CN113845659A - Network type polyimide resin with flexible side chain, preparation method thereof and application in gas separation - Google Patents
Network type polyimide resin with flexible side chain, preparation method thereof and application in gas separation Download PDFInfo
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- CN113845659A CN113845659A CN202111221757.XA CN202111221757A CN113845659A CN 113845659 A CN113845659 A CN 113845659A CN 202111221757 A CN202111221757 A CN 202111221757A CN 113845659 A CN113845659 A CN 113845659A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 96
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 85
- 238000000926 separation method Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 16
- GBLYTZIAPKMNET-UHFFFAOYSA-N CCCCCCC1C2=CC(CCCCCC)=C(CCCCCC)C(CCCCCC)=C2C(CCCCCC)=C1CCCCCC Chemical compound CCCCCCC1C2=CC(CCCCCC)=C(CCCCCC)C(CCCCCC)=C2C(CCCCCC)=C1CCCCCC GBLYTZIAPKMNET-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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 abstract description 9
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 150000008064 anhydrides Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- -1 hexahexyltriaminoindene Chemical compound 0.000 claims description 4
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical group C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 125000006159 dianhydride group Chemical group 0.000 claims 1
- YGPLLMPPZRUGTJ-UHFFFAOYSA-N truxene Chemical compound C1C2=CC=CC=C2C(C2=C3C4=CC=CC=C4C2)=C1C1=C3CC2=CC=CC=C21 YGPLLMPPZRUGTJ-UHFFFAOYSA-N 0.000 claims 1
- 238000001879 gelation Methods 0.000 abstract description 9
- 230000035699 permeability Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract description 5
- 239000013638 trimer Substances 0.000 abstract description 5
- 229920006254 polymer film Polymers 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000001131 transforming effect Effects 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 33
- 229910002092 carbon dioxide Inorganic materials 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
-
- 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
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
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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
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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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
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- 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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- 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
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Abstract
Network type polyimide resin with flexible side chain, preparation method thereof and application in gas separation, and mainly used for N2、O2、CO2Separating purity of micromolecular gasAnd (4) transforming. The network type polyimide resin takes hexa-hexyl indene trimer triamine and a dianhydride monomer (shown in figure 1) which is sold in the market as raw materials, and a polyamic acid solution is obtained through polycondensation reaction at room temperature. Then, a network type polyimide resin film with a flexible side chain is prepared through flat plate film laying and imidization. The obtained film has good gas selectivity and gas permeability. Due to the large-volume flexible side chain introduced into the polyimide resin amine monomer, the free volume of a network compact structure in the polymer and the degree of freedom of movement of a local chain segment are increased, so that the gas permeability of the polymer film material is improved, and the risk of gelation in the polycondensation reaction is effectively avoided. The polyimide film pair is CO2/N2、O2/N2Has approached or exceeded the 2008 Rebeson upper limit.
Description
Technical Field
The invention belongs to the technical field of membrane separation chemical industry, and relates to synthesis of microporous network type polyimide resin with good thermal stability and organic solvent resistance, a polymer film and a preparation method and application of a carbon film of the polymer film, which are suitable for greenhouse gas CO2Trapping and air separation.
Background
In order to meet the increasing global energy demand, the demand for fossil fuels is increasing, and thus a large amount of carbon dioxide generated by combustion is discharged into the human environment, directly resulting in severe global warming. Recently, membrane separation has attracted extensive attention with low energy consumption, low maintenance costs, and excellent stability, and the core membrane material plays a crucial role in membrane separation efficiency. To this end, carbon dioxide capture and oxyfuel combustion technologies based on membrane separation processes have gone into the public's field of view. Due to the advantages of high efficiency, strong mechanical properties and structural diversity, various polymer materials, such as polysulfone, cellulose acetate ketone, cellulose acetate, polyimide, etc., have been widely studied. Among them, polyimide has advantages such as a stable chemical structure and excellent mechanical properties, and thus has a high permeation flux and a high selectivity when separating a gas mixture, and thus polyimide is the most promising candidate for a membrane material and is widely used for the preparation of a gas separation membrane.
