CN113996193A - Copolyimide membrane, preparation method and application thereof in helium purification - Google Patents
Copolyimide membrane, preparation method and application thereof in helium purification Download PDFInfo
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- CN113996193A CN113996193A CN202111347659.0A CN202111347659A CN113996193A CN 113996193 A CN113996193 A CN 113996193A CN 202111347659 A CN202111347659 A CN 202111347659A CN 113996193 A CN113996193 A CN 113996193A
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- 239000012528 membrane Substances 0.000 title claims abstract description 54
- 229910052734 helium Inorganic materials 0.000 title abstract description 11
- 239000001307 helium Substances 0.000 title abstract description 9
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 title abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000000746 purification Methods 0.000 title abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 46
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- 239000007789 gas Substances 0.000 claims abstract description 28
- HDGLPTVARHLGMV-UHFFFAOYSA-N 2-amino-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenol Chemical compound NC1=CC(C(C(F)(F)F)C(F)(F)F)=CC=C1O HDGLPTVARHLGMV-UHFFFAOYSA-N 0.000 claims abstract description 8
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 239000000010 aprotic solvent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 229920001721 polyimide Polymers 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229940078552 o-xylene Drugs 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 238000006462 rearrangement reaction Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 150000004040 pyrrolidinones Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 39
- 230000001965 increasing effect Effects 0.000 abstract description 12
- 239000000178 monomer Substances 0.000 abstract description 9
- 150000004985 diamines Chemical class 0.000 abstract description 7
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000000919 ceramic Substances 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 150000008064 anhydrides Chemical class 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 description 13
- 230000008707 rearrangement Effects 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- -1 hexafluoroisopropylidene Chemical group 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000012856 packing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 6
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
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- 230000004580 weight loss Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
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- SICLLPHPVFCNTJ-UHFFFAOYSA-N 1,1,1',1'-tetramethyl-3,3'-spirobi[2h-indene]-5,5'-diol Chemical compound C12=CC(O)=CC=C2C(C)(C)CC11C2=CC(O)=CC=C2C(C)(C)C1 SICLLPHPVFCNTJ-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- 150000000183 1,3-benzoxazoles Chemical class 0.000 description 1
- ABADUMLIAZCWJD-UHFFFAOYSA-N 1,3-dioxole Chemical group C1OC=CO1 ABADUMLIAZCWJD-UHFFFAOYSA-N 0.000 description 1
- WHEVDDQAPKQQAV-UHFFFAOYSA-N 2-[4-(1h-benzimidazol-2-yl)phenyl]-1h-benzimidazole Chemical compound C1=CC=C2NC(C3=CC=C(C=C3)C=3NC4=CC=CC=C4N=3)=NC2=C1 WHEVDDQAPKQQAV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- 229920005548 perfluoropolymer Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B23/00—Noble gases; Compounds thereof
- C01B23/001—Purification or separation processes of noble gases
- C01B23/0036—Physical processing only
- C01B23/0042—Physical processing only by making use of membranes
- C01B23/0047—Physical processing only by making use of membranes characterised by the membrane
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- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention relates to a copolyimide membrane, a preparation method and application thereof in helium purification, belonging to the technical field of gas separation membranes. The preparation method adopts 9,9' -bis (4-aminophenyl) fluorene (Cardo) monomer and 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (APAF) as two diamine monomers, 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) as a common anhydride monomer to carry out chemical bonding to obtain a copolyimide polymer, and the polymer is transferred to a porous ceramic substrate by a simple dipping-pulling technology to form a thin selective layer. The ortho-hydroxyl groups on the APAF chain segment are thermally rearranged into a benzoxazole ring in situ, so that the rigidity and the porosity of the membrane are increased. In addition, the microporous structure of the 6FDA-APAF-Cardo membrane is controlled by regulating the APAF/Cardo ratio, so that the separation performance is changed along with the control, and the He permeability is effectively improved by the higher Cardo ratio.
Description
Technical Field
The invention relates to a copolyimide membrane, a preparation method and application thereof in helium purification, belonging to the technical field of gas separation membranes.
Background
Helium (He) has unique physicochemical properties, and plays an important role in the fields of magnetic resonance imaging, semiconductor manufacturing, aerospace, nuclear power plants and the like. Although the atmosphere contains a large amount of He, the extraction process is energy intensive because its concentration is only 5.2 ppm. Commercial helium is typically produced as a byproduct of north american natural gas, as concentrations can reach 4.05%. While helium concentrations in other natural gas reservoirs are as low as 0.2%, which are generally considered to be non-valuable gases due to the high cost of production and are thus vented to the atmosphere.
