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 PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- bis
- polyimide
- amino
- separation membrane
- dimethylphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 117
- 239000004642 Polyimide Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 127
- 239000012528 membrane Substances 0.000 claims abstract description 100
- 239000009719 polyimide resin Substances 0.000 claims abstract description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 18
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011737 fluorine Substances 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract 3
- 239000007789 gas Substances 0.000 claims description 63
- -1 hexafluoroisopropyl Chemical group 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 46
- 239000011521 glass Substances 0.000 claims description 40
- 229910001220 stainless steel Inorganic materials 0.000 claims description 40
- 239000010935 stainless steel Substances 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 33
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- 239000012456 homogeneous solution Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 24
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 22
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 20
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000008096 xylene Substances 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 12
- 150000008064 anhydrides Chemical class 0.000 claims description 12
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 150000004984 aromatic diamines Chemical class 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000012024 dehydrating agents Substances 0.000 claims description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001555 benzenes Chemical class 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- HKADMMFLLPJEAG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-enylbenzene Chemical group FC(F)(F)C=CC1=CC=CC=C1 HKADMMFLLPJEAG-UHFFFAOYSA-N 0.000 claims description 3
- XSIHKKFNDGFJLY-UHFFFAOYSA-N 4-[[3,5-bis(trifluoromethyl)phenyl]methyl]-2,6-dimethylaniline Chemical compound NC1=C(C=C(C=C1C)CC1=CC(=CC(=C1)C(F)(F)F)C(F)(F)F)C XSIHKKFNDGFJLY-UHFFFAOYSA-N 0.000 claims description 3
- BSESWBNMNWNFIN-UHFFFAOYSA-N CC1=CC(=CC(=C1N)C)CC2=CC=C(C=C2)C(F)(F)F Chemical compound CC1=CC(=CC(=C1N)C)CC2=CC=C(C=C2)C(F)(F)F BSESWBNMNWNFIN-UHFFFAOYSA-N 0.000 claims description 3
- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical compound C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract 1
- 238000001764 infiltration Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 48
- 239000012043 crude product Substances 0.000 description 38
- 239000000243 solution Substances 0.000 description 33
- 238000001914 filtration Methods 0.000 description 27
- 239000012295 chemical reaction liquid Substances 0.000 description 20
- 230000035699 permeability Effects 0.000 description 16
- 239000012298 atmosphere Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 13
- 238000004090 dissolution Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 7
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 0 *C(c1cc(*)c(C2*CC2)c(*)c1)(c(cc1*)cc(*)c1N)c(cc1N)cc(I)c1N Chemical compound *C(c1cc(*)c(C2*CC2)c(*)c1)(c(cc1*)cc(*)c1N)c(cc1N)cc(I)c1N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RDORBPFPNIZQSD-UHFFFAOYSA-N 1-(trifluoromethyl)-3-(3,3,3-trifluoroprop-1-enyl)benzene Chemical group FC(F)(F)C=CC1=CC=CC(=C1)C(F)(F)F RDORBPFPNIZQSD-UHFFFAOYSA-N 0.000 description 1
- ZVDSMYGTJDFNHN-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3-diamine Chemical compound CC1=CC(C)=C(N)C(C)=C1N ZVDSMYGTJDFNHN-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
Classifications
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- 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
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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
Technical Field
The invention relates to the technical field of membranes, in particular to a polyimide gas separation membrane with high permeability and high selectivity as well as a preparation method and application thereof.
Background
The membrane separation method for separating gas has the advantages of high separation efficiency, low energy loss, environmental protection, simple operation, safety, reliability, convenience in installation and debugging and the like, so that the membrane separation method is more and more widely applied to separation and purification of industrial gas in recent years. The membrane material is the core of the gas separation membrane technology, and the currently commercialized gas separation membrane materials are mainly polymer membranes such as Cellulose (CA), Polysulfone (PSF), Polydimethylsiloxane (PDMS), polyphenylene oxide (PPO), and the like. However, these gas separation membranes are not sufficiently heat resistant and have a glass transition temperature of not more than 200 ℃, and are therefore limited in some applications where temperature is a particular requirement.
Polyimide (PI) material has outstanding heat resistance and mechanical propertyIn recent years, attention has been paid to applications involving high temperature and high pressure and separation of acidic corrosive gases such as carbon dioxide. However, polyimide has relatively strong intermolecular force, dense molecular chain arrangement and low free volume fraction, so that a polyimide separation membrane has excellent gas selectivity but unsatisfactory gas permeability, and a commercial polyimide separation membrane has CO selectivity2Has a permeability coefficient of only 10 barrer. Researchers have improved the gas permeability of polyimide separation membranes by introducing bulky groups into the polyimide molecular structure to increase the fractional free volume. Ayala et al, by polymerizing 1, 3-bis (3, 4-dicarboxybenzoyl) 5-tert-butylbenzene and 1, 3-bis (3, 4-dicarboxybenzoyl) biphenyl, which are dianhydrides containing bulky side groups, with aromatic diamine 2, 2-bis (4-aminophenyl) hexafluoropropane, have a glass transition temperature of 265 ℃, and a polyimide separation membrane prepared therefrom has excellent gas selectivity for CO2The permeability coefficient of (D) was increased 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 polyimines. J Membr Sci,2003,215, 61-73). CN 101733027A discloses a polyimide separation membrane prepared by copolymerization of double-end amino polyether with long-chain structure, 1, 3-phenylenediamine and fluorine-containing aromatic dianhydride 4, 4' - (2, 2-hexafluoroisopropyl) diphthalic anhydride (6 FDA). The introduction of the long-chain copolymerization structure breaks the original regular arrangement of polymer molecular chains, so that the gas separation membrane can be used for CO separation2The permeability coefficient of (A) is increased to 77.89barrer for CO2/CH4The selection coefficient of (2) is up to 20.03. Calle et al, which have been used to prepare a polyimide separation membrane using 3,3,3 ', 4 ' - (5 ' -t-butyl-m-trimethylbenzene) tetracarboxylic dianhydride and 2,4, 6-trimethylm-phenylenediamine in a bulky structure, have excellent gas permeability and are capable of further improving gas permeability of the polyimide separation membrane, show excellent gas permeability to CO2Has a permeability coefficient of as high as 465barrer, but at the same time the gas selectivity is significantly reduced, and the CO is treated2/CH4Has a selection coefficient as low as11.7(Calle M,Garcia C,Lozano AE,de la Campa JG,de Abajo J,Alvarez C,Local chain mobilitydependence on molecular structure in polyimides with bulky side groups:Correlation with gas separation properties,J Membr Sci,2013,434,121-129)。
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a polyimide gas separation membrane with high permeability and high selectivity, which is prepared from polyimide resin with a fluorinated benzene side group structure.