The network type polyimide material has good plasticizing resistance, chemical/thermal stability and rich pore channel structure due to the unique highly cross-linked structure, so that the material is widely applied to the field of gas separation membranes. However, the highly crosslinked structure tends to result in a great decrease in the permeability of the polyimide film to various gases. On the other hand, the difficulty of easy gelation is also faced in the process of preparing the network type polyimide film material by adopting the in-situ crosslinking method. At present, the methods for overcoming gelation usually inhibit the gelation process by controlling the solid content or reducing the reaction temperature, but these methods cause many disadvantages in the film preparation process, such as: difficult film formation, large energy consumption and the like, seriously limit the application and development of the membrane in the field of gas separation membranes and lead the industrialization progress to be slow. Therefore, the design of the high-permeability network type polyimide film and the solution of the problem of easy gelation in the preparation process have important application values.
Disclosure of Invention
The invention aims to solve the problems of easy gelation, generally low gas flux and the like in the preparation reaction process of the traditional network type polyimide resin film, and provides a network type polyimide resin containing a large-volume flexible side chain, a preparation method of the resin film and a carbon film and application in gas separation.
In order to achieve the above object, the present invention specifically comprises:
1. a network type polyimide resin taking hexa-hexyl indene trimer as a cross-linking point is designed and synthesized, so that the gas separation performance of the polymer material is improved by regulating and controlling the structure of a monomer.
2. The network type polyimide resin film rich in bulky flexible side chains is designed and synthesized to improve the flexibility of resin film materials, and the introduced flexible side chains are utilized to increase the degree of freedom of partial chain segment movement and the free volume of a network compact structure in a polymer, so that the risk of gelation is effectively avoided, and the gas flux is improved to a great extent.
3. Provides a preparation method of the network type polyimide resin film with the flexible side chain and a carbon film.
4. The use of the above-described network type polyimide film having a flexible side chain in gas separation is provided.
5. Provides the application of the network type polyimide resin carbon membrane with the flexible side chain in gas separation.
The technical scheme of the invention is as follows:
a network type polyimide resin with flexible side chains has the following structural general formula:
in some preferred embodiments of the present invention, Ar is one of the following structural formulas:
the invention provides a series of network type polyimide resins, which are specifically compounds shown as formula HTUTA-ODPA, formula HTUTA-BTDA or formula HTUTA-6 FDA:
the invention also provides a preparation method of the network type polyimide resin with the flexible side chain, and the synthetic route is as follows:
ar in the above synthetic route has the same meaning as described for the polyimide resin.
The preparation method of the network type polyimide resin with the flexible side chain comprises the following steps:
according to the preparation method, hexahexyl indene trimer and commercial dianhydride (ODPA, BTDA, 6FDA) are used as reaction raw materials, amino groups in the hexahexyl indene trimer and anhydride groups in the dianhydride are fed according to the equal molar ratio of active functional groups, polycondensation reaction is carried out at room temperature, namely dianhydride DMF solution of the anhydride groups in the same molar amount as the amino groups is dropwise added into the hexahexyl indene trimer solution, and the mixture is vigorously stirred for 12-36 hours under the condition to prepare the polyamide acid solution, wherein the gelation phenomenon of the polyamide acid solution is effectively avoided due to the introduction of large-volume flexible side chains. And further imidized to obtain a polyimide resin.
The preparation method comprises the following specific steps:
drying the reaction flask at 120 ℃ for 3h, cooling to room temperature, adding hexahexyl indene triamine (HTUTA), vacuumizing, replacing with nitrogen, adding N, N-Dimethylformamide (DMF) into the reaction flask, stirring for dissolving, dropwise adding an anhydride DMF solution containing equimolar amino, and violently stirring for 12-36 h under the condition to obtain the polyamic acid solution. And (3) uniformly spreading the polyamic acid solution on a culture dish, slowly removing the solvent at the temperature of 50-80 ℃ under a vacuum condition, heating to the temperature of 250-350 ℃ at the heating rate of 1-5 ℃/min, keeping the temperature for 1-5 h to obtain a network type polyimide resin film, and further carbonizing at high temperature to prepare a corresponding carbon film.