Since Cellulose Acetate (CA) films were reported in 1960 s, polymer films were widely studied for He from N2And CH4Separating. He/CH for commercial CA films4The ideal selectivity is as high as 97, while He permeability is only 14Barrer (1 Barrer-10)-10cm3(STP)cm-2s-1cmHg-1). The permeability of Cellulose Triacetate (CTA) membranes was increased to 21.8Barrer by substituting hydroxyl groups with acetyl groups in the CA chain. Even the solution diffusion mechanism is widely used to explain in detail the permeation of gases through polymer membranes, and due to inertness, He permeation is essentially governed by diffusivity rather than adsorption. In this case, the perfluoropolymers containing dioxole rings of commercial Teflon AF, Cytop and Hyflon AD also have higher permeability than the conventional CA polymers. For example, Cytop membranes exhibit He permeability of 170Barrer, He/CH4The selectivity was 84. In polyimide films, 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) is introduced to inhibit intrablock migration, thereby increasing He diffusivity.
Due to CO in natural gas2Much higher than He, the permeability will be directly from natural gasKey criteria for He extraction. For He/CH4The He permeability of the gas, poly (orthoacyloxy amide) membrane, was 33Barrer with a selectivity of 106, however, for CO-containing2The permeability is reduced by 60 percent. He/CO of Nafion-117 film due to competitive adsorption2The selectivity dropped from 4.4 at 300psig to 3.74 at 400 psig. Commercial multilayer polyamide Reverse Osmosis (RO) membranes in He/CO2/N2/CH4He permeability of 27.6 GPU (1GPU ═ 3.3928 × 10) was obtained in the quaternary mixture-10mol m-2s-1Pa-1).
[ 1 ] in the prior art, a poly (p-phenylene benzobisimidazole) membrane (He/CH) with ultrahigh selectivity is prepared on a porous ceramic carrier through interfacial polymerization4Selectivity is>1000). He permeability reaches 45GPU at 373K, and can resist CO2Water vapor and hydrocarbons. However, due to the stacking of molecular chains in the polymer, He permeability is only-7.5 GPU at normal temperature.
【1】X.Wang,M.Shan,X.Liu,M.Wang,C.M.Doherty,D.Osadchii,F.Kapteijn, High-performance polybenzimidazole membranes for helium extraction from natural gas, ACS Appl.Mater.Interfaces 11(2019)20098-20103.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in the process of membrane separation and purification of helium, the polymer membrane in the prior art has the problems of low separation factor and low He permeation flux.
The invention prepares a polymer separation membrane, and a separation layer of the polymer separation membrane is a polymer obtained by chemically bonding a 9,9' -bis (4-aminophenyl) fluorene (Cardo) monomer and a 4,4' - (hexafluoroisopropylidene) diphthalic anhydride-2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FDA-APAF) polymer, wherein in the structure of the polymer, ortho-hydroxyl on an APAF chain segment is thermally rearranged into a benzoxazole ring in situ, so that the rigidity and the cavity of the membrane are increased, and high permeability in the He separation process is realized.
The technical scheme is as follows:
a copolyimide gas separation membrane having a selective separation layer having a repeating unit structure represented by the formula:
a thermally rearranged copolyimide gas separation membrane having a selective separation layer having a repeating unit structure represented by the formula:
the copolyimide gas separation membrane further comprises a support layer for supporting the selective separation layer.
The supporting layer is made of porous ceramic materials.
A preparation method of a copolyimide gas separation membrane comprises the following steps:
and 3, dissolving the polymer obtained in the step 2 in an aprotic solvent, applying the solution on a support layer, and drying.
In the step 1, the reaction temperature is 273-283K, and the reaction time is 5-20 h.
In the step 1, the molar ratio of the 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane to the 9,9' -bis (4-aminophenyl) fluorene is 8:2 to 2: 8.
In the step 1, the aprotic solvent is selected from pyrrolidones.
In the step 2, an entrainer is added during heating reflux.
The entrainer is o-xylene.
The reflux reaction temperature is 400 ℃ and 500K, and the time is 5-20 h.
In the step 3, the second organic solvent is one selected from N-methylpyrrolidone, N-dimethylformamide and dimethylacetamide; the concentration of the polymer in the aprotic solvent is 2.5 to 20 wt%.
In step 3, the temperature in the drying process is 373-423K.