The invention also aims to provide a preparation method and application of the resin and the gas separation membrane.
In order to achieve the purpose, the invention provides the following technical scheme:
a polyimide gas separation membrane prepared from a polyimide resin having a fluorinated phenyl pendant group structure, the polyimide resin having the general structural formula shown in formula I:
wherein Ar is selected from any one of the following groups:
x is CH3Or a combination of the two or more of F,
y is H or CH3，
L, M, N are the same or different and are independently selected from H, F or CF3And at least one of L, M, N is F or CF3，
n is an integer of 50 to 300.
According to the present invention, the number average molecular weight (M) of the polyimide resinn) The content of the organic solvent is 50000-200000 g/mol.
According to the invention, the thickness of the separation membrane is 25-75 μm. The gas separation membrane combines high gas permeability and high gas selectivity, specifically to CO2Permeability coefficient PCO of2Not less than 180barrer, up to 280 barrer; to CO2/CH4The selection factor of (2) is over 30 and up to 40. At the same time, the gas separation membrane exhibits excellent heat resistance (glass transition temperature T thereof)gBetween 340 and 380 ℃) and mechanical properties (tensile strength T thereofsBetween 90 and 120 MPa).
The invention also provides a preparation method of the polyimide resin in the gas separation membrane, which is characterized by comprising the following steps: under the protection of inert gas, dissolving aromatic diamine with a fluorine-containing benzene side group structure shown in a formula II in an organic solvent, then adding aromatic dianhydride shown in a formula III to obtain the polyimide resin,
wherein,
x, Y, L, M, N and Ar are as defined for formula I.
Preferably, after the formula II and the formula III are stirred until all the components are dissolved to obtain a homogeneous solution, adding a catalyst and a dehydrating agent, heating to react, removing the dehydrating agent after the reaction is finished, cooling, and pouring a precipitating agent to obtain the polyimide resin:
in the above method, the aromatic dianhydride represented by the formula III is specifically 4,4 '- (hexafluoroisopropyl) diphthalic anhydride (6FDA), 4' - (2,2, 2-trifluoromethyl-1-phenyl-ethylene) diphthalic anhydride (3FDA), 4 '- [2,2, 2-trifluoromethyl-1- (3-trifluoromethylphenyl) -ethylene ] diphthalic anhydride (HFDA), 4' - [2,2, 2-trifluoromethyl-1- (3, 5-bistrifluoromethylphenyl) -ethylene ] diphthalic anhydride (9FDA), triptycene-2, 3,6, 7-Tetracarboxylic Dianhydride (TDA), 1, 4-bis (3 ', 4' -dicarboxyphenoxy) triptycene dianhydride (TODA), 9-bis (3, 4-dianhdinophenoxyphenyl) fluorene (BAOFL).
In the above method, the aromatic diamine having a fluorinated benzene-containing pendant group structure represented by formula II is specifically α, α -bis (4-amino-3, 5-dimethylphenyl) -1- (4 ' -trifluoromethylphenyl) methane, α -bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 5 ' -bistrifluoromethylphenyl) methane, α -bis (4-amino-3, 5-dimethylphenyl) -1- (4 ' -fluorophenyl) methane, α -bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 5 ' -difluorophenyl) methane, α -bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 4 ', 5 ' -trifluorophenyl) methane, α -bis (4-amino-3, 5-dimethylphenyl) -1- (4 ' -trifluoromethylphenyl) ethane, α -bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 5 ' -bistrifluoromethylphenyl) ethane, α -bis (4-amino-3, 5-dimethylphenyl) -1- (4 ' -fluorophenyl) ethane, α -bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 5 ' -difluorophenyl) ethane, α -bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 4 ', 5' -trifluorophenyl) ethane, α -bis (4-amino-3, 5-difluorophenyl) -1- (4 '-trifluoromethylphenyl) methane, α -bis (4-amino-3, 5-difluorophenyl) -1- (4' -fluorophenyl) methane, α -bis (4-amino-3, 5-difluorophenyl) -1- (4 '-trifluoromethylphenyl) ethane, α -bis (4-amino-3, 5-difluorophenyl) -1- (4' -fluorophenyl) ethane.
The organic solvent is selected from at least one of N-methylpyrrolidone (NMP), gamma-butyrolactone, dimethyl sulfoxide (DMSO), N-dimethylacetamide (DMAc) and N, N-Dimethylformamide (DMF).
The catalyst is selected from one of isoquinoline, quinoline, triethylamine or pyridine.
The dehydrating agent is toluene or xylene.
The precipitant is selected from at least one of water, methanol, ethanol, propanol, butanol or isopropanol.
The feeding molar ratio of the aromatic diamine with the fluorine-containing benzene side group structure to the aromatic dianhydride is 0.95-1.05: 1.0.
the solid content of the homogeneous solution is 25-40 wt.%.
The feeding molar ratio of the catalyst to the aromatic dianhydride is 0.05-0.1: 1.0.
the temperature for heating and reacting is 140-180 ℃; the time is 8-12 hours.
The invention also provides a preparation method of the polyimide gas separation membrane, which comprises the following steps:
dissolving the polyimide resin with the fluorine-containing phenyl side group structure in an organic solvent to obtain the resin solution, coating the resin solution on a substrate, drying, immersing in deionized water, and stripping to obtain the polyimide gas separation membrane.
In the above method for preparing a gas separation membrane, the organic solvent is at least one selected from the group consisting of N-methylpyrrolidone (NMP), γ -butyrolactone, dimethyl sulfoxide (DMSO), N-dimethylacetamide (DMAc), and N, N-Dimethylformamide (DMF).
The substrate material is a glass plate or a stainless steel plate.
The solid content of the resin solution is 25-45 wt.%.
In the drying step, the temperature is 80-200 ℃ and the time is 3-5 hours.
The invention also provides the application of the polyimide gas separation membrane, which is used for separating and recovering carbon dioxide.
The separation and recovery comprises the separation of carbon dioxide and methane in the biogas, the removal of acid gases such as carbon dioxide in the natural gas, or the recovery of carbon dioxide in tertiary oil recovery in the oil field.