The invention also provides a preparation method of the polyimide resin carbon film, which comprises the following steps:
and heating the synthesized network type polyimide resin film with the flexible side chain to 400-800 ℃ at the heating rate of 1-5 ℃/min, and keeping the temperature for 0.5-4 h to obtain the polyimide resin carbon film.
The novel three-dimensional network type polyimide resin film and the carbon film provided by the invention can be used for gas separation, and the gas separation film can be used for CO in the atmosphere2Trapping, acid natural gas purification, air separation and the like.
Using 4cm2Under a pressure of 0.2MPa, respectively for N2、O2And CO2The permeability of (a) was tested, and the test results were: o is2Permeability coefficient of 9.5-18.4 Barrer, CO2The permeability coefficient of 60.6 to 96.7Barrer,CO2/N2selectivity of (2) is 25.3 to 35.1, O2/N2The selectivity of (A) is 4.5-5.8.
Using 2cm2Under the pressure of 0.2MPa, the polyimide resin carbon films are respectively aligned to N2、O2And CO2The permeability of (A) was measured, and the result of the measurement was O2Permeability coefficient of 780.4-1280.3 Barrer, CO2Permeability coefficient of 3900.2-4752.6 Barrer, CO2/N2Selectivity of (1) is 11.0 to 15.7, O2/N2The selectivity of (a) is 3.1 to 4.2.
The invention has the advantages and beneficial effects that:
1. the prepared polyimide resin can effectively improve the permeability coefficient of the polymer material to gas due to the introduction of large-volume flexible side chains in the amine monomer.
2. The prepared network type polyimide resin film rich in large-volume flexible side chains can effectively avoid the gelation phenomenon in the condensation polymerization reaction process of the polyimide resin and reduce the energy loss in the reaction process.
3. The polyimide resin film HTUTA-6FDA has the best separation performance, and CO2Permeability coefficient of 96.7Barrer, O2A transmission coefficient of 18.40 Barrer; CO 22/N2Selectivity coefficient of 35.1, O2/N2Selectivity coefficient of 5.8.
4. The polyimide resin Carbon film HTUTA-6FDA has the best gas separation performance, and CO24752.60Barrer, O21280.30 Barrer; CO 22/N2Selectivity of (2) about 15.7, O2/N2Selectivity of (a) is about 4.2.
Drawings
FIG. 1 shows a monomer chemical structure of a polyimide resin.
FIG. 2 is a graph showing the gas separation characteristics of a polyimide resin film of the present invention, wherein (a) a polyimide resin film O having an upper limit of Apocynum2Permeability and O2/N2Selectivity relationship, (b) polyimide resin film CO having an upper limit of Apocynum2Permeability and CO2/N2The relationship of selectivity.
FIG. 3 is a graph showing the gas separation characteristics of a polyimide resin carbon film according to the present invention, wherein (a) a polyimide resin carbon film O having an upper limit of Apocynum2Permeability and O2/N2Selectivity relation, (b) polyimide resin carbon film CO with Apocynon upper limit2Permeability and CO2/N2The relationship of selectivity.
Detailed Description
The invention will be further elucidated by means of specific embodiments in the following description, which are given by way of example and do not limit the scope of protection of the invention.
The preparation method of the gas separation membrane mainly comprises the following two parts: preparing a network type polyimide resin film with a flexible side chain and preparing a polyimide resin carbon film.
Example 1: preparation of polyimide resin Film HTUTA-ODPA
Drying a reaction flask at 120 ℃ for 3h, cooling to room temperature, adding 0.25g (0.280mmol) of hexahexyl indene triamine (HTUTA) into the flask, vacuumizing for 30min, replacing nitrogen for three times, adding N, N-Dimethylformamide (DMF) into the reaction flask, stirring until the N, N-Dimethylformamide (DMF) is completely dissolved, dropwise adding 0.13 g (0.42mmol) of DMF solution containing ODPA, violently stirring for 24h at room temperature to prepare polyamic acid solution, pouring the prepared polyamic acid solution into a dry culture dish, uniformly paving the bottom of the dish, removing the solvent at 60 ℃ in vacuum until a Film is formed, peeling the obtained Film, and then carrying out thermal imidization at 280 ℃ for 2h (at the heating rate of 3 ℃/min) to obtain the polyimide resin Film HTUTA-ODPA.
