, and in particular to a kind of application of polyimides in gas separation.
Background technology
In the past few decades, the poromerics of 2nm is less than in gas separation (GS) field aperture size, as organic and inorganic is miscellaneous The metal-organic framework materials (MOFs) of change, covalent organic framework material (COFs), super cross-linked polymer poromerics (HCPs) Significant progress has been obtained with conjugated polymer poromerics (MCPs).
And based on polymer matrix seperation film because its is easily prepared, controllable and gas is distilled and absorbed compared to Conventional cryogenic Body isolation technics has the characteristics that low energy consumption, has received widespread attention.A kind of good gas separation membrane should have good Gas-premeable and corresponding high gas-selectively.1991, Robeson proposed that both gas-premeable and gas-selectively are This rises the contradictory relation (trade-off effects) of that drop, and this effect was proved in theory by Freeman later.In 2008, Robeson reach the standard grade (Robesonupper-bound) updated on the basis of 1991.Now, Robeson reach the standard grade into To weigh a kind of Experience norms of film properties.Therefore, researcher is pursuing design one kind and is reaching the standard grade more than Robeson always, The excellent polymer film of gas permeability.
Polyimides is as a kind of high performance material, because its excellent heat, chemical stability, good mechanical performance are wide It is general to apply in fields such as aerospace, electronic apparatus, gas separation.But although traditional polyimides is with good selection Property, but the permeability of film is often relatively low, limits its application in gas separation membrane field.
The content of the invention
In view of this, the technical problem to be solved in the present invention is in answering in providing a kind of polyimides and being separated in gas With polyimides provided by the invention also passes through after preparing film forming while with good selectivity with higher gas Property.
The present invention provides a kind of application of polyimides with structure shown in Formulas I in gas separation：
Wherein, R loses the residue after two amino, n ＞ 0 for diamine compound.
In Formulas I, n is the integer that the degree of polymerization is greater than zero, it is preferred that n=1~10000.Two horizontal line "-" represent connection Key.
One or more of the R in following group：
Wherein, 5% heat decomposition temperature >=400 DEG C under the polyimide resin nitrogen；Surveyed by BET test methods Specific surface area >=100m2/g。
In the present invention, it is described to be with the preparation method of the polyimides of structure shown in Formulas I：
2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride and binary primary amine are obtained having structure shown in Formulas I by polycondensation reaction Polyimide resin.Referring to Fig. 1, Fig. 1 is the route schematic diagram that the present invention prepares polyimides.
Specifically, comprise the following steps：
A) under the conditions of protective atmosphere, by 2,3,2 ', 3 '-bibenzene tetracarboxylic dianhydride, catalyst and alcohols solvent mixing, obtain To solution；
B solvent is removed after the mixed solution) is refluxed 0.5~2h, obtains sticky mixture；
C) polar solvent of binary primary amine and organic solvent are added into the sticky mixture, at 70~90 DEG C Under the conditions of reaction 1~2 it is small when after be warming up to again 180~210 DEG C reaction 2~12 it is small when；
D) by step C) obtained reaction product and precipitant mix, sediment is obtained, the sediment is washed and done It is dry, obtain having the polyimides of structure shown in Formulas I.
First, under the conditions of protective atmosphere, by 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, catalyst and alcohols solvent mix Close, obtain solution.
Wherein, the protective atmosphere is selected from nitrogen or inert gas, and the inert gas is preferably argon gas.
The catalyst is one or more in triethylamine, tripropyl amine (TPA) and tri-n-butylamine；The alcohols solvent be selected from methanol, One or more in ethanol, normal propyl alcohol and n-butanol.
By 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, catalyst and alcohols solvent mixing, are stirred the present invention at 70~100 DEG C Mix to being completely dissolved, obtain mixed solution；
Then, the mixed solution is refluxed 0.5~2h, then removes solvent, wherein, the side for removing solvent Method is：
Water knockout drum is connected on reflux, opens big nitrogen amount, solvent is taken out of and is sticked up to solution system becomes, agitating device Untill (such as magneton) is fixed up.
After removing solvent, sticky mixture is obtained.The polar solvent of binary primary amine and organic solvent are added to described In sticky mixture, when reaction 1~2 is small under conditions of 70~90 DEG C after to be warming up to 180~210 DEG C of reactions again 2~12 small When；
Wherein, the binary primary amine is selected from 2,4,6-trimethyl m-phenylenediamine, tetramethyl-para-phenylene diamine, and 3,3 ', 5,5 '-four Methyl biphenyl amine, 2,2- double (4- aminophenyls) hexafluoropropane, 2,2- double (3- amino -4- aminomethyl phenyls) hexafluoropropane, 2,2 ' - Two (trifluoromethyl) -4,4 '-benzidine, 4,4 '-diaminourea -3,3 '-dimethyl dinaphthalene, 1,5- naphthylenediamine, 3,3 '-diamino Base dinaphthalene, 2,8- diaminostilbenes, 3,7,9- dimethyl -6H, 12H-5,11- methyldiphenyl [b, f] [1,5] diazocines, 2,8- Diaminourea -4,10- dimethyl -6H, 12H-5,11- methyldiphenyl [b, f] [1,5] diazocine, 3,9- diaminourea -4,10- bis- Methyl -6H, 12H-5,11- methyldiphenyl [b, f] [1,5] diazocine, 2,6- diaminourea -9,10- dimethyl -9H, 10H- second Support anthracene, -1,3,3- trimethyl indenes of 6- amino -1- (4- aminophenyls), 2,2- bis- (3- methyl -4- aminophenyls) adamantane, 4, 6- dihydroxy m-phenylene diamine (MPD)s, 2,6- diaminourea triptycenes, 2,16- diaminourea -5H, 12H-5,12- [1,2] bridge phenylenes and four Benzene, 5,5 '-diaminourea -3,3,3 ', 3 '-tetramethyl -2,2 ', 3,3 '-tetrahydrochysene -1,1 '-spiral shell is double [indenes], and 5,5 '-diaminourea -6, 6 '-dihydroxy -3,3,3 ', 3 '-tetramethyl -2,2 ', 3,3 '-tetrahydrochysene -1,1 '-spiral shell is double [indenes], and 2,2 '-diaminourea -9,9 '-spiral shell pair Fluorenes, 2,2 '-diaminourea -3,3 '-dihydroxy -9,9 '-spiro-bisfluorene, 2,2 '-diaminourea -3,3 '-two bromo- 9, in 9 '-spiro-bisfluorene It is one or more.
The polar solvent is in metacresol, parachlorophenol, 1-methyl-2-pyrrolidinone and DMAC N,N' dimethyl acetamide It is one or more.
It is one or more that the organic solvent is selected from toluene, benzene, dimethylbenzene, dichloroethanes and dichloropropane.
The molar ratio of 2,2 ', the 3,3 '-bibenzene tetracarboxylic dianhydride and binary primary amine is 1:1；The toluene and polarity are molten The volume of agent is 1:(2~6), are preferably 1:(3~5).
Then, with precipitant mix after the product cooling above-mentioned heating reacted, preferably the product for heating reaction is poured into In precipitating reagent, sediment is obtained.Collect and fully washed after precipitating, is dry, obtain polyimides.The precipitating reagent be selected from methanol, One or more in ethanol, acetone and water
In certain specific embodiments of the invention, by described there is the polyimides of structure shown in Formulas I to be prepared into gas Body seperation film is applied in gas separation.