The invention has the beneficial effects that:
the polyimide gas separation membrane provided by the invention has high permeability and high selectivity, has excellent heat resistance and mechanical property, and is more suitable for separating and recovering carbon dioxide. Specifically, the invention adopts aromatic dianhydride containing a bulky structure and aromatic diamine containing a fluorine-containing benzene side group structure to prepare polyimide. Dianhydride containing a large-volume structure is combined with diamine with a large side group, so that the close packing of molecular chains can be effectively inhibited, the molecular chain spacing is increased, and the free volume fraction of a polymer is improved, so that more micropores which are beneficial to gas transmission are provided, and the gas permeability of a separation membrane is improved; meanwhile, the fluorine-containing group is introduced into the polymer structure, and the dissolving process of carbon dioxide gas is accelerated by utilizing the interaction between fluorine atoms and carbon dioxide molecules, so that the permeability of the separation membrane to carbon dioxide is further improved; in addition, the rigid polymer backbone structure not only can obtain polyimide with excellent heat resistance, but also is beneficial to maintaining high gas selectivity specific to the polyimide separation membrane.
Drawings
Fig. 1 is an infrared spectrum of the polyimide separation membrane prepared in example 1.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from published sources unless otherwise specified. In the present invention, the percentage content and the percentage concentration are both the mass percentage content and the mass percentage concentration unless otherwise specified.
Example 1 preparation of polyimide gas separation Membrane
In-situ preparationAdding 39.85 g (0.1 mol) of α -bis (4-amino-3, 5-dimethylphenyl) -1- (4 '-trifluoromethylphenyl) methane and 126 g of N-methylpyrrolidone (NMP) into a three-neck flask with a mechanical stirring device, a water separator, a nitrogen inlet and outlet and a thermometer, stirring the mixture under the protection of nitrogen until the mixture is completely dissolved, adding 44.42 g (0.1 mol) of 4, 4' - (hexafluoroisopropyl) diphthalic anhydride (6FDA) to obtain a homogeneous solution with the solid content of 40 wt.%, adding 0.65 g (0.005 mol) of isoquinoline and 21 g of toluene into the homogeneous solution, heating the reaction system to 180 ℃ for 12 hours, evaporating the toluene, stopping heating, cooling the reaction liquid to 80-120 ℃, pouring the cooled reaction liquid into methanol to obtain a fibrous crude product, collecting the precipitated crude product, repeatedly washing the crude product with methanol and water, filtering, crushing and drying the obtained polyimide resin, wherein the yield is 97%, and the number average molecular weight (M) isn) Is 1.69 × 105g/mol。
Dissolving the polyimide resin in N-methylpyrrolidone (NMP) to obtain a resin solution with the solid content of 40 wt.%, filtering, defoaming in vacuum, coating the resin solution on a glass plate or a stainless steel plate with a smooth surface, heating and baking the glass plate or the stainless steel plate in a stepped manner at 80 ℃/1 hour, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour and 200 ℃/1 hour in the air atmosphere, immersing the glass plate or the stainless steel plate in deionized water to automatically strip the separation membrane, and drying in vacuum at 120 ℃ to obtain the polyimide separation membrane with a certain thickness.
FT-IR(film,cm-1)：2925,1787,1733,1622,1527,1487,1440,1369,1298,1257,1209,1145,1110,1045,723。
The thickness of the separation film can be controlled by adjusting the model of the coating roller. The main properties of the polyimide separation membrane are shown in table 1.
Example 2 preparation of polyimide gas separation Membrane
34.85 g (0.1 mol) α -bis (4-amino-3, 5-dimethylphenyl) -1- (4 'was charged in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet and outlet, and a thermometer'147 g of-fluorophenyl) methane and N, N-dimethylacetamide (DMAc) were stirred under nitrogen to complete dissolution, and 44.42 g (0.1 mol) of 4, 4' - (hexafluoroisopropyl) diphthalic anhydride (6FDA) were added to give a homogeneous solution with a solids content of 35 wt.%. 1.29 g (0.01 mol) of quinoline and 25 g of xylene were added to the above homogeneous solution, and after the reaction system was heated to 140 ℃ and reacted for 12 hours, xylene was distilled off, and the heating was stopped. Cooling the reaction liquid to 80-120 ℃, pouring the reaction liquid into ethanol to obtain a fibrous crude product, collecting the precipitated crude product, repeatedly washing the crude product with ethanol and water, filtering, crushing and drying to obtain the polyimide resin, wherein the yield is 98%, and the number average molecular weight (M) isn) Is 1.99 × 105g/mol。
Dissolving the polyimide resin in N-methylpyrrolidone (NMP) to obtain a resin solution with the solid content of 40 wt.%, filtering, defoaming in vacuum, coating the resin solution on a glass plate or a stainless steel plate with a smooth surface, heating and baking the glass plate or the stainless steel plate in a stepped manner at 80 ℃/1 hour, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour and 200 ℃/1 hour in the air atmosphere, immersing the glass plate or the stainless steel plate in deionized water to automatically strip the separation membrane, and drying in vacuum at 120 ℃ to obtain the polyimide separation membrane with a certain thickness. The thickness of the separation film can be controlled by adjusting the model of the coating roller. The main properties of the polyimide separation membrane are shown in table 1.
Example 3 preparation of polyimide gas separation Membrane
38.44 g (0.1 mol) of α -bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 4', 5 '-trifluorophenyl) methane and 154 g of N-methylpyrrolidone (NMP) are added into a three-neck flask provided with a mechanical stirring device, a water separator, a nitrogen inlet and a nitrogen outlet and a thermometer, after stirring till complete dissolution under the protection of nitrogen, 44.42 g (0.1 mol) of 4, 4' - (hexafluoroisopropyl) diphthalic anhydride (6FDA) is added to obtain a homogeneous solution with the solid content of 35 wt.%, 1.29 g (0.01 mol) of quinoline and 26 g of toluene are added into the homogeneous solution, after the reaction system is heated to 180 ℃ and reacts for 10 hours, the toluene is distilled off, and the reaction is stoppedStopping heating. Cooling the reaction liquid to 80-120 ℃, pouring the reaction liquid into ethanol to obtain a fibrous crude product, collecting the precipitated crude product, repeatedly washing the crude product with ethanol and water, filtering, crushing and drying to obtain the polyimide resin, wherein the yield is 99%, and the number average molecular weight (M) isn) Is 1.86 × 105g/mol。
Dissolving the polyimide resin in N-methylpyrrolidone (NMP) to obtain a resin solution with the solid content of 40 wt.%, filtering, defoaming in vacuum, coating the resin solution on a glass plate or a stainless steel plate with a smooth surface, heating and baking the glass plate or the stainless steel plate in a stepped manner at 80 ℃/1 hour, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour and 200 ℃/1 hour in the air atmosphere, immersing the glass plate or the stainless steel plate in deionized water to automatically strip the separation membrane, and drying in vacuum at 120 ℃ to obtain the polyimide separation membrane with a certain thickness. The thickness of the separation film can be controlled by adjusting the model of the coating roller. The main properties of the polyimide separation membrane are shown in table 1.