Example 2: preparation of polyimide resin Film HTUTA-BTDA
Drying a reaction flask at 120 ℃ for 3h, cooling to room temperature, adding 0.25g (0.280mmol) of hexahexyl indene triamine (HTUTA) into the flask, vacuumizing for 30min, replacing nitrogen for three times, adding N, N-Dimethylformamide (DMF) into the reaction flask, stirring until the N, N-Dimethylformamide (DMF) is completely dissolved, dropwise adding 0.12 g (0.42mmol) of DMF solution containing BTDA, violently stirring for 24h at room temperature to prepare polyamic acid solution, pouring the prepared polyamic acid solution into a dry culture dish, uniformly paving the bottom of the dish, removing the solvent at 60 ℃ in vacuum until a Film is formed, peeling the obtained Film, and then carrying out thermal imidization at 280 ℃ for 2h (at the heating rate of 3 ℃/min) to obtain the polyimide resin Film HTUTA-BTDA.
Example 3: preparation of polyimide resin Film HTUTA-6FDA-1
The reaction flask was dried at 120 ℃ for 3h, cooled to room temperature, 0.25g (0.280mmol) of hexahexyl indantriamine (HTUTA) was added to the flask, then evacuated for 30min, nitrogen was replaced three times, N-Dimethylformamide (DMF) was added to the reaction flask, stirred until completely dissolved, a solution of 6FDA in 0.19g (0.42mmol) of DMF was added dropwise, and stirred vigorously at room temperature for 24h to prepare a polyamic acid solution. Pouring the prepared polyamic acid solution into a dry culture dish, uniformly paving the culture dish at the bottom of the dish, removing the solvent at 60 ℃ in vacuum until a Film is formed, peeling the obtained Film, and then performing thermal imidization at 280 ℃ for 2h (at the heating rate of 1 ℃/min) to obtain the polyimide resin Film HTUTA-6 FDA-1.
Example 4: preparation of polyimide resin Film HTUTA-6FDA-2
The reaction flask was dried at 120 ℃ for 3h, cooled to room temperature, 0.25g (0.280mmol) of hexahexyl indantriamine (HTUTA) was added to the flask, then evacuated for 30min, nitrogen was replaced three times, N-Dimethylformamide (DMF) was added to the reaction flask, stirred until completely dissolved, a solution of 6FDA in 0.19g (0.42mmol) of DMF was added dropwise, and stirred vigorously at room temperature for 24h to prepare a polyamic acid solution. Pouring the prepared polyamic acid solution into a dry culture dish, uniformly paving the culture dish at the bottom of the dish, removing the solvent at 60 ℃ in vacuum until a Film is formed, peeling the obtained Film, and then performing thermal imidization at 280 ℃ for 2h (at the heating rate of 3 ℃/min) to obtain the polyimide resin Film HTUTA-6 FDA-2.
Example 5: preparation of polyimide resin Film HTUTA-6FDA-3
The reaction flask was dried at 120 ℃ for 3h, cooled to room temperature, 0.25g (0.280mmol) of hexahexyl indantriamine (HTUTA) was added to the flask, then evacuated for 30min, nitrogen was replaced three times, N-Dimethylformamide (DMF) was added to the reaction flask, stirred until completely dissolved, a solution of 6FDA in 0.19g (0.42mmol) of DMF was added dropwise, and stirred vigorously at room temperature for 24h to prepare a polyamic acid solution. Pouring the prepared polyamic acid solution into a dry culture dish, uniformly paving the culture dish at the bottom of the dish, removing the solvent at 60 ℃ in vacuum until a Film is formed, peeling the obtained Film, and then performing thermal imidization at 280 ℃ for 2h (at the heating rate of 5 ℃/min) to obtain the polyimide resin Film HTUTA-6 FDA-3.