Wherein, the gas separation membrane is preferably prepared as follows：
Polyimides with structure shown in Formulas I is dissolved in organic solvent, obtains solution；
Dried after the mixed solution is coated on substrate surface, then carry out temperature programming and the demoulding, obtain gas separation Film.
The present invention first mixes the polyimide resin with structure shown in Formulas I with organic solvent, obtains mixed solution. Wherein, the organic solvent is selected from metacresol, 1-methyl-2-pyrrolidinone, n,N-dimethylacetamide, chloroform, dichloromethane Alkane, dioxane and tetrahydrofuran are one or more；Wherein, in the mixed solution, there is the polyimides of structure shown in Formulas I The mass concentration of resin is 3~20%, i.e., the solid content in described mixed solution is 3~20%.
After obtaining mixed solution, the mixed solution is coated on substrate surface, the method for the invention to the coating is simultaneously It is not particularly limited, it is preferred to use the tape casting.
Then, the substrate for being coated with mixed solution is dried, the temperature of the drying is preferably 60-80 DEG C, described The dry time is preferably 8-20h；
Dry laggard line program heating, the condition of described program heating are：
Be warming up to 80~100 DEG C of insulations 6~10 it is small when after be warming up to 130~150 DEG C of insulations 2~5 it is small when, then be warming up to When 200~250 DEG C of insulations 2~5 are small.
Present invention also offers a kind of gas separation membrane, is prepared by the polyimide resin with structure shown in Formulas I,
Wherein, R loses the residue after two amino, n ＞ 0 for diamine compound.
One or more of the R in following group：
As described above, this will not be repeated here for the preparation method of the gas separation membrane.
Gas separation membrane of the present invention carries out gas separation test, O at 1bar and 35 DEG C2Infiltration coefficient be 157.34barrer, N2Infiltration coefficient be 39.93barrer, CO2Infiltration coefficient be 684.28barrer, CH4Infiltration system Number is 36.38barrer O2/N2Selection coefficient be more than 3.94, CO2/CH4Selection coefficient be more than 18.81,5% nitrogen Lower thermal weight loss is more than 400 DEG C.Therefore, in biological air carbon dioxide and methane separation, the removal of natural air carbon dioxide and Recycling of carbon dioxide etc. has preferable application prospect in oil extraction in oil field.
What the present invention was polymerize by introducing with twist structured 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride and diamine monomer The polyimides with good filming ability is obtained.Synthesized polyimides cost is relatively low, while has higher ratio surface Product, heat endurance, gas-selectively and gas-premeable, in gas separation such as:Biological air carbon dioxide and methane separation, naturally Have a good application prospect in the removal of air carbon dioxide and oil extraction in oil field in the recycling of carbon dioxide.
Compared with prior art, the present invention provides a kind of polyimides with structure shown in Formulas I in gas separation Application.The present invention is obtained by introducing with what twist structured 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride and diamine monomer polymerize The polyimides with good filming ability is arrived.Synthesized polyimides cost is relatively low, at the same have higher specific surface area, Heat endurance, gas-selectively and gas-premeable, in gas separation such as:Biological air carbon dioxide and methane separation, natural gas Have a good application prospect in the removal of carbon dioxide and oil extraction in oil field in the recycling of carbon dioxide.
Polyimide resin provided by the invention is prepared into corresponding powder, and specific surface area is carried out by BET test methods Test, surveys specific surface area and is up to 658m2/g.The film prepared carries out gas separation test, O at 1bar and 35 DEG C2Ooze Saturating coefficient is 157.34barrer, N2Infiltration coefficient be 39.93barrer, CO2Infiltration coefficient be 684.28barrer, CH4 Infiltration coefficient be 36.38barrer O2/N2Selection coefficient be more than 3.94, CO2/CH4Selection coefficient for 18.81 with On, thermal weight loss is more than 400 DEG C under 5% nitrogen.
Brief description of the drawings
Fig. 1 is the route schematic diagram that the present invention prepares polyimides；
Fig. 2 is nitrogen adsorption-desorption isotherm of the resulting polymers at a temperature of 77K in embodiment 8；
Fig. 3 is the hot weightless picture of resulting polymers in embodiment 8；
Fig. 4 is the infrared spectrum of resulting polymers in embodiment 8；
Fig. 5 is the nuclear magnetic spectrogram of resulting polymers in embodiment 8.
Embodiment
For a further understanding of the present invention, with reference to embodiment to polyimides provided by the invention in gas separation Application illustrate, protection scope of the present invention is not limited by the following examples.
Embodiment 1：
In the present embodiment, the structural formula of polyimides is as follows：
Specifically preparation method is：Under nitrogen protection, by 1.4285g 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride is added to branch In mouth bottle, 2.45g triethylamines and 15mL ethanol are added, 80 DEG C of magnetic agitations is heated to being completely dissolved, continues back after dissolving Stream stirring 1h, then connects water knockout drum and opens big nitrogen amount, and ethanol is taken out of untill the glutinous magneton of solution system change is fixed up, is added Enter the 0.7975g tetramethyl-para-phenylene diamines of 4mLN- methyl pyrrolidones dissolving, add 1mL toluene, 80 DEG C of one hours of reaction After be warming up to 190 DEG C, react some hours becomes untill glutinous magneton is fixed up until reaction system, is cooled to 80 DEG C and adds 5mLN- methyl pyrrolidones dilute.Solution is poured into ethanol, obtains stringy solids.Polymer chloroform dissolves again with methanol Separate out, after being repeated three times, the lower 120 DEG C of drying of vacuum.
The polyimides of gained is configured to the solution that solid content is 10% with n,N-dimethylacetamide, using the tape casting On the glass plate for being spread over cleaning.Glass plate is put into again and is dried in film case, dries 8h at 80 DEG C.Then, glass plate is put Enter in vacuum drying oven, according to following steps temperature programming：100 DEG C/10h, 150 DEG C/5h, 200 DEG C/5h.Treat that temperature is down to room temperature Afterwards, glass plate demoulding into the water is taken out, you can obtain film.
Specific surface area test is carried out by BET test methods, specific surface area is surveyed and reaches 186m2/g.The film prepared exists 1bar and 35 DEG C carries out gas separation test, O2Infiltration coefficient be 35.05barrer, N2Infiltration coefficient be 7.29barrer, CO2Infiltration coefficient be 178.76barrer, CH4Infiltration coefficient be 4.91barrer O2/N2Selection coefficient be 4.81, CO2/CH4Selection coefficient be 36.40, under 5% nitrogen thermal weight loss be 497 DEG C.
Embodiment 2：
In the present embodiment, the structural formula of polyimides is as follows：
Specifically preparation method is：Under nitrogen protection, by 0.8925g 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride is added to branch In mouth bottle, 1.53g triethylamines and 15mL ethanol are added, 80 DEG C of magnetic agitations is heated to being completely dissolved, continues back after dissolving Stream stirring 1h, then connects water knockout drum and opens big nitrogen amount, and ethanol is taken out of untill the glutinous magneton of solution system change is fixed up, is added Enter the 0.7291g 3,3',5,5'-tetramethylbenzidine of 4mLN- methyl pyrrolidones dissolving, add 1mL toluene, 80 DEG C anti- 190 DEG C are warming up to after answering a hour, some hours is reacted untill the glutinous magneton of reaction system change is fixed up, is cooled to 80 DEG C And add the dilution of 5mLN- methyl pyrrolidones.Solution is poured into ethanol, obtains stringy solids.Polymer chloroform dissolves again Separated out with methanol, after being repeated three times, the lower 120 DEG C of drying of vacuum.