Example 4 preparation of polyimide gas separation Membrane
Adding 48.05 g (0.1 mol) of α -bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 5 ' -bistrifluoromethylphenyl) ethane and 218 g of gamma-butyrolactone into a three-neck flask provided with a mechanical stirrer, a water separator, a nitrogen inlet and outlet and a thermometer, stirring under the protection of nitrogen until the materials are completely dissolved, adding 45.23 g (0.1 mol) of 4,4 ' - (2,2, 2-trifluoromethyl-1-phenyl-ethylene) phthalic anhydride (3FDA) to obtain a homogeneous solution with a solid content of 30 wt.%, adding 1.03 g (0.008 mol) of isoquinoline and 36 g of toluene into the homogeneous solution, heating the reaction system to 180 ℃ for 8 hours, evaporating the toluene, stopping heating, cooling the reaction liquid to 80-120 ℃, pouring into an ethanol/water mixed liquid (ethanol/water volume ratio is 3:1) to obtain a fibrous crude product, collecting the precipitated crude product, repeatedly washing with ethanol and water, crushing, drying, filtering and obtaining a polyimide resin with a yield of 96 percent and a number average molecular weight M of polyimiden) Is 1.47 × 105g/mol。
Dissolving the polyimide resin in gamma-butyrolactone to obtain a resin solution with the solid content of 30 wt.%, filtering, defoaming in vacuum, coating the resin solution on a glass plate or a stainless steel plate with a smooth surface, heating and baking the glass plate or the stainless steel plate in a stepped manner at the temperature of 80 ℃/1 hour, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour and 200 ℃/1 hour in the air atmosphere, immersing the glass plate or the stainless steel plate in deionized water to automatically strip the separation membrane, and drying in vacuum at the temperature of 120 ℃ to obtain the polyimide separation membrane with a certain thickness. The thickness of the separation film can be controlled by adjusting the model of the coating roller. The main properties of the polyimide separation membrane are shown in table 1.
Example 5 preparation of polyimide gas separation Membrane
Adding 38.25 g (0.105 mol) of α -bis (4-amino-3, 5-difluorophenyl) -1- (4 '-fluorophenyl) methane and 195 g of N, N-dimethylacetamide (DMAc) into a three-neck flask provided with a mechanical stirring device, a water separator, a nitrogen inlet and outlet and a thermometer, stirring under the protection of nitrogen until the materials are completely dissolved, adding 45.23 g (0.1 mol) of 4, 4' - (2,2, 2-trifluoromethyl-1-phenyl-ethylidene) diphenylanhydride (3FDA) to obtain a homogeneous solution with the solid content of 30 wt.%, adding 1.01 g (0.01 mol) of triethylamine and 32 g of xylene into the homogeneous solution, heating the reaction system to 140 ℃ for 12 hours, evaporating the xylene, stopping heating, cooling the reaction liquid to 80-120 ℃, pouring into propanol to obtain a fibrous crude product, collecting the precipitated crude product, repeatedly washing with propanol and water, filtering, crushing and drying to obtain the polyimide resin with the yield of 97%, and the number average molecular weight (M)n) Is 6.4 × 104g/mol。
Dissolving the polyimide resin in N, N-dimethylacetamide (DMAc) to obtain a resin solution with the solid content of 35 wt.%, filtering, defoaming in vacuum, coating the resin solution on a glass plate or a stainless steel plate with a smooth surface, heating and drying the glass plate or the stainless steel plate in a stepped manner at 80 ℃/1 hour, 120 ℃/1 hour, 160 ℃/1 hour and 180 ℃/1 hour in the air atmosphere, immersing the glass plate or the stainless steel plate in deionized water to automatically strip the separation membrane, and drying in vacuum at 120 ℃ to obtain the polyimide separation membrane with a certain thickness. The thickness of the separation film can be controlled by adjusting the model of the coating roller. The main properties of the polyimide separation membrane are shown in table 1.
Example 6 preparation of polyimide gas separation Membrane
36.64 g (0.1 mol) of α -bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 5 ' -difluorophenyl) methane and 133 g of N, N-Dimethylformamide (DMF) were placed in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet and outlet and a thermometer, and after stirring under nitrogen atmosphere until complete dissolution, 52.03 g (0.1 mol) of 4,4 ' - [2,2, 2-trifluoromethyl-1- (3-trifluoromethylphenyl) -ethylene]Phthalic anhydride (HFDA), resulting in a homogeneous solution with a solids content of 40 wt.%. 0.63 g (0.008 mol) of triethylamine and 22 g of xylene are added into the homogeneous solution, the temperature of the reaction system is raised to 140 ℃ for reaction for 10 hours, the xylene is distilled out, and the heating is stopped. Cooling the reaction liquid to 80-120 ℃, pouring the reaction liquid into methanol to obtain a fibrous crude product, collecting the precipitated crude product, repeatedly washing the crude product with methanol and water, filtering, crushing and drying to obtain the polyimide resin, wherein the yield is 98%, and the number average molecular weight (M) isn) Is 1.74 × 105g/mol。
Dissolving the polyimide resin in N, N-dimethylacetamide (DMAc) to obtain a resin solution with a solid content of 45 wt.%, filtering, defoaming in vacuum, coating the resin solution on a glass plate or a stainless steel plate with a smooth surface, heating and drying the glass plate or the stainless steel plate in a stepped manner at 80 ℃/1 hour, 120 ℃/1 hour, 160 ℃/1 hour and 180 ℃/1 hour in the air atmosphere, immersing the glass plate or the stainless steel plate in deionized water to automatically strip the separation membrane, and drying in vacuum at 120 ℃ to obtain the polyimide separation membrane with a certain thickness. The thickness of the separation film can be controlled by adjusting the model of the coating roller. The main properties of the polyimide separation membrane are shown in table 1.