And 4, heating the film obtained in the step 3 in inert gas to perform thermal rearrangement reaction of polyimide.
The thermal rearrangement reaction temperature is 650-800K, and the time is 0.5-3 h.
Use of the above-described copolyimide membrane for gas separation of He.
The mixed gas to be separated in the gas separation also contains N2Or CH4。
Advantageous effects
The preparation method adopts 9,9' -bis (4-aminophenyl) fluorene (Cardo) monomer and 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (APAF) as two diamine monomers, 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) as a common anhydride monomer to carry out chemical bonding to obtain a copolyimide polymer, and transfers the polymer to a porous ceramic substrate by a simple dipping-pulling technology to form a thin selective layer. The ortho-hydroxyl groups on the APAF chain segment are thermally rearranged into a benzoxazole ring in situ, so that the rigidity and the porosity of the membrane are increased. In addition, the microporous structure of the 6FDA-APAF-Cardo membrane is controlled by regulating the APAF/Cardo ratio, so that the separation performance is changed along with the control, and the He permeability is effectively improved by the higher Cardo ratio. This polymer film also exhibits high stability (1100h) and resistance to impurities.
Drawings
FIG. 1 is a diagram of a precursor of a synthesized copolyimide1H NMR spectra with APAF to Cardo ratios ranging from 8:2, 5:5 and 2: 8.
Fig. 2 is a typical wide angle X-ray diffraction (WAXD) plot of copolyimide precursor films (M1-M3) and thermally rearranged films (TR M1-TR M3), with X/y being 8:2, 5:5, and 2: 8.
Fig. 3 is a graph of the results of characterization of the carrier film of (d). (a) A surface of the support membrane at a coating concentration of 5 wt.% and (b) a cross-sectional SEM; (c) the relationship between the concentration of the solution and the thickness and viscosity of the selection layer; XPS spectra of precursor film (top) and thermal rearrangement film (TR) (bottom): (d) a C1s fitted curve and (e) an N1s fitted curve; (f) the concentration versus viscosity relationship of the copolyimide/NMP system; (f) thermal rearrangement conversion rate.
FIG. 4 is a binary mixture separation performance of a 6FDA-APAF-Cardo membrane. (a) Equimolar mixture of He/CH4Temperature-related properties at 0.1 MPa; (b) He/CH of support film drawn based on 2008Robeson upper limit line4Separation performance was compared by converting permeability to permeability, with pink circles tested at 298K and 0.1MPa assuming a film thickness of 60 μm. Blue circles indicate equimolar mixtures of He/CH at 298K4And He/N2The feed pressure-related property of; (c) and (d) He/N for the same conditions2And (5) separating.
FIG. 5 is a graph of APAF to Cardo ratio vs He/CH4(a) And He/N2(b) The effect of the separation of the mixture.
FIG. 6 is a stability test result of (a) He/CH feed mole fraction vs. 6FDA-APAF-Cardo carrier membrane at 0.1MPa and 298K4(solid line) and He/N2(dotted line) impact of separation performance; (b) under the test conditions of 298K and 0.1MPa, hydrocarbon pair supporting film He/CH4And He/N2Influence of the separation performance (5 mol% ethane is marked with striped areas; bar graph representation compares to aging performance of commercial membranes).
Detailed Description
Example 16 Synthesis of FDA-APAF-Cardo Co-polyimide
The synthesis process comprises the following two steps:
(1) 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) was used as the homoanhydride, 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisAPF) and 9,9' -bis (4-aminophenyl) fluorene (Cardo) were used as the diamine monomers. The method comprises the following specific steps that a four-neck round-bottom flask is respectively filled with hydroxyl-containing diamine (bisaPAF) with three proportions: non-hydroxy diamines (Cardo) respectively ═ 8: 2mmol, 5: 5mmol and 2:8 mmol. 20mL of LNMP was added and stirred vigorously to dissolve the diamine. When all the powder was completely dissolved, 10mmol6FDA was poured into the round bottom flask. In the first stage, the reaction mixture was mechanically stirred under a flowing nitrogen atmosphere for 12 hours to synthesize polyamic acid. The reaction temperature was controlled at 278K by means of an ice bath.
(2) The imidization was carried out by vigorously stirring at 453K under a Dean-Stark reflux apparatus for 8 hours. 10mL of o-xylene as an entrainer was added to the reaction mixture in step (1) to remove water as a reaction by-product. After completion of the reaction, the resulting solution was mixed into a mixture of methanol and water (1:3), and vigorously stirred to remove o-xylene and NMP. After at least three washes, the polymer was dried in a vacuum oven at 423K for 24 hours.