The polyimides of gained is configured to the solution that solid content is 10% with n,N-dimethylacetamide, using the tape casting On the glass plate for being spread over cleaning.Glass plate is put into again and is dried in film case, dries 8h at 80 DEG C.Then, glass plate is put Enter in vacuum drying oven, according to following steps temperature programming：100 DEG C/10h, 150 DEG C/5h, 200 DEG C/5h.Treat that temperature is down to room temperature Afterwards, glass plate demoulding into the water is taken out, you can obtain film.
Specific surface area test is carried out by BET test methods, specific surface area is surveyed and reaches 193m2/g.The film prepared exists 1bar and 35 DEG C carries out gas separation test, O2Infiltration coefficient be 38.02barrer, N2Infiltration coefficient be 8.09barrer, CO2Infiltration coefficient be 178.76barrer, CH4Infiltration coefficient be 5.38barrer O2/N2Selection coefficient be 4.70, CO2/CH4Selection coefficient be 33.21, under 5% nitrogen thermal weight loss be 485 DEG C.
Embodiment 3：
In the present embodiment, the structural formula of polyimides is as follows：
Specifically preparation method is：Under nitrogen protection, by 0.7863g 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride is added to branch In mouth bottle, 1.35g triethylamines and 15mL ethanol are added, 80 DEG C of magnetic agitations is heated to being completely dissolved, continues back after dissolving Stream stirring 1h, then connects water knockout drum and opens big nitrogen amount, and ethanol is taken out of untill the glutinous magneton of solution system change is fixed up, is added Enter the 0.9683g 2 of 4mLN- methyl pyrrolidones dissolving, double (3- amino -4- aminomethyl phenyls) hexafluoropropane of 2-, add 1mL Toluene, 190 DEG C are warming up to after 80 DEG C of one hours of reaction, react some hours until reaction system become glutinous magneton be fixed up into Only, 80 DEG C are cooled to and adds the dilution of 5mLN- methyl pyrrolidones.Solution is poured into ethanol, obtains stringy solids.Polymer Separated out with chloroform dissolving again with methanol, after being repeated three times, the lower 120 DEG C of drying of vacuum.
The polyimides of gained is configured to the solution that solid content is 10% with n,N-dimethylacetamide, using the tape casting On the glass plate for being spread over cleaning.Glass plate is put into again and is dried in film case, dries 8h at 80 DEG C.Then, glass plate is put Enter in vacuum drying oven, according to following steps temperature programming：100 DEG C/10h, 150 DEG C/5h, 200 DEG C/5h.Treat that temperature is down to room temperature Afterwards, glass plate demoulding into the water is taken out, you can obtain film.
Specific surface area test is carried out by BET test methods, specific surface area is surveyed and reaches 228m2/g.The film prepared exists 1bar and 35 DEG C carries out gas separation test, O2Infiltration coefficient be 36.89barrer, N2Infiltration coefficient be 7.90barrer, CO2Infiltration coefficient be 183.38barrer, CH4Infiltration coefficient be 5.50barrer O2/N2Selection coefficient be 4.67, CO2/CH4Selection coefficient be 33.37, under 5% nitrogen thermal weight loss be 487 DEG C.
Embodiment 4：
In the present embodiment, the structural formula of polyimides is as follows：
Specifically preparation method is：Under nitrogen protection, by 0.9127g 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride is added to branch In mouth bottle, 1.57g triethylamines and 15mL ethanol are added, 80 DEG C of magnetic agitations is heated to being completely dissolved, continues back after dissolving Stream stirring 1h, then connects water knockout drum and opens big nitrogen amount, and ethanol is taken out of untill the glutinous magneton of solution system change is fixed up, is added Enter the 0.9934g2 of 4mLN- methyl pyrrolidones dissolving, 2 '-two (trifluoromethyl) -4,4 '-benzidine, adds 1mL first Benzene, 190 DEG C are warming up to after 80 DEG C of one hours of reaction, react some hours untill the glutinous magneton of reaction system change is fixed up, It is cooled to 80 DEG C and adds the dilution of 5mLN- methyl pyrrolidones.Solution is poured into ethanol, obtains stringy solids.Polymer is used Chloroform dissolving again with methanol separates out, after being repeated three times, the lower 120 DEG C of drying of vacuum.
The polyimides of gained is configured to the solution that solid content is 10% with n,N-dimethylacetamide, using the tape casting On the glass plate for being spread over cleaning.Glass plate is put into again and is dried in film case, dries 8h at 80 DEG C.Then, glass plate is put Enter in vacuum drying oven, according to following steps temperature programming：100 DEG C/10h, 150 DEG C/5h, 200 DEG C/5h.Treat that temperature is down to room temperature Afterwards, glass plate demoulding into the water is taken out, you can obtain film.
Specific surface area test is carried out by BET test methods, specific surface area is surveyed and reaches 107m2/g.The film prepared exists 1bar and 35 DEG C carries out gas separation test, O2Infiltration coefficient be 31.06barrer, N2Infiltration coefficient be 6.65barrer, CO2Infiltration coefficient be 136.24barrer, CH4Infiltration coefficient be 4.08barrer O2/N2Selection coefficient be 4.67, CO2/CH4Selection coefficient be 33.37, under 5% nitrogen thermal weight loss be 490 DEG C.
Embodiment 5：
In the present embodiment, the structural formula of polyimides is as follows：
Specifically preparation method is：Under nitrogen protection, by 0.8027g 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride is added to branch In mouth bottle, 1.38g triethylamines and 15mL ethanol are added, 80 DEG C of magnetic agitations is heated to being completely dissolved, continues back after dissolving Stream stirring 1h, then connects water knockout drum and opens big nitrogen amount, and ethanol is taken out of untill the glutinous magneton of solution system change is fixed up, is added Entering the 0.8524g 4 of 4mLN- methyl pyrrolidones dissolving, 4 '-diaminourea -3,3 '-dimethyl dinaphthalene adds 1mL toluene, and 80 190 DEG C are warming up to after DEG C one hour of reaction, some hours is reacted until reaction system becomes sticks untill magneton is fixed up, is cooled to 80 DEG C and add 5mLN- methyl pyrrolidones dilution.Solution is poured into ethanol, obtains stringy solids.Polymer chloroform is molten Again with methanol is solved to separate out, after being repeated three times, the lower 120 DEG C of drying of vacuum.
The polyimides of gained is configured to the solution that solid content is 10% with n,N-dimethylacetamide, using the tape casting On the glass plate for being spread over cleaning.Glass plate is put into again and is dried in film case, dries 8h at 80 DEG C.Then, glass plate is put Enter in vacuum drying oven, according to following steps temperature programming：100 DEG C/10h, 150 DEG C/5h, 200 DEG C/5h.Treat that temperature is down to room temperature Afterwards, glass plate demoulding into the water is taken out, you can obtain film.