Example 7 preparation of polyimide gas separation Membrane
41.25 g (0.1 mol) of α -bis (4-amino-3, 5-dimethylphenyl) -1- (4 '-trifluoromethylphenyl) ethane and 173 g of N-methylpyrrolidone (NMP) were placed in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet and outlet and a thermometer, and after stirring under nitrogen atmosphere until complete dissolution, 52.03 g (0.1 mol) of 4, 4' - [2,2, 2-trifluoromethyl-1- (3-trifluoromethylphenyl) -ethylene]Phthalic anhydride (HFDA), resulting in a homogeneous solution with a solids content of 35 wt.%. 0.65 g (0.005 mol) of isoquinoline and 29 g of toluene were added to the above homogeneous solution, the reaction system was heated to 180 ℃ and reacted for 8 hours, and then toluene was distilled off, and the heating was stopped. Cooling the reaction solution to 80-120 ℃, pouring the reaction solution into a methanol/water mixed solution (methanol/water volume ratio is 1:1) to obtain a fibrous crude product, collecting the precipitated crude product, repeatedly washing the crude product with methanol and water, filtering, crushing and drying to obtain the polyimide resin, wherein the yield is 97%, and the number average molecular weight (M) isn) Is 1.27 × 105g/mol。
Dissolving the polyimide resin in gamma-butyrolactone to obtain a resin solution with the solid content of 35 wt.%, filtering, defoaming in vacuum, coating the resin solution on a glass plate or a stainless steel plate with a smooth surface, performing step heating and baking at 80 ℃/1 hour, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour and 200 ℃/1 hour in the air atmosphere, immersing the glass plate or the stainless steel plate in deionized water to automatically strip the separation membrane, and performing vacuum drying at 120 ℃ to obtain the polyimide separation membrane with a certain thickness. The thickness of the separation film can be controlled by adjusting the model of the coating roller. The main properties of the polyimide separation membrane are shown in table 1.
Example 8 preparation of polyimide gas separation Membrane
43.50 g (0.105 mol) of α -bis (4-amino-3, 5-difluorophenyl) -1- (4' -trifluoromethylphenyl) methane and 287 g of dimethyl sulfoxide (DMSO) were placed in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet and outlet, and a thermometer, and stirred under nitrogen atmosphereAfter complete dissolution, 52.03 g (0.1 mol) of 4, 4' - [2,2, 2-trifluoromethyl-1- (3-trifluoromethylphenyl) -ethylene are added]Phthalic anhydride (HFDA), resulting in a homogeneous solution with 25 wt.% solids. 0.79 g (0.01 mol) of pyridine and 48 g of toluene are added into the homogeneous solution, the reaction system is heated to 160 ℃ for reaction for 12 hours, the toluene is evaporated, and the heating is stopped. Cooling the reaction liquid to 80-120 ℃, pouring the reaction liquid into propanol to obtain a fibrous crude product, collecting the precipitated crude product, repeatedly washing the crude product with propanol and water, filtering, crushing and drying to obtain the polyimide resin, wherein the yield is 96%, and the number average molecular weight (M) isn) Is 7.03 × 104g/mol。
Dissolving the polyimide resin in dimethyl sulfoxide (DMSO) to obtain a resin solution with the solid content of 30 wt.%, filtering, defoaming in vacuum, coating on a glass plate or a stainless steel plate with a smooth surface, heating and baking at 80 ℃/1 hour, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour and 200 ℃/1 hour in steps in the air atmosphere, immersing the glass plate or the stainless steel plate in deionized water to automatically strip the separation membrane, and drying in vacuum at 120 ℃ to obtain the polyimide separation membrane with a certain thickness. The thickness of the separation film can be controlled by adjusting the model of the coating roller. The main properties of the polyimide separation membrane are shown in table 1.
Example 9 preparation of polyimide gas separation Membrane
36.25 g (0.1 mol) of α -bis (4-amino-3, 5-dimethylphenyl) -1- (4 '-fluorophenyl) ethane and 177 g of N-methylpyrrolidone (NMP) were placed in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet and outlet and a thermometer, and after stirring under nitrogen atmosphere until complete dissolution, 58.83 g (0.1 mol) of 4, 4' - [2,2, 2-trifluoromethyl-1- (3, 5-bistrifluoromethylphenyl) -ethylene were added]Phthalic anhydride (9FDA) to give a homogeneous solution with a solids content of 35 wt.%. 1.29 g (0.01 mol) of quinoline and 29 g of toluene were added to the above homogeneous solution, and after the reaction system was heated to 180 ℃ and reacted for 10 hours, toluene was distilled off, and the heating was stopped. Cooling the reaction liquid to 80-120 DEG CPouring into methanol/water mixture (methanol/water volume ratio of 3:1) to obtain fibrous crude product, collecting precipitated crude product, washing with methanol and water repeatedly, filtering, pulverizing, and oven drying to obtain polyimide resin with yield of 97% and number average molecular weight (M)n) Is 1.51 × 105g/mol。
Dissolving the polyimide resin in N, N-dimethylacetamide (DMAc) to obtain a resin solution with the solid content of 35 wt.%, filtering, defoaming in vacuum, coating the resin solution on a glass plate or a stainless steel plate with a smooth surface, heating and drying the glass plate or the stainless steel plate in a stepped manner at 80 ℃/1 hour, 120 ℃/1 hour, 160 ℃/1 hour and 180 ℃/1 hour in the air atmosphere, immersing the glass plate or the stainless steel plate in deionized water to automatically strip the separation membrane, and drying in vacuum at 120 ℃ to obtain the polyimide separation membrane with a certain thickness. The thickness of the separation film can be controlled by adjusting the model of the coating roller. The main properties of the polyimide separation membrane are shown in table 1.
Example 10 preparation of polyimide gas separation Membrane
39.85 g (0.1 mol) of α -bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 4', 5 '-trifluorophenyl) ethane and 148 g of N, N-Dimethylformamide (DMF) were placed in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet and outlet and a thermometer, and after stirring under nitrogen atmosphere until complete dissolution, 58.83 g (0.1 mol) of 4, 4' - [2,2, 2-trifluoromethyl-1- (3, 5-bistrifluoromethylphenyl) -ethylene]Phthalic anhydride (9FDA) to give a homogeneous solution with a solids content of 40 wt.%. 0.40 g (0.005 mol) of pyridine and 25 g of xylene are added into the homogeneous solution, the temperature of the reaction system is raised to 140 ℃ for reaction for 12 hours, then the xylene is distilled out, and the heating is stopped. Cooling the reaction liquid to 80-120 ℃, pouring the reaction liquid into isopropanol to obtain a fibrous crude product, collecting the precipitated crude product, repeatedly washing the crude product with isopropanol and water, filtering, crushing and drying to obtain the polyimide resin, wherein the yield is 97%, and the number average molecular weight (M) isn) Is 1.36 × 105g/mol。
Dissolving the polyimide resin in dimethyl sulfoxide (DMSO) to obtain a resin solution with the solid content of 35 wt.%, filtering, defoaming in vacuum, coating on a glass plate or a stainless steel plate with a smooth surface, heating and baking at 80 ℃/1 hour, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour and 200 ℃/1 hour in steps in the air atmosphere, immersing the glass plate or the stainless steel plate in deionized water to automatically strip the separation membrane, and drying in vacuum at 120 ℃ to obtain the polyimide separation membrane with a certain thickness. The thickness of the separation film can be controlled by adjusting the model of the coating roller. The main properties of the polyimide separation membrane are shown in table 1.