The o-hydroxy copolyimide precursor is obtained through the steps.
The reaction process is as follows:
example 2
A self-supporting film was prepared using the polymer obtained in example 1, with the following steps:
three different films were prepared according to the same method. The above polymer was dissolved in NMP to form a 5% polymer solution under vigorous stirring for 12 hours. Then, after vacuum filtration through a 0.45 μm PTFE membrane, the solution was cast onto a flat bottom petri dish. The casting solution was transferred to a vacuum oven with an increasing temperature gradient of 353K for 6 hours, 373K for 6 hours, 393K for 2 hours and 423K for 2 hours to slowly evaporate the solvent. As the solvent evaporated, the precursor film was peeled off from the round bottom petri dish to obtain a transparent film with a thickness of about 60 μm. To further remove residual solvent and complete imidization, the resulting film was placed in a tube furnace and heated at a heating rate of 5K/min, maintained at 573K, for 3 hours. Three precursor films with different ratios (8:2, 5:5 and 2:8) between APAF and Cardo were named M1, M2 and M3. The o-hydroxy copolyimide precursor was further thermally rearranged to 723K at a rate of 1K/min under an Ar atmosphere and maintained at this temperature for 1 hour, and then slowly cooled to room temperature. The prepared poly (benzoxazole-co-imide) (TR-PBOI) membranes were designated TR-M1, TR-M2, and TR-M3.
The reaction formula is as follows:
example 3
The polymer obtained in example 1 is loaded on the surface of a ceramic support to prepare a support membrane, and the preparation method comprises the following steps:
an equimolar polymer solution of diamine was chosen to prepare a 6FDA-Cardo: APAF (5:5) support membrane. Support films having various solution concentrations (2.5%, 5%, 10%, 20% wt.) were produced by the dip-and-pull method, using NMP as the solvent. The specific route is that the ceramic carrier with sealed edge is inverted, immersed into the prepared solution and then placed into a fume hood for 0.5 hour for defoaming, so as to avoid defects. The vacuum oven was set at 333K, 353K, 373K, 453K to remove the solvent slowly. Finally, the film with the yellow selective layer was transferred under Ar atmosphere to a tube furnace and heated to 723K for 1 hour. The resulting asymmetric membranes showed different selective layer thicknesses.
In the following separation experiments, gas separation was performed using the 5% wt. porous ceramic-supported polymer membrane obtained in this example.
Characterization of the Polymer
Characterization of NMR:
a mixture of a diamine prepared as described in example 1 by modulating hydroxyl containing groups (bisAPAF, x): three hydroxy-copolyimide precursors were synthesized with a molar ratio of non-hydroxy diamine (Cardo, y) 8:2, 5:5 and 2: 8.1H nmr spectroscopy was used to confirm the success of the synthesis (figure 1). Chemical shifts of 7.3-7.4ppm (a-e) and 7.6ppm (f) are attributed to the aromatic proton signal of the Cardo segment, demonstrating successful polymerization of 6FDA and Cardo monomers. The presence of APAF is well documented by chemical shifts of 10.5ppm, 7.1ppm, 7.2ppm, and 7.5ppm (j, i, h, and g). Three 1H NMR analyses with different APAF to Cardo ratiosReflecting different peak intensities. In general, the peak intensity of the ortho hydroxyl proton signal (j) gradually decreases as the APAF ratio decreases, while the peak intensities of a-e increase as the Cardo segment increases. No chemical shift was found at 6.5ppm, which should be attributed to the amide proton. The results show that the polyamic acid is completely converted to a copolyimide by high temperature imidization and further heat treatment at 573K.
The polymer parameter test results are as follows:
the number average molecular weight (Mn) of the polyimide precursor exceeds 30000g mol-1Weight average molecular weight (Mw) higher than 60000g mol-1The ideal polydispersity index (PDI) is shown in Table 1. For comparison, the molecular weight of 6FDA-bisAPAF polyimide was investigated: mn 21300 Mw 97200, polydispersity 4.2. Our hydroxy copolyamide has a higher molecular weight and lower polydispersity than 6 FDA-bisAPAF. This is because the high reactivity of 6FDA, APAF and Cardo produces a long backbone, easily producing a membrane with high mechanical strength.