Specific surface area test is carried out by BET test methods, specific surface area is surveyed and reaches 560m2/g.The film prepared exists 1bar and 35 DEG C carries out gas separation test, O2Infiltration coefficient be 94.74barrer, N2Infiltration coefficient be 24.17barrer CO2Infiltration coefficient be 457.47barrer, CH4Infiltration coefficient be 19.07barrer O2/N2Selection Coefficient is 3.92, CO2/CH4Selection coefficient be 23.99, under 5% nitrogen thermal weight loss be 493 DEG C.
Embodiment 6：
In the present embodiment, the structural formula of polyimides is as follows：
Specifically preparation method is：Under nitrogen protection, by 0.8035g 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride is added to branch In mouth bottle, 1.38g triethylamines and 15mL ethanol are added, 80 DEG C of magnetic agitations is heated to being completely dissolved, continues back after dissolving Stream stirring 1h, then connects water knockout drum and opens big nitrogen amount, and ethanol is taken out of untill the glutinous magneton of solution system change is fixed up, is added Enter the 0.8423g 2,8- diaminostilbenes of 4mLN- methyl pyrrolidones dissolving, 3,7,9- dimethyl -6H, 12H-5,11- methyl two Benzene [b, f] [1,5] diazocine, adds 1mL toluene, is warming up to 190 DEG C after 80 DEG C of one hours of reaction, reacts some hours Untill the glutinous magneton of reaction system change is fixed up, it is cooled to 80 DEG C and adds the dilution of 5mLN- methyl pyrrolidones.Solution is fallen Enter in ethanol, obtain stringy solids.Polymer is separated out with chloroform dissolving again with methanol, after being repeated three times, lower 120 DEG C of vacuum Drying.
The polyimides of gained is configured to the solution that solid content is 10% with n,N-dimethylacetamide, using the tape casting On the glass plate for being spread over cleaning.Glass plate is put into again and is dried in film case, dries 8h at 80 DEG C.Then, glass plate is put Enter in vacuum drying oven, according to following steps temperature programming：100 DEG C/10h, 150 DEG C/5h, 200 DEG C/5h.Treat that temperature is down to room temperature Afterwards, glass plate demoulding into the water is taken out, you can obtain film.
Specific surface area test is carried out by BET test methods, specific surface area is surveyed and reaches 510m2/g.The film prepared exists 1bar and 35 DEG C carries out gas separation test, O2Infiltration coefficient be 80.38barrer, N2Infiltration coefficient be 20.01barrer CO2Infiltration coefficient be 397.28barrer, CH4Infiltration coefficient be 16.00barrer O2/N2Selection Coefficient is 4.01, CO2/CH4Selection coefficient be 24.83, under 5% nitrogen thermal weight loss be 473 DEG C.
Embodiment 7：
In the present embodiment, the structural formula of polyimides is as follows：
Specifically preparation method is：Under nitrogen protection, by 0.8322g 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride is added to branch In mouth bottle, 1.43g triethylamines and 15mL ethanol are added, 80 DEG C of magnetic agitations is heated to being completely dissolved, continues back after dissolving Stream stirring 1h, then connects water knockout drum and opens big nitrogen amount, and ethanol is taken out of untill the glutinous magneton of solution system change is fixed up, is added Enter 0.7930g 2,8- diaminourea -4,10- dimethyl -6H, the 12H-5,11- methyldiphenyls of 4mLN- methyl pyrrolidones dissolving [b, f] [1,5] diazocine, adds 1mL toluene, is warming up to 190 DEG C after 80 DEG C of one hours of reaction, it is straight to react some hours Untill the glutinous magneton of reaction system change is fixed up, it is cooled to 80 DEG C and adds the dilution of 5mLN- methyl pyrrolidones.Solution is poured into In ethanol, stringy solids are obtained.Polymer is separated out with chloroform dissolving again with methanol, after being repeated three times, the lower 120 DEG C of bakings of vacuum It is dry.
The polyimides of gained is configured to the solution that solid content is 10% with n,N-dimethylacetamide, using the tape casting On the glass plate for being spread over cleaning.Glass plate is put into again and is dried in film case, dries 8h at 80 DEG C.Then, glass plate is put Enter in vacuum drying oven, according to following steps temperature programming：100 DEG C/10h, 150 DEG C/5h, 200 DEG C/5h.Treat that temperature is down to room temperature Afterwards, glass plate demoulding into the water is taken out, you can obtain film.
Specific surface area test is carried out by BET test methods, specific surface area is surveyed and reaches 351m2/g.The film prepared exists 1bar and 35 DEG C carries out gas separation test, O2Infiltration coefficient be 54.70barrer, N2Infiltration coefficient be 12.40barrer CO2Infiltration coefficient be 252.11barrer, CH4Infiltration coefficient be 8.30barrer O2/N2Selection Coefficient is 4.40, CO2/CH4Selection coefficient be 30.40, under 5% nitrogen thermal weight loss be 460 DEG C.
Embodiment 8：
In the present embodiment, the structural formula of polyimides is as follows：
Specifically preparation method is：Under nitrogen protection, by 0.8214g 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride is added to branch In mouth bottle, 1.42g triethylamines and 15mL ethanol are added, 80 DEG C of magnetic agitations is heated to being completely dissolved, continues back after dissolving Stream stirring 1h, then connects water knockout drum and opens big nitrogen amount, and ethanol is taken out of untill the glutinous magneton of solution system change is fixed up, is added Enter 0.7827g 3,9- diaminourea -4,10- dimethyl -6H, the 12H-5,11- methyldiphenyls of 4mLN- methyl pyrrolidones dissolving [b, f] [1,5] diazocine, adds 1mL toluene, is warming up to 190 DEG C after 80 DEG C of one hours of reaction, it is straight to react some hours Untill the glutinous magneton of reaction system change is fixed up, it is cooled to 80 DEG C and adds the dilution of 5mLN- methyl pyrrolidones.Solution is poured into In ethanol, stringy solids are obtained.Polymer is separated out with chloroform dissolving again with methanol, after being repeated three times, the lower 120 DEG C of bakings of vacuum It is dry.
Obtained polyimides is subjected to the detection of infrared and nuclear-magnetism, the result is shown in Fig. 2 and Fig. 3, Fig. 2 is gained in embodiment 8 The infrared spectrum of polymer.Fig. 3 is the nuclear magnetic spectrogram of resulting polymers in embodiment 8.
The polyimides of gained is configured to the solution that solid content is 10% with n,N-dimethylacetamide, using the tape casting On the glass plate for being spread over cleaning.Glass plate is put into again and is dried in film case, dries 8h at 80 DEG C.Then, glass plate is put Enter in vacuum drying oven, according to following steps temperature programming：100 DEG C/10h, 150 DEG C/5h, 200 DEG C/5h.Treat that temperature is down to room temperature Afterwards, glass plate demoulding into the water is taken out, you can obtain film.
Specific surface area test is carried out by BET test methods, specific surface area is surveyed and reaches 417m2/g.The film prepared exists 1bar and 35 DEG C carries out gas separation test, O2Infiltration coefficient be 67.30barrer, N2Infiltration coefficient be 16.70barrer CO2Infiltration coefficient be 338.20barrer, CH4Infiltration coefficient be 9.90barrer O2/N2Selection Coefficient is 4.03, CO2/CH4Selection coefficient be 34.16, under 5% nitrogen thermal weight loss be 483 DEG C.It is in embodiment 8 referring to Fig. 4 Nitrogen adsorption-desorption isotherm of the resulting polymers at a temperature of 77K.Fig. 5 is the thermal weight loss of resulting polymers in embodiment 8 Figure.