Example 11 preparation of polyimide gas separation Membrane
39.72 g (0.105 mol) α -bis (4-amino-3, 5-difluorophenyl) -1- (4 '-fluorophenyl) ethane and 230 g N, N-Dimethylformamide (DMF) were placed in a three-necked flask equipped with mechanical stirring, a water separator, a nitrogen inlet and outlet and a thermometer, and after stirring under nitrogen atmosphere until complete dissolution, 58.83 g (0.1 mol) 4, 4' - [2,2, 2-trifluoromethyl-1- (3, 5-bistrifluoromethylphenyl) -ethylene]Phthalic anhydride (9FDA) to give a homogeneous solution with a solids content of 30 wt.%. 0.79 g (0.01 mol) of pyridine and 38 g of xylene are added into the homogeneous solution, the reaction system is heated to 140 ℃ for reaction for 12 hours, then the xylene is distilled out, and the heating is stopped. Cooling the reaction liquid to 80-120 ℃, pouring the reaction liquid into isopropanol to obtain a fibrous crude product, collecting the precipitated crude product, repeatedly washing the crude product with isopropanol and water, filtering, crushing and drying to obtain the polyimide resin, wherein the yield is 96%, and the number average molecular weight (M) isn) Is 5.01 × 104g/mol。
Dissolving the polyimide resin in N, N-Dimethylformamide (DMF) to obtain a resin solution with the solid content of 25 wt.%, filtering, defoaming in vacuum, coating the resin solution on a glass plate or a stainless steel plate with a smooth surface, performing step heating and baking at 80 ℃/1 hour, 120 ℃/1 hour and 160 ℃/1 hour in the air atmosphere, immersing the glass plate or the stainless steel plate in deionized water to automatically strip the separation membrane, and performing vacuum drying at 120 ℃ to obtain the polyimide separation membrane with a certain thickness. The thickness of the separation film can be controlled by adjusting the model of the coating roller. The main properties of the polyimide separation membrane are shown in table 1.
Example 12 preparation of polyimide gas separation Membrane
44.31 g (0.095 mol) of α -bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 5' -bistrifluoromethylphenyl) methane and 195 g of gamma-butyrolactone are added into a three-neck flask provided with a mechanical stirring device, a water separator, a nitrogen inlet and outlet and a thermometer, after stirring under the protection of nitrogen until the materials are completely dissolved, 39.43 g (0.1 mol) of triptycene-2, 3,6, 7-Tetracarboxylic Dianhydride (TDA) is added to obtain a homogeneous solution with the solid content of 30 wt.%, 0.65 g (0.005 mol) of isoquinoline and 32 g of xylene are added into the homogeneous solution, the reaction system is heated to 180 ℃ to react for 12 hours, the xylene is evaporated, the heating is stopped, the reaction liquid is cooled to 80-120 ℃, then poured into butanol to obtain a fibrous crude product, the precipitated crude product is collected, and the crude product is repeatedly washed by butanol and water, crushed and dried to obtain the polyimide resin with the yield of 97 percent and the number average molecular weight (M)n) Is 8.15 × 104g/mol。
Dissolving the polyimide resin in gamma-butyrolactone to obtain a resin solution with the solid content of 30 wt.%, filtering, defoaming in vacuum, coating the resin solution on a glass plate or a stainless steel plate with a smooth surface, heating and baking the glass plate or the stainless steel plate in a stepped manner at the temperature of 80 ℃/1 hour, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour and 200 ℃/1 hour in the air atmosphere, immersing the glass plate or the stainless steel plate in deionized water to automatically strip the separation membrane, and drying in vacuum at the temperature of 120 ℃ to obtain the polyimide separation membrane with a certain thickness. The thickness of the separation film can be controlled by adjusting the model of the coating roller. The main properties of the polyimide separation membrane are shown in table 1.
Example 13 preparation of polyimide gas separation Membrane
Adding 38.05 g (0.1 mol) of α -bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 5' -difluorophenyl) ethane and 178 g of dimethyl sulfoxide (DMSO) into a three-neck flask provided with a mechanical stirring device, a water separator, a nitrogen inlet and a thermometer, stirring under the protection of nitrogen until the materials are completely dissolved, adding 57.85 g (0.1 mol) of 1, 4-bis (3 ', 4' -dicarboxyphenoxy) triptycene dianhydride (TODA) to obtain a homogeneous solution with the solid content of 35 wt.%, adding 0.50 g (0.005 mol) of triethylamine and 30 g of xylene into the homogeneous solution, heating the reaction system to 160 ℃ for reaction for 12 hours, evaporating the xylene, stopping heating, cooling the reaction liquid to 80-120 ℃, pouring the cooled reaction liquid into ethanol to obtain a fibrous crude product, collecting the precipitated crude product, repeatedly washing with ethanol and water, filtering, crushing and drying to obtain the polyimide resin with the yield of 97 percent and the number average molecular weight (M)n) Is 9.24 × 104g/mol。
Dissolving the polyimide resin in N, N-dimethylacetamide (DMAc) to obtain a resin solution with the solid content of 40 wt.%, filtering, defoaming in vacuum, coating the resin solution on a glass plate or a stainless steel plate with a smooth surface, heating and drying the glass plate or the stainless steel plate in a stepped manner at 80 ℃/1 hour, 120 ℃/1 hour, 160 ℃/1 hour and 180 ℃/1 hour in the air atmosphere, immersing the glass plate or the stainless steel plate in deionized water to automatically strip the separation membrane, and drying in vacuum at 120 ℃ to obtain the polyimide separation membrane with a certain thickness. The thickness of the separation film can be controlled by adjusting the model of the coating roller. The main properties of the polyimide separation membrane are shown in table 1.