TABLE 1 Polymer parameters
Method for testing thermal conversion: TGA measurements were performed on a thermogravimetric analyzer device by monitoring the mass loss of polymer upon heating the sample. In N2Under protection, the temperature range is set to 298K to 1273K, and the speed is 5 K.min-1. Percent thermal conversion was calculated as the ratio of actual weight loss to theoretical mass loss:
the actual weight loss is CO in the thermal rearrangement process2Actual mass loss (%) released, theoretical weight loss is a calculated value of theoretical weight loss from conversion of the hydroxyl-containing polyimide segment to the corresponding PBO segment through a rearrangement process.
Wide angle X-ray diffraction (WAXD) test:
the incorporation of bulky Cardo fragments can hinder chain stacking of the polymer backbone, which is beneficial for improving permeability. Wide angle X-ray diffraction (WAXD) was used to evaluate polymer chain packing characteristics FIG. 2. All films showed two diffraction peaks, representing the average interchain packing density of ordered domains and pi-pi packing in molecular scale packing. As expected, d-spacing showed a monotonic increase as the Cardo fraction increased from 20% to 80%, whether it was a precursor film or a thermally rearranged film. For example, d-spacing of TR M3 is increased compared to TR M1
It is highlighted that a higher Cardo composition results in a lower chain packing density. After 1h of thermal rearrangement at 726K, the peak was shifted to higher angles. In M2, d-spacing is
And
after rearrangement to higher
And
the d-spacing increases, indicating a greater free volume fraction (FFV), which is significantly related to gas separation performance.
X-ray photoelectron spectroscopy (XPS) test:
the chemical composition of the precursor and TR film surfaces were distinguished by X-ray photoelectron spectroscopy (XPS, a-b of fig. 3) to demonstrate thermal rearrangement of the chains. The protonated N-C ═ O group (a, C1s of fig. 3) is evidenced by a signal of 288.5 eV. Due to the heat treatment, part of the imide ring was converted into a benzoxazole ring, and the peak area was significantly decreased from 33.5% to 10.0%. In the curve fitted to N1s (b in fig. 3), an additional peak (C ═ N) at 397.9eV from the transformed benzoxazole ring, except that the same C — N — C bond in the imide ring was designated 399.0eV, further indicating the success of benzoxazole cyclization.
Separation Performance
Use of copolyimides prepared with equimolar APAF and Cardo, Carrier Membrane Pair He/CH prepared at 5% wt. concentration4And He/N2The separation performance of the mixture was evaluated. The blank support showed a He permeability of about 1532 GPUs and a He/CH of 2.64And (4) selectivity. The 6FDA-APAF-Cardo film showed excellent He/CH at 298K and 0.1MPa test conditions4Selectivity of 74, He/N2He permeability was-40 GPU at 50. The membrane performance tested at higher temperatures and feed pressures not only exceeded He/CH of 2008Robeson4And He/N2The upper limit [ 2 ] but also exceeds various most advanced membranes including PBDI, PIM, Poly (PFMD) and TR-PBOI membranes (fig. 4).
To further understand the effect of Cardo on film performance, we performed He/CH on self-supporting films4And He/N2Mixture separation performance was evaluated (fig. 5). The He permeability increases significantly with increasing Cardo moiety. For the precursor film, the He permeability increased significantly from 112.9Barrer to 2127.5 Barrer with increasing Cardo ratio, but He/CH4The selectivity of the pair only drops from 124.8 to 38.2. At He/N2The same trend occurs in the system, with an increase in He permeability from 124.5Barrer to 2120.3Barrer, with a decrease from 112.4 to 31.4. This is due to the presence of a bulkier Cardo moiety, which effectively suppresses chain packing and suppresses local rotational mobility of the polymer chains, resulting in high free volume (FFV).
The same phenomenon occurs in Thermally Rearranged (TR) membranes. Furthermore, the He permeability of the TR-film is significantly higher than the corresponding precursor, which may be associated with rigid benzoxazole units and form large microcavities. For example, TR M2 films have He permeability up to 844.8Barrer, about 3.6 times higher than M2 films, but He/CH4The selectivity of the separation decreased only from 85.7 to 63.8. The results obtained highlight the advancement of these TR films. Both the thermal rearrangement of the 6FDA-APAF fragment and the increase of the Cardo moiety contribute to the improvement of permeability. TR M3 has a higher Cardo addition, the highest He permeability, at He/CH4In 3027Barrer in He/N22880Barrer in the system, which indicates that Cardo plays a more critical role in enhancing permeability. The resulting high permeability is competitive in large-scale industrial production. Generally, high pressure driving force and expansion of membrane area are always used to increase He production. However, these measures tend to cause shrinkage of the active layer, plasticization of the film and excessive energy consumption. High He permeability is the most effective means of increasing permeability.
In addition, high performance membranes with excellent stability are critical for long term separation applications. However, physical aging often severely affects the separation performance of high free volume fraction polymers. We evaluated the durability of TR films for a time span of 1100 hours. Even with such thin membranes, the membranes showed a weak permeability reduction, He 13%, CH, as shown in region b of FIG. 6422% of N2The content was 19%. For comparison (bar chart), Brandon et al report [ 3 ] that the permeability of polysulfone, Matrimid, and poly (dimethylsiloxane) membranes decreased to over 50% after about 1000 hours of aging with various gases. The novel spirobiindane polymers exhibit a 20% He permeability decrease over 140 hours. Polyimide films based on glassy 6FDA (6FDA-6FpDA) track changes in gas permeability, with a 30% decrease in He permeability and N in 1000 hours2The permeability is reduced by 60%. This can be attributed to the Cardo structure of the tetra-phenyl ring attached to the quaternary carbon resulting in a strong rotational hindrance of the phenyl group. In addition, benzoxazoles formed by thermal rearrangement prevent the phenylene heterocycles from rotating due to the high torsional energy barrier, resulting in a stable microstructure. He, CH due to competitive adsorption of hydrocarbons (stripe region near 900 h)4And N2The permeability of (a) slightly decreases with the introduction of 5 mol% ethane. He permeability decreased by 8.5%. CH (CH)4And N2The decrease due to the competitive effect is more obvious, resulting in He/CH4And He/N2The selectivity was higher with an increase of 5.4%. After removal of ethane, the separation performance was restored to the previous state. DD3R film showed a 19% He permeability decrease after ethane incorporation.
【2】L.M.Robeson,The upper bound revisited,J.Membr.Sci.320(2008)390-400.
【3】B.W.Rowe,B.D.Freeman,D.R.Paul,Physical aging of ultrathin glassy polymer films tracked by gas permeability,Polymer 50(2009)5565-5575。
Claims (10)
1. A copolyimide gas separation membrane characterized in that a selective separation layer thereof has any one of the repeating unit structures represented by the following formulae:
2. the copolyimide gas separation membrane according to claim 1, further comprising a support layer for supporting a selective separation layer.
3. The copolyimide gas separation membrane according to claim 2, wherein the support layer is a porous ceramic material.
4. A method for preparing a copolyimide gas separation membrane is characterized by comprising the following steps:
step 1, adding 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 9,9' -bis (4-aminophenyl) fluorene into an aprotic solvent to perform polymerization reaction;
step 2, heating and refluxing the reaction mixture obtained in the step 1, adding a mixture of alcohol and water for washing, and drying the obtained polymer;
and 3, dissolving the polymer obtained in the step 2 in an aprotic solvent, applying the solution on a support layer, and drying.
5. The method for preparing a copolyimide gas separation membrane as described in claim 4, wherein in the step 1, the reaction temperature is 273-283K, and the reaction time is 5-20 h; in the step 1, the molar ratio of 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane to 9,9' -bis (4-aminophenyl) fluorene is 8:2-2: 8; the aprotic solvent is selected from the group consisting of pyrrolidinones.
6. The method for producing a copolyimide gas separation membrane as described in claim 4, wherein in the step 2, an entrainer is added at the time of temperature rise and reflux; the entrainer is o-xylene; the reflux reaction temperature is 400 ℃ and 500K, and the time is 5-20 h.
7. The method for producing a copolyimide gas separation membrane according to claim 4, wherein in the step 3, the aprotic solvent is one selected from the group consisting of N-methylpyrrolidone, N-dimethylformamide, and dimethylacetamide; the concentration of the polymer in the aprotic solvent is from 2.5 to 20 wt%; in step 3, the temperature in the drying process is 373-423K.
8. The method for producing a copolyimide gas separation membrane according to claim 4, further comprising a step 4 of heating the membrane obtained in the step 3 in an inert gas to perform thermal rearrangement reaction of polyimide; the thermal rearrangement reaction temperature is 650-800K, and the time is 0.5-3 h.
9. Use of the copolyimide film of claim 1 in gas separation for He.
10. The use according to claim 9, wherein the gas mixture to be separated in the gas separation further comprises N2Or CH4。
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