Example 6: preparation of polyimide resin Carbon film HTUTA-ODPA
The polyimide resin film mask HTUTA-ODPA obtained in example 1 was heated to 550 ℃ at a heating rate of 5 ℃/min and maintained at that temperature for 2 hours, thereby preparing a polyimide resin Carbon film mask HTUTA-ODPA.
Example 7: preparation of polyimide resin Carbon film HTUTA-BTDA
The polyimide resin film mask HTUTA-BTDA obtained in example 2 is heated to 550 ℃ at a heating rate of 5 ℃/min and is kept at the temperature for a period of 2 hours, and then the polyimide resin Carbon film mask HTUTA-BTDA can be prepared.
Example 8: preparation of polyimide resin Carbon film HTUTA-6FDA-1
A polyimide resin Carbon Film HTUTA-6FDA-1 was prepared by heating the polyimide resin Film HTUTA-6FDA-1 obtained in example 3 to 550 ℃ at a temperature rise rate of 5 ℃/min and maintaining the temperature for 2 hours.
Example 9: preparation of polyimide resin Carbon film HTUTA-6FDA-2
A polyimide resin Carbon Film HTUTA-6FDA-2 was prepared by heating the polyimide resin Film HTUTA-6FDA-2 obtained in example 4 to 550 ℃ at a temperature rise rate of 5 ℃/min and maintaining the temperature for 2 hours.
Example 10: preparation of polyimide resin Carbon film HTUTA-6FDA-3
A polyimide resin Carbon Film HTUTA-6FDA-3 was prepared by heating the polyimide resin Film HTUTA-6FDA-3 obtained in example 5 to 550 ℃ at a temperature rise rate of 5 ℃/min and maintaining the temperature for 2 hours.
Example 11: gas separation characteristic test of polyimide resin film
The gas separation characteristic test method of the polyimide resin film is a constant volume variable pressure method: under the conditions of 303.15K and 0.2MPa working pressure, 4cm is used2Respectively testing the polyimide films of2、O2And CO2Permeability of (2). The test results of the film are as follows: o is2Permeability coefficient of 9.5-18.4 Barrer, CO2Permeability coefficient of 60.6-96.7 Barrer, CO2/N2Selectivity of (2) is 25.3 to 35.1, O2/N2The selectivity of (A) is 4.5-5.8.
Wherein, the polyimide resin Film HTUTA-6FDA-2 has the best separation performance, and CO2Permeability coefficient of 96.7Barrer, O2A transmission coefficient of 18.40 Barrer; CO 22/N2Selectivity coefficient of 35.1, O2/N2Selectivity coefficient of 5.8.
Example 12: gas separation performance test of polyimide resin carbon membrane
The gas separation characteristic test method of the polyimide resin carbon membrane is a constant volume variable pressure method: under the working pressure conditions of 303.15K and 0.2MPa, 2cm is used2Respectively testing the polyimide films of2、O2And CO2Permeability of (2). The test results were as follows: o is2Permeability coefficient of 780.4-1280.3 Barrer, CO2Permeability coefficient of 3900.2-4752.6 Barrer, CO2/N2Selectivity of (1) is 11.0 to 15.7, O2/N2The selectivity of (a) is 3.1 to 4.2.
Wherein, the polyimide resin Carbon film HTUTA-6FDA-2 has the best gas separation performance, and CO24752.60Barrer, O21280.30 Barrer; CO 22/N2Selectivity of (2) about 15.7, O2/N2Selectivity of (a) is about 4.2. The results of gas separation performance are shown in FIGS. 2 and 3, gas vs. CO2/N2，CO2/O2The separation performance of (a) is close to the upper limit of Robeson in 2008. Test results show that the prepared polyimide resin film and the carbon film thereof have good gas permeability coefficient and gas selectivity and show great industrial application potential.