Example 14 preparation of polyimide gas separation Membrane
44.98 g (0.105 mol) of α -bis (4-amino-3, 5-difluorophenyl) -1- (4' -trifluoromethylphenyl) ethane and 203 g of N-methylpyrrolidone (NMP) are added into a three-neck flask provided with a mechanical stirring device, a water separator, a nitrogen inlet and outlet and a thermometer, after stirring until complete dissolution under the protection of nitrogen, 64.26 g (0.1 mol) of 9, 9-bis (3, 4-dianhdridyloxyphenyl) fluorene (BAOFL) are added to obtain the productTo a homogeneous solution with a solids content of 35 wt.%. 0.65 g (0.005 mol) of quinoline and 34 g of toluene were added to the above homogeneous solution, and after the reaction system was heated to 180 ℃ and reacted for 10 hours, toluene was distilled off, and the heating was stopped. Cooling the reaction solution to 80-120 ℃, pouring the reaction solution into an ethanol/water mixed solution (ethanol/water volume ratio is 1:1) to obtain a fibrous crude product, collecting the precipitated crude product, repeatedly washing the crude product with ethanol and water, filtering, crushing and drying to obtain the polyimide resin, wherein the yield is 96%, and the number average molecular weight (M) is 96%n) Is 5.93 × 104g/mol。
Dissolving the polyimide resin in N, N-dimethylacetamide (DMAc) to obtain a resin solution with the solid content of 30 wt.%, filtering, defoaming in vacuum, coating the resin solution on a glass plate or a stainless steel plate with a smooth surface, heating and drying the glass plate or the stainless steel plate in a stepped manner at 80 ℃/1 hour, 120 ℃/1 hour, 160 ℃/1 hour and 180 ℃/1 hour in the air atmosphere, immersing the glass plate or the stainless steel plate in deionized water to automatically strip the separation membrane, and drying in vacuum at 120 ℃ to obtain the polyimide separation membrane with a certain thickness. The thickness of the separation film can be controlled by adjusting the model of the coating roller. The main properties of the polyimide separation membrane are shown in table 1.
TABLE 1 Main Properties of polyimide gas separation Membrane
aHeat resistance was determined by dynamic mechanical analysis, where TgThe glass transition temperature.
bThe mechanical properties are measured by a universal material testing machine according to GB/T1040.3-2006, TSIs the tensile strength.
cThe gas separation performance is measured according to ISO15105-1 by VAC-V2 pressure difference method gas permeameter test under the conditions of 1 atmosphere/30 deg.C and separation membrane sample thickness of 50 μm, gas permeability coefficient P unit is barrer, 1barrer is 1barrer 1 × 10-10cm3(STP)cm/cm2s cmHg, selection coefficient α ═ PA/PB。
Claims (12)
1. A polyimide gas separation membrane for separating and recovering carbon dioxide, which is prepared from a polyimide resin having a fluorinated benzene side group structure, wherein the polyimide resin has a general structural formula shown in the following formula I:
wherein Ar is selected from any one of the following groups:
x is CH3Or a combination of the two or more of F,
y is H or CH3，
L, M, N are the same or different and are independently selected from H, F or CF3And at least one of L, M, N is F or CF3，
n is an integer of 50 to 300.
2. The gas separation membrane according to claim 1, wherein the polyimide resin has a number average molecular weight (M)n) The content of the organic solvent is 50000-200000 g/mol.
3. The gas separation membrane according to claim 1 or 2, wherein the thickness of the separation membrane is 25 to 75 μm.
4. A method for producing a polyimide resin in a gas separation membrane according to any one of claims 1 to 3, comprising the steps of:
under the protection of inert gas, dissolving aromatic diamine with a fluorine-containing benzene side group structure shown in a formula II in an organic solvent, and then adding aromatic dianhydride shown in a formula III to obtain the polyimide resin:
wherein,
x, Y, L, M, N and Ar are as defined for formula I.
5. The method as claimed in claim 4, wherein the polyimide resin is obtained by stirring the aromatic diamine represented by the formula II and the aromatic dianhydride represented by the formula III until all the aromatic diamine and the aromatic dianhydride are dissolved to obtain a homogeneous solution, adding a catalyst and a dehydrating agent, heating to react, removing the dehydrating agent after the reaction is finished, cooling, and pouring a precipitant into the solution.
6. The process according to claim 4 or 5, wherein the aromatic dianhydride of formula III is 4,4 '- (hexafluoroisopropyl) diphthalic anhydride (6FDA), 4' - (2,2, 2-trifluoromethyl-1-phenyl-ethylene) diphthalic anhydride (3FDA), 4 '- [2,2, 2-trifluoromethyl-1- (3-trifluoromethylphenyl) -ethylene ] diphthalic anhydride (HFDA), 4' - [2,2, 2-trifluoromethyl-1- (3, 5-bistrifluoromethylphenyl) -ethylene ] diphthalic anhydride (9FDA), triptycene-2, 3,6, 7-Tetracarboxylic Dianhydride (TDA), 1, 4-bis (3 ', 4' -dicarboxyphenoxy) triptycene dianhydride (TODA) or 9, 9-bis (3, 4-dianhdhenoxyphenyl) fluorene (BAOFL);
the aromatic diamine with the fluorine-containing benzene side group structure shown in the formula II is alpha, alpha-bis (4-amino-3, 5-dimethylphenyl) -1- (4 ' -trifluoromethylphenyl) methane, alpha-bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 5 ' -bistrifluoromethylphenyl) methane, alpha-bis (4-amino-3, 5-dimethylphenyl) -1- (4 ' -fluorophenyl) methane, alpha-bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 5 ' -difluorophenyl) methane, alpha-bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 4 ', 5 ' -trifluorophenyl) methane, α -bis (4-amino-3, 5-dimethylphenyl) -1- (4 ' -trifluoromethylphenyl) ethane, α -bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 5 ' -bistrifluoromethylphenyl) ethane, α -bis (4-amino-3, 5-dimethylphenyl) -1- (4 ' -fluorophenyl) ethane, α -bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 5 ' -difluorophenyl) ethane, α -bis (4-amino-3, 5-dimethylphenyl) -1- (3 ', 4 ', 5' -trifluorophenyl) ethane, α -bis (4-amino-3, 5-difluorophenyl) -1- (4 '-trifluoromethylphenyl) methane, α -bis (4-amino-3, 5-difluorophenyl) -1- (4' -fluorophenyl) methane, α -bis (4-amino-3, 5-difluorophenyl) -1- (4 '-trifluoromethylphenyl) ethane or α, α -bis (4-amino-3, 5-difluorophenyl) -1- (4' -fluorophenyl) ethane.
7. The method of claim 5, wherein the organic solvent is selected from at least one of N-methylpyrrolidone (NMP), γ -butyrolactone, dimethyl sulfoxide (DMSO), N-dimethylacetamide (DMAc), and N, N-Dimethylformamide (DMF);
the catalyst is selected from one of isoquinoline, quinoline, triethylamine or pyridine;
the dehydrating agent is toluene or xylene;
the precipitant is selected from at least one of water, methanol, ethanol, propanol, butanol or isopropanol.
8. The method according to claim 5, wherein the feeding molar ratio of the aromatic diamine with the fluorinated benzene side group structure to the aromatic dianhydride is 0.95-1.05: 1.0;
the solid content of the homogeneous solution is 25-40 wt.%;
the feeding molar ratio of the catalyst to the aromatic dianhydride is 0.05-0.1: 1.0;
the temperature for heating and reacting is 140-180 ℃; the time is 8-12 hours.