Embodiment 9：
In the present embodiment, the structural formula of polyimides is as follows：
Specifically preparation method is：Under nitrogen protection, by 0.8762g 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride is added to branch In mouth bottle, 1.51g triethylamines and 15mL ethanol are added, 80 DEG C of magnetic agitations is heated to being completely dissolved, continues back after dissolving Stream stirring 1h, then connects water knockout drum and opens big nitrogen amount, and ethanol is taken out of untill the glutinous magneton of solution system change is fixed up, is added Enter the 0.7873g 2 of 4mLN- methyl pyrrolidones dissolving, 6- diaminourea -9,10- dimethyl -9H, 10H- ethylene anthracenes, add 1mL toluene, 190 DEG C are warming up to after 80 DEG C of one hours of reaction, react some hours until reaction system becomes glutinous magneton and is fixed up Untill, it is cooled to 80 DEG C and adds the dilution of 5mLN- methyl pyrrolidones.Solution is poured into ethanol, obtains stringy solids.Polymerization Thing is separated out with chloroform dissolving again with methanol, after being repeated three times, the lower 120 DEG C of drying of vacuum.
The polyimides of gained is configured to the solution that solid content is 10% with n,N-dimethylacetamide, using the tape casting On the glass plate for being spread over cleaning.Glass plate is put into again and is dried in film case, dries 8h at 80 DEG C.Then, glass plate is put Enter in vacuum drying oven, according to following steps temperature programming：100 DEG C/10h, 150 DEG C/5h, 200 DEG C/5h.Treat that temperature is down to room temperature Afterwards, glass plate demoulding into the water is taken out, you can obtain film.
Specific surface area test is carried out by BET test methods, specific surface area is surveyed and reaches 327m2/g.The film prepared exists 1bar and 35 DEG C carries out gas separation test, O2Infiltration coefficient be 51.98barrer, N2Infiltration coefficient be 11.40barrer CO2Infiltration coefficient be 228.32barrer, CH4Infiltration coefficient be 7.85barrer O2/N2Selection Coefficient is 4.56, CO2/CH4Selection coefficient be 29.07, under 5% nitrogen thermal weight loss be 468 DEG C.
Embodiment 10：
In the present embodiment, the structural formula of polyimides is as follows：
Specifically preparation method is：Under nitrogen protection, by 0.9541g 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride is added to branch In mouth bottle, 1.64g triethylamines and 15mL ethanol are added, 80 DEG C of magnetic agitations is heated to being completely dissolved, continues back after dissolving Stream stirring 1h, then connects water knockout drum and opens big nitrogen amount, and ethanol is taken out of untill the glutinous magneton of solution system change is fixed up, is added Enter 0.8639g 6- amino -1- (4- aminophenyls) -1,3,3- trimethyl indenes of 4mLN- methyl pyrrolidones dissolving, add 1mL toluene, 190 DEG C are warming up to after 80 DEG C of one hours of reaction, react some hours until reaction system becomes glutinous magneton and is fixed up Untill, it is cooled to 80 DEG C and adds the dilution of 5mLN- methyl pyrrolidones.Solution is poured into ethanol, obtains stringy solids.Polymerization Thing is separated out with chloroform dissolving again with methanol, after being repeated three times, the lower 120 DEG C of drying of vacuum.
The polyimides of gained is configured to the solution that solid content is 10% with n,N-dimethylacetamide, using the tape casting On the glass plate for being spread over cleaning.Glass plate is put into again and is dried in film case, dries 8h at 80 DEG C.Then, glass plate is put Enter in vacuum drying oven, according to following steps temperature programming：100 DEG C/10h, 150 DEG C/5h, 200 DEG C/5h.Treat that temperature is down to room temperature Afterwards, glass plate demoulding into the water is taken out, you can obtain film.
Specific surface area test is carried out by BET test methods, specific surface area is surveyed and reaches 298m2/g.The film prepared exists 1bar and 35 DEG C carries out gas separation test, O2Infiltration coefficient be 47.32barrer, N2Infiltration coefficient be 10.49barrer CO2Infiltration coefficient be 219.58barrer, CH4Infiltration coefficient be 7.28barrer O2/N2Selection Coefficient is 4.51, CO2/CH4Selection coefficient be 30.09, under 5% nitrogen thermal weight loss be 465 DEG C.
Embodiment 11：
In the present embodiment, the structural formula of polyimides is as follows：
Specifically preparation method is：Under nitrogen protection, by 0.9328g 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride is added to branch In mouth bottle, 1.60g triethylamines and 15mL ethanol are added, 80 DEG C of magnetic agitations is heated to being completely dissolved, continues back after dissolving Stream stirring 1h, then connects water knockout drum and opens big nitrogen amount, and ethanol is taken out of untill the glutinous magneton of solution system change is fixed up, is added Enter the 1.0986g 2 of 4mLN- methyl pyrrolidones dissolving, 2- bis- (3- methyl -4- aminophenyls) adamantane, adds 1mL first Benzene, 190 DEG C are warming up to after 80 DEG C of one hours of reaction, react some hours untill the glutinous magneton of reaction system change is fixed up, It is cooled to 80 DEG C and adds the dilution of 5mLN- methyl pyrrolidones.Solution is poured into ethanol, obtains stringy solids.Polymer is used Chloroform dissolving again with methanol separates out, after being repeated three times, the lower 120 DEG C of drying of vacuum.
The polyimides of gained is configured to the solution that solid content is 10% with n,N-dimethylacetamide, using the tape casting On the glass plate for being spread over cleaning.Glass plate is put into again and is dried in film case, dries 8h at 80 DEG C.Then, glass plate is put Enter in vacuum drying oven, according to following steps temperature programming：100 DEG C/10h, 150 DEG C/5h, 200 DEG C/5h.Treat that temperature is down to room temperature Afterwards, glass plate demoulding into the water is taken out, you can obtain film.
Specific surface area test is carried out by BET test methods, specific surface area is surveyed and reaches 487m2/g.The film prepared exists 1bar and 35 DEG C carries out gas separation test, O2Infiltration coefficient be 78.95barrer, N2Infiltration coefficient be 19.16barrer CO2Infiltration coefficient be 369.78barrer, CH4Infiltration coefficient be 14.77barrer O2/N2Selection Coefficient is 4.12, CO2/CH4Selection coefficient be 25.03, under 5% nitrogen thermal weight loss be 464 DEG C.
Embodiment 12：
In the present embodiment, the structural formula of polyimides is as follows：
Specifically preparation method is：Under nitrogen protection, by 0.7672g 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride is added to branch In mouth bottle, 1.32g triethylamines and 15mL ethanol are added, 80 DEG C of magnetic agitations is heated to being completely dissolved, continues back after dissolving Stream stirring 1h, then connects water knockout drum and opens big nitrogen amount, and ethanol is taken out of untill the glutinous magneton of solution system change is fixed up, is added Enter 4mLN- methyl pyrrolidones dissolving 0.8720g 2,16- diaminourea -5H, 12H-5,12- [1,2] bridge phenylene aphthacene, 1mL toluene is added, 190 DEG C are warming up to after 80 DEG C of one hours of reaction, reacts some hours until reaction system becomes glutinous magneton Untill being fixed up, it is cooled to 80 DEG C and adds the dilution of 5mLN- methyl pyrrolidones.Solution is poured into ethanol, is obtained Filamentous solid Body.Polymer is separated out with chloroform dissolving again with methanol, after being repeated three times, the lower 120 DEG C of drying of vacuum.
The polyimides of gained is configured to the solution that solid content is 10% with n,N-dimethylacetamide, using the tape casting On the glass plate for being spread over cleaning.Glass plate is put into again and is dried in film case, dries 8h at 80 DEG C.Then, glass plate is put Enter in vacuum drying oven, according to following steps temperature programming：100 DEG C/10h, 150 DEG C/5h, 200 DEG C/5h.Treat that temperature is down to room temperature Afterwards, glass plate demoulding into the water is taken out, you can obtain film.
Specific surface area test is carried out by BET test methods, specific surface area is surveyed and reaches 607m2/g.The film prepared exists 1bar and 35 DEG C carries out gas separation test, O2Infiltration coefficient be 124.74barrer, N2Infiltration coefficient be 32.34barrer CO2Infiltration coefficient be 554.38barrer, CH4Infiltration coefficient be 27.46barrer O2/N2Selection Coefficient is 3.95, CO2/CH4Selection coefficient be 20.19, under 5% nitrogen thermal weight loss be 488 DEG C.
Embodiment 13：
In the present embodiment, the structural formula of polyimides is as follows：
Specifically preparation method is：Under nitrogen protection, by 0.8537g 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride is added to branch In mouth bottle, 1.47g triethylamines and 15mL ethanol are added, 80 DEG C of magnetic agitations is heated to being completely dissolved, continues back after dissolving Stream stirring 1h, then connects water knockout drum and opens big nitrogen amount, and ethanol is taken out of untill the glutinous magneton of solution system change is fixed up, is added Enter 4mLN- methyl pyrrolidones dissolving 0.9820g 5,5 '-diaminourea -6,6 '-dihydroxy -3,3,3 ', 3 '-tetramethyl -2, 2 ', 3,3 '-tetrahydrochysene -1,1 '-spiral shell is double [indenes], adds 1mL toluene, 190 DEG C are warming up to after 80 DEG C of one hours of reaction, if reaction Dry hour untill the glutinous magneton of reaction system change is fixed up, is cooled to 80 DEG C and adds the dilution of 5mLN- methyl pyrrolidones.Will Solution is poured into ethanol, obtains stringy solids.Polymer is separated out with chloroform dissolving again with methanol, after being repeated three times, vacuum Lower 120 DEG C of drying.
The polyimides of gained is configured to the solution that solid content is 10% with n,N-dimethylacetamide, using the tape casting On the glass plate for being spread over cleaning.Glass plate is put into again and is dried in film case, dries 8h at 80 DEG C.Then, glass plate is put Enter in vacuum drying oven, according to following steps temperature programming：100 DEG C/10h, 150 DEG C/5h, 200 DEG C/5h.Treat that temperature is down to room temperature Afterwards, glass plate demoulding into the water is taken out, you can obtain film.
Specific surface area test is carried out by BET test methods, specific surface area is surveyed and reaches 376m2/g.The film prepared exists 1bar and 35 DEG C carries out gas separation test, O2Infiltration coefficient be 61.78barrer, N2Infiltration coefficient be 13.79barrer CO2Infiltration coefficient be 283.71barrer, CH4Infiltration coefficient be 9.13barrer O2/N2Selection Coefficient is 4.48, CO2/CH4Selection coefficient be 31.08, under 5% nitrogen thermal weight loss be 482 DEG C.
Embodiment 14：
In the present embodiment, the structural formula of polyimides is as follows：
Specifically preparation method is：Under nitrogen protection, by 0.8783g 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride is added to branch In mouth bottle, 1.51g triethylamines and 15mL ethanol are added, 80 DEG C of magnetic agitations is heated to being completely dissolved, continues back after dissolving Stream stirring 1h, then connects water knockout drum and opens big nitrogen amount, and ethanol is taken out of untill the glutinous magneton of solution system change is fixed up, is added Enter 4mLN- methyl pyrrolidones dissolving 1.5052g 2,2 '-diaminourea -3,3 '-two bromo- 9,9 '-spiro-bisfluorene, adds 1mL Toluene, 190 DEG C are warming up to after 80 DEG C of one hours of reaction, react some hours until reaction system become glutinous magneton be fixed up into Only, 80 DEG C are cooled to and adds the dilution of 5mLN- methyl pyrrolidones.Solution is poured into ethanol, obtains stringy solids.Polymer Separated out with chloroform dissolving again with methanol, after being repeated three times, the lower 120 DEG C of drying of vacuum.
The polyimides of gained is configured to the solution that solid content is 10% with n,N-dimethylacetamide, using the tape casting On the glass plate for being spread over cleaning.Glass plate is put into again and is dried in film case, dries 8h at 80 DEG C.Then, glass plate is put Enter in vacuum drying oven, according to following steps temperature programming：100 DEG C/10h, 150 DEG C/5h, 200 DEG C/5h.Treat that temperature is down to room temperature Afterwards, glass plate demoulding into the water is taken out, you can obtain film.
Specific surface area test is carried out by BET test methods, specific surface area is surveyed and reaches 658m2/g.The film prepared exists 1bar and 35 DEG C carries out gas separation test, O2Infiltration coefficient be 157.34barrer, N2Infiltration coefficient be 39.93barrer CO2Infiltration coefficient be 684.28barrer, CH4Infiltration coefficient be 36.38barrer O2/N2Selection Coefficient is 3.94, CO2/CH4Selection coefficient be 18.81, under 5% nitrogen thermal weight loss be 491 DEG C.
Comparative example 1：
In the present embodiment, the structural formula of polyimides is as follows：
Specifically preparation method is：Under nitrogen protection, by 1.1708g 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids, 0.7389g The benzene first of 2,8- diaminourea -4,10- dimethyl -6H, 12H-5,11- methyldiphenyl [b, f] [1,5] diazocines and 0.1608g Acid is added in polymerization bottle, adds 10g metacresols, is heated to 90 DEG C of stirrings to being completely dissolved.180 DEG C are warming up to after dissolving instead Answer 12h.After reaction, add metacresol dilution and be cooled to 90 DEG C again, solution is poured into ethanol, obtains stringy solids.It is poly- Compound is separated out with chloroform dissolving again with methanol, after being repeated three times, the lower 120 DEG C of drying of vacuum.
The polyimides of gained is configured to the solution that solid content is 10% with n,N-dimethylacetamide, using the tape casting On the glass plate for being spread over cleaning.Glass plate is put into again and is dried in film case, dries 8h at 80 DEG C.Then, glass plate is put Enter in vacuum drying oven, according to following steps temperature programming：100 DEG C/10h, 150 DEG C/5h, 200 DEG C/5h.Treat that temperature is down to room temperature Afterwards, glass plate demoulding into the water is taken out, you can obtain film.
Specific surface area test is carried out by BET test methods, specific surface area is surveyed and reaches 76m2/g.The film prepared exists 1bar and 35 DEG C carries out gas separation test, O2Infiltration coefficient be 24.5barrer, N2Infiltration coefficient be 5.1barrer, CO2Infiltration coefficient be 120.4barrer, CH4Infiltration coefficient be 3.3barrer O2/N2Selection coefficient be 4.8, CO2/ CH4Selection coefficient be 36.5, under 5% nitrogen thermal weight loss be 454 DEG C.
Comparative example 2：
In the present embodiment, the structural formula of polyimides is as follows：
Specifically preparation method is：Under nitrogen protection, by 1.1486g 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids, 0.7249g The benzene first of 3,9- diaminourea -4,10- dimethyl -6H, 12H-5,11- methyldiphenyl [b, f] [1,5] diazocines and 0.1577g Acid is added in polymerization bottle, adds 10g metacresols, is heated to 90 DEG C of stirrings to being completely dissolved.180 DEG C are warming up to after dissolving instead Answer 12h.After reaction, add metacresol dilution and be cooled to 90 DEG C again, solution is poured into ethanol, obtains stringy solids.It is poly- Compound is separated out with chloroform dissolving again with methanol, after being repeated three times, the lower 120 DEG C of drying of vacuum.
The polyimides of gained is configured to the solution that solid content is 10% with n,N-dimethylacetamide, using the tape casting On the glass plate for being spread over cleaning.Glass plate is put into again and is dried in film case, dries 8h at 80 DEG C.Then, glass plate is put Enter in vacuum drying oven, according to following steps temperature programming：100 DEG C/10h, 150 DEG C/5h, 200 DEG C/5h.Treat that temperature is down to room temperature Afterwards, glass plate demoulding into the water is taken out, you can obtain film.
Specific surface area test is carried out by BET test methods, specific surface area is surveyed and reaches 314m2/g.The film prepared exists 1bar and 35 DEG C carries out gas separation test, O2Infiltration coefficient be 39.2barrer, N2Infiltration coefficient be 9.12barrer, CO2Infiltration coefficient be 194.5barrer, CH4Infiltration coefficient be 5.7barrer O2/N2Selection coefficient be 4.3, CO2/ CH4Selection coefficient be 34.1, under 5% nitrogen thermal weight loss be 457 DEG C.
The gas separating property for the polymer that embodiment 7 and 8 and comparative example 1 and 2 are obtained is summarized, and is shown in Table 1.Table 1 contrasts for 7 and 8 resulting polymers of the present embodiment with the gas separating property of 1 and 2 resulting polymers of comparative example.
1 the present embodiment 7 of table and 8 resulting polymers are contrasted with the gas separating property of 1 and 2 resulting polymers of comparative example
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (10)

1. a kind of application of polyimides with structure shown in Formulas I in gas separation,
Wherein, R loses the residue after two amino, n ＞ 0 for diamine compound.
2. application according to claim 1, it is characterised in that one or more of the R in following group：
3. application according to claim 1 or 2, it is characterised in that 5% thermal decomposition temperature under the polyimide resin nitrogen >=400 DEG C of degree；Specific surface area >=the 100m surveyed by BET test methods2/g。
4. application according to claim 1, it is characterised in that described that there is the polyimide resin of structure shown in Formulas I Preparation method is：
2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride and binary primary amine are obtained having to the polyamides of structure shown in Formulas I by polycondensation reaction Imide resin.
5. application according to claim 4, it is characterised in that comprise the following steps：
A) under the conditions of protective atmosphere, by 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, catalyst and alcohols solvent mixing, are mixed Close solution；
B solvent is removed after the mixed solution) is refluxed 0.5~2h, obtains sticky mixture；
C) polar solvent of binary primary amine and organic solvent are added into the sticky mixture, under conditions of 70~90 Reaction 1~2 it is small when after be warming up to again 180~210 DEG C reaction 2~12 it is small when；
D) by step C) obtained reaction product and precipitant mix, sediment is obtained, the sediment is washed and dried, is obtained To the polyimides with structure shown in Formulas I.
6. application according to claim 4 or 5, it is characterised in that binary primary amine is selected from 2,4,6-trimethyl m-phenylenediamine, Tetramethyl-para-phenylene diamine, 3,3',5,5'-tetramethylbenzidine, 2,2- double (4- aminophenyls) hexafluoropropane, 2,2- double (3- ammonia Base -4- aminomethyl phenyls) hexafluoropropane, 2,2 '-two (trifluoromethyl) -4,4 '-benzidine, 4,4 '-diaminourea -3,3 '-two Methyl dinaphthalene, 1,5- naphthylenediamine, 3,3 '-diaminourea dinaphthalene, 2,8- diaminostilbenes, 3,7,9- dimethyl -6H, 12H-5,11- first Base hexichol [b, f] [1,5] diazocine, 2,8- diaminourea -4,10- dimethyl -6H, 12H-5,11- methyldiphenyls [b, f] [1, 5] diazocine, 3,9- diaminourea -4,10- dimethyl -6H, 12H-5,11- methyldiphenyl [b, f] [1,5] diazocines, 2,6- Diaminourea -9,10- dimethyl -9H, 10H- ethylene anthracene, -1,3,3- trimethyl indenes of 6- amino -1- (4- aminophenyls), 2,2- bis- (3- methyl -4- aminophenyls) adamantane, 4,6- dihydroxy m-phenylene diamine (MPD)s, 2,6- diaminourea triptycenes, 2,16- diaminourea -5H, 12H-5,12- [1,2] bridge phenylene aphthacene, 5,5 '-diaminourea -3,3,3 ', 3 '-tetramethyl -2,2 ', 3,3 '-tetrahydrochysene -1, 1 '-spiral shell is double [indenes], and 5,5 '-diaminourea -6,6 '-dihydroxy -3,3,3 ', 3 '-tetramethyl -2,2 ', 3,3 '-tetrahydrochysene -1,1 '-spiral shell pair [indenes], 2,2 '-diaminourea -9,9 '-spiro-bisfluorene, 2,2 '-diaminourea -3,3 '-dihydroxy -9,9 '-spiro-bisfluorene, 2,2 '-diaminourea - One or more in 3,3 '-two bromo- 9,9 '-spiro-bisfluorenes.
7. application according to claim 5, it is characterised in that the catalyst is selected from triethylamine, tripropyl amine (TPA) and tri-n-butylamine Middle one or more；One or more of the alcohols solvent in methanol, ethanol, normal propyl alcohol and n-butanol；The protection Atmosphere is selected from nitrogen or inert gas；The polar solvent is selected from metacresol, parachlorophenol, 1-methyl-2-pyrrolidinone and N, N- bis- One or more in methylacetamide, one or more of the precipitating reagent in methanol, ethanol, acetone and water；It is described One or more of the organic solvent in toluene, benzene, dimethylbenzene, dichloroethanes and dichloropropane；Described 2,2 ', 3,3 '-connection Pyromellitic dianhydride and the molar ratio of binary primary amine are 1:1；The volume of the toluene and polar solvent is 1:2~1:6.
8. application according to claim 5, it is characterised in that prepare the polyimides with structure shown in Formulas I It is applied into gas separation membrane in gas separation.
9. application according to claim 8, it is characterised in that the gas separation membrane is prepared as follows：
Polyimides with structure shown in Formulas I is dissolved in organic solvent, obtains solution；
The drying after substrate surface by the solution coating, then temperature programming and the demoulding are carried out, obtain gas separation membrane.
10. application according to claim 8, it is characterised in that the organic solvent is selected from metacresol, N- crassitudes Ketone, DMAC N,N' dimethyl acetamide, chloroform, dichloromethane, dioxane, tetrahydrofuran are one or more；
In the mixed solution, the mass concentration with the polyimide resin of structure shown in Formulas I is 3%-20%；
The temperature of the drying is 60~80 DEG C, and the time of the drying is 8~20h；
Described program heating condition be：
Be warming up to 80~100 DEG C of insulations 6~10 it is small when after be warming up to 130~150 DEG C of insulations 2~5 it is small when, then be warming up to 200~ When 250 DEG C of insulations 2~5 are small.
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108579471A (en) * 2018-05-03 2018-09-28 南京工业大学 A kind of preparation method of triptyl polyimide separation membrane
WO2019246235A1 (en) * 2018-06-21 2019-12-26 Dupont Electronics, Inc. Polymers for use in electronic devices
CN112275147A (en) * 2020-09-01 2021-01-29 中国科学院山西煤炭化学研究所 Self-polymerization microporous polyimide gas separation membrane and preparation method and application thereof
CN112439319A (en) * 2020-11-16 2021-03-05 中蓝晨光化工有限公司 Solvent-resistant PBO nanofiltration 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
CN113372554A (en) * 2021-06-10 2021-09-10 中国科学院宁波材料技术与工程研究所 Semi-alicyclic polyimide and application of film thereof in gas separation
CN113549008A (en) * 2021-07-20 2021-10-26 吉林大学 Diamine monomer containing aryl substituted pyridine structure, preparation and application thereof, Teleger base polymer, preparation and application thereof
CN114395127A (en) * 2021-12-29 2022-04-26 山东华夏神舟新材料有限公司 Polyimide resin for fluorine-containing gas separation and preparation method thereof
CN114716676A (en) * 2022-05-11 2022-07-08 浙江工业大学 Application of polyimide in gas separation membrane
CN115477757A (en) * 2021-05-31 2022-12-16 中国科学院宁波材料技术与工程研究所 Thermal rearrangement polymer based on 2,2', 3' -biphenyl tetracarboxylic dianhydride and preparation method and application thereof
CN115584023A (en) * 2021-12-13 2023-01-10 中国科学院福建物质结构研究所 Application of benzocarbazole modified polyimide material as gas separation membrane
CN115926220A (en) * 2022-12-08 2023-04-07 安徽方胜电子科技有限公司 Bending-resistant colorless transparent PI film and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005012397A2 (en) * 2003-07-26 2005-02-10 The University Of Manchester Microporous polymer material
CN102112203A (en) * 2008-07-02 2011-06-29 环球油品公司 Mixed matrix membranes incorporating microporous polymers as fillers
CN102227252A (en) * 2008-09-30 2011-10-26 宇部兴产株式会社 Asymmetric gas separation membrane, and gas separation method
CN103619455A (en) * 2011-06-17 2014-03-05 霍尼韦尔国际公司 Thin film gas separation membrane
CN104010718A (en) * 2011-10-18 2014-08-27 帝国创新有限公司 Membranes for separation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005012397A2 (en) * 2003-07-26 2005-02-10 The University Of Manchester Microporous polymer material
CN102112203A (en) * 2008-07-02 2011-06-29 环球油品公司 Mixed matrix membranes incorporating microporous polymers as fillers
CN102227252A (en) * 2008-09-30 2011-10-26 宇部兴产株式会社 Asymmetric gas separation membrane, and gas separation method
CN103619455A (en) * 2011-06-17 2014-03-05 霍尼韦尔国际公司 Thin film gas separation membrane
CN104010718A (en) * 2011-10-18 2014-08-27 帝国创新有限公司 Membranes for separation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ZHENGGONG WANG等: "Tröger’s Base-Based Microporous Polyimide Membranes for High-Performance Gas Separation", 《ACS MARCRO LETT.》 *
中国科学院膜应用推广中心情报部: "《膜信息荟萃 第六集 膜技术的开发与应用汇编》", 31 December 1994 *
王震等: "基于2,3,2’,3’-联苯四甲酸二酐气体分离膜的制备", 《中国化学会2017全国高分子学术论文报告会摘要集》 *

Cited By (21)

* Cited by examiner, † Cited by third party
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CN108619924A (en) * 2018-05-03 2018-10-09 南京工业大学 A kind of triptyl polyimide separation membrane
CN108579471A (en) * 2018-05-03 2018-09-28 南京工业大学 A kind of preparation method of triptyl polyimide separation membrane
CN108619924B (en) * 2018-05-03 2021-04-27 南京工业大学 Triptycenyl polyimide separation membrane
WO2019246235A1 (en) * 2018-06-21 2019-12-26 Dupont Electronics, Inc. Polymers for use in electronic devices
CN112469691A (en) * 2018-06-21 2021-03-09 杜邦电子公司 Polymers for use in electronic devices
CN112275147A (en) * 2020-09-01 2021-01-29 中国科学院山西煤炭化学研究所 Self-polymerization microporous polyimide gas separation membrane and preparation method and application thereof
CN112439319B (en) * 2020-11-16 2022-10-14 中蓝晨光化工有限公司 Solvent-resistant PBO nanofiltration membrane and preparation method thereof
CN112439319A (en) * 2020-11-16 2021-03-05 中蓝晨光化工有限公司 Solvent-resistant PBO nanofiltration 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
CN115477757B (en) * 2021-05-31 2024-04-05 中国科学院宁波材料技术与工程研究所 Thermal rearrangement polymer based on 2,2', 3' -biphenyl tetracarboxylic dianhydride, and preparation method and application thereof
CN115477757A (en) * 2021-05-31 2022-12-16 中国科学院宁波材料技术与工程研究所 Thermal rearrangement polymer based on 2,2', 3' -biphenyl tetracarboxylic dianhydride and preparation method and application thereof
CN113372554B (en) * 2021-06-10 2022-08-16 中国科学院宁波材料技术与工程研究所 Semi-alicyclic polyimide and application of film thereof in gas separation
CN113372554A (en) * 2021-06-10 2021-09-10 中国科学院宁波材料技术与工程研究所 Semi-alicyclic polyimide and application of film thereof in gas separation
CN113549008A (en) * 2021-07-20 2021-10-26 吉林大学 Diamine monomer containing aryl substituted pyridine structure, preparation and application thereof, Teleger base polymer, preparation and application thereof
CN113549008B (en) * 2021-07-20 2023-02-24 吉林大学 Diamine monomer containing aryl substituted pyridine structure, preparation and application thereof, teleger base polymer, preparation and application thereof
CN115584023A (en) * 2021-12-13 2023-01-10 中国科学院福建物质结构研究所 Application of benzocarbazole modified polyimide material as gas separation membrane
CN114395127B (en) * 2021-12-29 2023-08-22 山东华夏神舟新材料有限公司 Polyimide resin for separating fluorine-containing gas and preparation method thereof
CN114395127A (en) * 2021-12-29 2022-04-26 山东华夏神舟新材料有限公司 Polyimide resin for fluorine-containing gas separation and preparation method thereof
CN114716676A (en) * 2022-05-11 2022-07-08 浙江工业大学 Application of polyimide in gas separation membrane
CN115926220A (en) * 2022-12-08 2023-04-07 安徽方胜电子科技有限公司 Bending-resistant colorless transparent PI film and preparation method thereof
CN115926220B (en) * 2022-12-08 2023-09-26 安徽方胜电子科技有限公司 Bending-resistant colorless transparent PI film and preparation method thereof

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