Claims (7)
1. A network type polyimide resin having a flexible side chain, characterized by having the following chemical structure:
wherein Ar is one of the following structural formulas:
2. the networked polyimide resin according to claim 1, wherein the polyimide resin is a compound of formula HTUTA-ODPA, formula HTUTA-BTDA, or formula HTUTA-6 FDA:
3. the method for preparing a network type polyimide resin having flexible side chains according to claim 1, wherein hexahexyltriaminoindene and a commercially available dianhydride are reacted with each other through the amino group (-NH) which is a reactive functional group of triamine2) Feeding the dianhydride and anhydride groups (-CO-O-CO-) of dianhydride in an equal molar ratio, performing polycondensation reaction at room temperature to prepare a polyamic acid solution, and further performing imidization to obtain polyimide resin; wherein the bulky side chain built on the truxene parent body is-C6H13(ii) a The dianhydride is ODPA, BTDA or 6FDA, but is not limited to these three dianhydrides.
4. The method for preparing the network type polyimide resin with the flexible side chain according to claim 3, wherein the polycondensation reaction is performed at room temperature, the polycondensation reaction process is that a dianhydride DMF solution of anhydride groups with the molar quantity equal to that of amino groups is dropwise added into a hexahexyl indene triamine solution, the mixture is vigorously stirred for 12-36 h under the condition to obtain a polyamic acid solution, the synthesized polyamic acid solution is uniformly spread on a culture dish, the solvent is slowly removed under the vacuum condition of 50-80 ℃, then the temperature is increased to 250-350 ℃ at the temperature increasing rate of 1-5 ℃/min, and the temperature is maintained for 1-5 h, so that the network type polyimide resin film with the flexible side chain is obtained.
5. Use of the network type polyimide resin film prepared by the method of claim 4 for gas separation, wherein the polyimide resin film is used for CO in the atmosphere2Trapping, sour natural gas purification, or air separation.
6. A preparation method of a network type polyimide resin carbon film is characterized in that the network type polyimide resin film in claim 4 is heated to 400-800 ℃ at a heating rate of 1-5 ℃/min and is kept at the temperature for 0.5-4 h to prepare the polyimide resin carbon film.
7. The use of the network type polyimide resin carbon membrane prepared by the method of claim 6 for gas separation, wherein: the polyimide resin carbon film can be used for CO in atmosphere2Trapping, sour natural gas purification, or air separation.
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| CN116144176A (en) * | 2023-04-19 | 2023-05-23 | 山东华夏神舟新材料有限公司 | Polyimide composition, film, preparation method and application thereof |
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| US5015270A (en) * | 1989-10-10 | 1991-05-14 | E. I. Du Pont De Nemours And Company | Phenylindane-containing polyimide gas separation membranes |
| US5266100A (en) * | 1992-09-02 | 1993-11-30 | E. I. Du Pont De Nemours And Company | Alkyl substituted polyimide, polyamide and polyamide-imide gas separation membranes |
| CN103467316A (en) * | 2013-09-30 | 2013-12-25 | 湖北大学 | Synthesis of triamine containing truxene structure and polyimide thereof |
| CN111363148A (en) * | 2020-03-26 | 2020-07-03 | 天津理工大学 | Preparation method of binaphthyl network type polyimide resin and film and application of binaphthyl network type polyimide resin and film in gas separation |
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| US5015270A (en) * | 1989-10-10 | 1991-05-14 | E. I. Du Pont De Nemours And Company | Phenylindane-containing polyimide gas separation membranes |
| US5266100A (en) * | 1992-09-02 | 1993-11-30 | E. I. Du Pont De Nemours And Company | Alkyl substituted polyimide, polyamide and polyamide-imide gas separation membranes |
| CN103467316A (en) * | 2013-09-30 | 2013-12-25 | 湖北大学 | Synthesis of triamine containing truxene structure and polyimide thereof |
| CN111363148A (en) * | 2020-03-26 | 2020-07-03 | 天津理工大学 | Preparation method of binaphthyl network type polyimide resin and film and application of binaphthyl network type polyimide resin and film in gas separation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116144176A (en) * | 2023-04-19 | 2023-05-23 | 山东华夏神舟新材料有限公司 | Polyimide composition, film, preparation method and application thereof |
| CN116144176B (en) * | 2023-04-19 | 2023-08-15 | 山东华夏神舟新材料有限公司 | Polyimide composition, film, preparation method and application thereof |
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