9. A method for producing a polyimide gas separation membrane for separation and recovery of carbon dioxide according to any one of claims 1 to 3, comprising the steps of:
dissolving the polyimide resin with the fluorine-containing phenyl side group structure in an organic solvent to obtain the resin solution, coating the resin solution on a substrate, drying, immersing in deionized water, and stripping to obtain the polyimide gas separation membrane.
10. The method of claim 9, wherein the organic solvent is at least one selected from the group consisting of N-methylpyrrolidone (NMP), γ -butyrolactone, dimethyl sulfoxide (DMSO), N-dimethylacetamide (DMAc), and N, N-Dimethylformamide (DMF);
the substrate is a glass plate or a stainless steel plate;
the solid content of the resin solution is 25-45 wt.%;
in the drying step, the temperature is 80-200 ℃ and the time is 3-5 hours.
11. Use of the polyimide gas separation membrane of any one of claims 1 to 3 for separation and recovery of carbon dioxide.
12. Use according to claim 11, wherein the separation and recovery comprises separation of carbon dioxide and methane in biogas, removal of acid gases including carbon dioxide in natural gas, or recovery of carbon dioxide in tertiary oil recovery in oil fields.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510249582.1A CN104829853B (en) | 2015-05-15 | 2015-05-15 | A kind of polyimide gas separating film and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510249582.1A CN104829853B (en) | 2015-05-15 | 2015-05-15 | A kind of polyimide gas separating film and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104829853A CN104829853A (en) | 2015-08-12 |
| CN104829853B true CN104829853B (en) | 2017-12-12 |
Family
ID=53808074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510249582.1A Active CN104829853B (en) | 2015-05-15 | 2015-05-15 | A kind of polyimide gas separating film and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104829853B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921037B (en) * | 2016-06-22 | 2018-03-30 | 辽宁科技大学 | A kind of preparation method of the porous gas separation membrane material with thermic rigid structure |
| CN106139934B (en) * | 2016-07-07 | 2017-09-12 | 南京工业大学 | Preparation method of triptycene-based polymer separation membrane |
| CN107376672B (en) * | 2017-06-23 | 2020-05-22 | 江南大学 | Green preparation method of polyimide gas separation membrane |
| CN107638815B (en) * | 2017-10-20 | 2019-09-27 | 大连欧科膜技术工程有限公司 | A kind of cellulose acetate anisotropic membrane and its application |
| CN107778504B (en) * | 2017-10-31 | 2020-09-08 | 吉林省中科聚合工程塑料有限公司 | Continuous preparation method of soluble polyarylethersulfone film |
| 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 |
| AU2022297493A1 (en) * | 2021-06-23 | 2024-01-18 | Beijing Research Institute Of Chemical Industry, China Petroleum & Chemical Corporation | Polyimide copolymer and film, preparation methods therefor and applications thereof, and system and method 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 |
| CN115232026B (en) * | 2022-07-19 | 2024-07-30 | 东华大学 | Cyano diamine-containing cyano functionalized polyimide mixed matrix membrane and preparation thereof |
| CN115382357A (en) * | 2022-08-04 | 2022-11-25 | 北京石大油源科技开发有限公司 | Adapt to medium and high concentration CO 2 Membrane separation technology with high-efficiency capture |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1970527A (en) * | 2005-11-23 | 2007-05-30 | 中国科学院化学研究所 | Diamine derivative containing fluorinated aromatic ateral group and its preparation method |
| JP5915376B2 (en) * | 2011-05-30 | 2016-05-11 | セントラル硝子株式会社 | Gas separation membrane |
| CN103619455B (en) * | 2011-06-17 | 2016-05-04 | 霍尼韦尔国际公司 | Film gas diffusion barrier |
-
2015
- 2015-05-15 CN CN201510249582.1A patent/CN104829853B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104829853A (en) | 2015-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104829853B (en) | A kind of polyimide gas separating film and preparation method and application | |
| CN111019133B (en) | Polyimide resin for gas separation membrane, preparation method thereof and method for preparing polyimide gas separation membrane by using polyimide resin | |
| Wu et al. | Preparation and gas permeation of crown ether-containing co-polyimide with enhanced CO2 selectivity | |
| CN106279685A (en) | Polyimide material, its preparation method and application of based on Teller lattice alkali structure | |
| CN114591503B (en) | Soluble poly (benzimidazole-co-imide) polymer and preparation and application thereof | |
| Wang et al. | Sub-Tg cross-linked thermally rearranged polybenzoxazole derived from phenolphthalein diamine for natural gas purification | |
| CN111116912A (en) | Polyimide resin, preparation method thereof and method for preparing polyimide film/cross-linked polyimide film by using polyimide resin | |
| KR101568119B1 (en) | Polyimide-polyethylene glycol copolymer pervaporation membranes and preparation method thereof | |
| CN114395127A (en) | Polyimide resin for fluorine-containing gas separation and preparation method thereof | |
| CN101225169B (en) | Sulfur fluoro self-crosslinkable polyimide material and preparation method thereof | |
| US11851559B2 (en) | BCDA-based semi-alicyclic homo- or co-polyimide membrane materials for gas separation and the preparation method thereof | |
| KR20140048056A (en) | Polyimide based polymeric compound and asymmetric hollow fiber membranes containing the same for gas separation | |
| CN110591092B (en) | Polyimide high polymer material based on 2, 5-diallyloxy p-phenylenediamine monomer and preparation method thereof | |
| Shin et al. | Solution-processable methyl-substituted semi-alicyclic homo-and co-polyimides and their gas permeation properties | |
| CN116284776A (en) | Polyetherimide and preparation method and application thereof | |
| CN114716676A (en) | Application of polyimide in gas separation membrane | |
| KR101477710B1 (en) | Novel polyimide derivatives, preparation method thereof and polymer gas separation membrane comprising the same | |
| KR101441344B1 (en) | Co- POLYIMIDES WITH HIGH GAS PERMEABILITY AND SELECTIVITY AND METHODS OF SYNTHESIS THEREOF | |
| CN113244788A (en) | Synthetic method and application of polyimide gas separation membrane material | |
| JP2010202864A (en) | New polyimide | |
| CN112876678A (en) | Soluble polyimide containing hexamethyl substitution structure and preparation method and application thereof | |
| CN118437170B (en) | Preparation method of hyperbranched polyimide separation membrane for carbon dioxide separation | |
| CN118290733B (en) | Polyimide with high fluorine content, gas separation membrane, and preparation method and application thereof | |
| CN114797507B (en) | Structure, preparation method and application of polyimide copolymer gas separation membrane with plasticizing effect resistance | |
| CN115869788B (en) | Polyimide random copolymer with triptycene structure, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |