CN113372554A - Semi-alicyclic polyimide and application of film thereof in gas separation - Google Patents

Semi-alicyclic polyimide and application of film thereof in gas separation Download PDF

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CN113372554A
CN113372554A CN202110650607.4A CN202110650607A CN113372554A CN 113372554 A CN113372554 A CN 113372554A CN 202110650607 A CN202110650607 A CN 202110650607A CN 113372554 A CN113372554 A CN 113372554A
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alicyclic polyimide
polyimide film
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diamine
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CN113372554B (en
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阎敬灵
路瑶
王震
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Ningbo Institute of Material Technology and Engineering of CAS
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    • B01D—SEPARATION
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Abstract

The invention discloses semi-alicyclic polyimide and an application of a film thereof in gas separation. The semi-alicyclic polyimide has a structure represented by the following formula:
Figure DDA0003110861920000011
wherein n is more than 10 and less than 500. The film prepared from the semi-alicyclic polyimide has high specific surface area and gas permeability coefficient, and the gas separation performance of the film is excellentThe method has good application prospect in the aspects of industrial hydrogen purification and recovery application in a commercial gas separation membrane and a corresponding hexafluoro dianhydride gas separation membrane.

Description

Semi-alicyclic polyimide and application of film thereof in gas separation
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an application of a semi-alicyclic polyimide film in gas separation.
Background
The gas membrane separation technology is a green technology for converting mixed gas into two or more single gases with different components according to different permeation rates of the mixed gas penetrating through a membrane under the pushing of pressure, and has the advantages of low energy consumption, simple operation, small occupied area and the like compared with the traditional pressure swing adsorption technology and cryogenic separation technology. Since the 70 s in the 20 th century, gas membrane separation technology has been widely used for separation of oxygen and nitrogen in air, separation of carbon dioxide and methane in natural gas, separation of hydrogen in purge gas of synthetic ammonia, and the like.
There are two important parameters for measuring gas separation performance: permeability coefficient and selectivity coefficient. In 1991, Robeson proposed a limit for polymer properties, namely the upper limit of Robeson, describing the check-in effect of permeability coefficient and selectivity coefficient. In order to realize high permeation flux and high separation efficiency, the polymeric membrane should have high permeability coefficient and selectivity coefficient, so that the upper limit of Robeson is broken through, and the preparation of a high-performance separation material becomes a main development direction in the field. An ideal gas separation membrane material needs to have high permeability coefficient and selectivity coefficient, and also needs to have good mechanical property, thermodynamic stability and membrane forming processability, and polyimide containing nitrogen aromatic heterocycle is increasingly valued in the field of gas separation membranes due to the fact that the structure is rich and easy to design, and the comprehensive performance is optimal.
Currently, only polyimide separation membranes have been commercialized
Figure BDA0003110861900000011
And
Figure BDA0003110861900000012
it has good mechanical properties, thermodynamic stability and high selectivity coefficient, but due to low permeability coefficient and separation efficiency: (
Figure BDA0003110861900000013
H2、CO2、O2、N2、CH4Permeability coefficients of 27.2, 7, 2, 0.28 and 0.21 Barrer;
Figure BDA0003110861900000014
H2、CO2、O2、N2、CH4permeability coefficients of 9.09, 1.37, 0.4, 0.05 and 0.03Barrer), limiting its industrial application. A large number of practical researches show that the polyimide has a rigid framework structure, loose molecular chain segments and large free volume, and has better gas separation performance. Based on the above thought and current situation, a polyimide separation membrane material having both a high gas permeability coefficient and a high selectivity coefficient is yet to be developed.
Disclosure of Invention
The invention mainly aims to provide semi-alicyclic polyimide and an application of a film thereof in gas separation so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides an application of a semi-alicyclic polyimide film in gas separation, wherein the semi-alicyclic polyimide film is prepared from semi-alicyclic polyimide, and the semi-alicyclic polyimide has a structure shown in a formula (I):
Figure BDA0003110861900000021
wherein n is more than 10 and less than 500, and R is selected from the structures shown by any one or the combination of more than two of the following formulas:
Figure BDA0003110861900000022
wherein the dashed line represents the position of the amino group access.
Embodiments of the present invention also provide a semi-alicyclic polyimide having a structure represented by formula (I):
Figure BDA0003110861900000031
wherein n is more than 10 and less than 500, and R is selected from the structures shown by any one or the combination of more than two of the following formulas:
Figure BDA0003110861900000032
wherein the dashed line represents the position of the amino group access.
The embodiment of the invention also provides a semi-alicyclic polyimide film which is made of the semi-alicyclic polyimide.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the semi-alicyclic polyimide film provided by the invention, by introducing norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride with a rigid twisted structure, on one hand, the rigidity of a molecular chain framework is increased, and the mobility of a molecular chain segment is reduced; on the other hand, the ordered stacking degree of the polyimide molecular chain segments is destroyed, the acting force between the molecular chains is weakened, the molecular chain spacing is increased, the free volume and the specific surface area of the polyimide are increased, and the specific surface area is as high as 567m2/g；
(2) The semi-alicyclic polyimide film pair H provided by the invention2、CO2、O2、N2、CH4The permeability coefficients are respectively as high as 1285, 1110, 334, 95 and 121Barrer, the defects of low permeability coefficient and low separation efficiency of the commercial polyimide gas separation membrane are overcome, and the gas separation efficiency is greatly improved;
(3) the semi-alicyclic polyimide film provided by the invention has separation performance on hydrogen/methane and hydrogen/nitrogen close to or exceeding the Robeson upper limit in 2008, is superior to the corresponding hexafluorodianhydride polyimide separation performance, and has great potential in industrial hydrogen purification and recovery application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIGS. 1 a-1 e are nuclear magnetic images of semi-alicyclic polyimide films in examples 1-5 of the present invention;
FIG. 2 is an infrared spectrum of a semi-alicyclic polyimide film in examples 1 to 5 of the present invention;
FIGS. 3 a-3 b are semi-alicyclic polyimide films according to examples 1-5 of the present invention and a pair of hexafluorodianhydride and seven commercial gas separation membranes according to the prior art H2/CH4、H2/N2Gas separation performance diagram of (1).
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of the embodiments of the present invention provides an application of a semi-alicyclic polyimide film in gas separation, where the semi-alicyclic polyimide film is prepared from a semi-alicyclic polyimide, and the semi-alicyclic polyimide has a structure shown in formula (I):
Figure BDA0003110861900000041
wherein n is more than 10 and less than 500, and R is selected from the structures shown by any one or the combination of more than two of the following formulas:
Figure BDA0003110861900000051
wherein the dashed line represents the position of the amino group access.
In some more specific embodiments, the method for preparing the semi-alicyclic polyimide film comprises the following steps:
reacting a mixed reaction system containing norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride, diamine, a catalyst and a solvent at the temperature of 60-80 ℃ for 1-2 hours under a protective atmosphere to obtain a prepolymer;
heating the prepolymer to 150-200 ℃, and continuously reacting for 6-12 hours to obtain semi-alicyclic polyimide;
and performing film formation treatment on the semi-alicyclic polyimide to obtain the semi-alicyclic polyimide film.
Further, the diamines include 2, 2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl (TFMB), 3, 3 ', 5, 5' -Tetramethylbiphenyldiamine (TMB), 6-amino-1- (4-aminophenyl) -1, 3, 3-trimethylindene (DAPI), 1, 3-bis (3-aminophenoxy) benzene (1, 3, 3-APB), 2, 5-dimethyl-1, 4-phenylenediamine (DPD), 1, 5-Naphthalenediamine (NPD), 2, 8-diamino-4, 10-dimethyl-6H, 12H-5, 11-methylbenzyl [ b, f ] [1, 5] diazocine (TBDA-1), 3, 9-diamino-4, 10-dimethyl-6H, 12H-5, 11-methylbenzhydr [ b, f ] [1, 5] diazocine (TBDA-2), 9-bis (4-aminophenyl) fluorene (BMF), 2 '-diamino-9, 9' -Spirobifluorene (SBF), 4 '-diamino-3, 3' -dimethylbinaphthyl (AMMA), 9-bis (4-amino-3-tolyl) fluorene (BAMF), 2 '-diamino-3, 3' -dibromo-9, 9 '-spirobifluorene (BSBF), 2' -diamino-3, 3 '-dimethyl-9, 9' -spirobifluorene (CSBF), 2, 6-Diaminotriptycene (DAT), 3, 7-dimethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobuta [1, 2-b ] biphenyl-2, 8-diamine/3, 8-dimethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobuta [1, 2-b ] biphenyl-2, 7-diamine (CANAL-1), 1, 3, 7, 9-tetramethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobuta [1, 2-b ] biphenyl-2, 8-diamine/1, 3, 6, 8-tetramethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, any one or a combination of two or more of 10-methylbenzo [3, 4] cyclobutane [1, 2-b ] biphenyl-2, 7-diamine (CANAL-2), 4, 6-dimethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobutane [1, 2-b ] biphenyl-2, 8-diamine/4, 9-dimethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobutane [1, 2-b ] biphenyl-2, 7-diamine (CANAL-3), and is not limited thereto.
Further, the catalyst includes a basic catalyst and/or an acidic catalyst, and is not limited thereto.
Further, the basic catalyst includes isoquinoline and/or triethylamine, and is not limited thereto.
Further, the acid catalyst includes benzoic acid and/or p-hydroxybenzoic acid, and is not limited thereto.
Further, the solvent includes any one or a combination of two or more of m-cresol, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone, and is not limited thereto.
Further, the protective atmosphere includes a nitrogen atmosphere and/or an inert gas atmosphere.
Further, the inert gas atmosphere includes argon and/or helium, and is not limited thereto.
In some more specific embodiments, the method for preparing the semi-alicyclic polyimide film further comprises: after the reaction for preparing the semi-alicyclic polyimide is completed, the obtained mixture is subjected to purification and drying treatment, and then film forming treatment is performed.
Further, the purification treatment comprises: and performing Soxhlet extraction on the obtained mixture for 12-24 h.
Further, the solvent used in the soxhlet extraction includes ethanol, and is not limited thereto.
Further, the purification treatment comprises: dissolving the obtained mixture in organic solvent, precipitating with mixed solution of ethanol and water, and filtering.
Further, the organic solvent includes any one or a combination of two or more of tetrahydrofuran, dichloromethane, chloroform, m-cresol, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone, and is not limited thereto.
In some more specific embodiments, the film formation process comprises: and dissolving the semi-alicyclic polyimide in an organic solvent, and then carrying out film forming treatment by adopting a tape casting method to obtain the semi-alicyclic polyimide film.
Further, the organic solvent includes any one or a combination of two or more of tetrahydrofuran, dichloromethane, chloroform, m-cresol, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone, and is not limited thereto.
In some more specific embodiments, the application comprises: and separating hydrogen by using the semi-alicyclic polyimide film.
Further, the application specifically includes: the semi-alicyclic polyimide film is used for separating hydrogen from hydrogen/methane mixed gas or hydrogen/nitrogen mixed gas.
In some more specific embodiments, the semi-alicyclic polyimide film has a thickness of 60 to 80 μm.
Further, the specific surface area of the semi-alicyclic polyimide film is more than 90m2/g。
Further, the specific surface area of the semi-alicyclic polyimide film is as high as 567m2/g。
In another aspect of the embodiments of the present invention, there is also provided a semi-alicyclic polyimide having a structure represented by formula (I):
Figure BDA0003110861900000071
wherein n is more than 10 and less than 500, and R is selected from the structures shown by any one or the combination of more than two of the following formulas:
Figure BDA0003110861900000072
wherein the dashed line represents the position of the amino group access.
Another aspect of the embodiments of the present invention also provides a method for preparing the semi-alicyclic polyimide film, including:
(1) mixing norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6, 6 "-tetracarboxylic dianhydride (CpODA), a diamine, a catalyst, and a solvent under an inert atmosphere;
(2) and reacting the mixed system for 1-2h at the temperature of 60-80 ℃ to obtain the prepolymer.
(3) And continuously heating to 150 ℃ and 200 ℃, reacting for 6-12h, pouring the reaction system into a mixed solution of ethanol and water to separate out filiform precipitates, filtering, purifying and drying to obtain the polyimide with the structure shown in the formula (I).
(4) Dissolving polyimide in an organic solvent, forming a film and drying to obtain the semi-alicyclic polyimide film.
Further, the diamines include 2, 2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl (TFMB), 3, 3 ', 5, 5' -Tetramethylbiphenyldiamine (TMB), 6-amino-1- (4-aminophenyl) -1, 3, 3-trimethylindene (DAPI), 1, 3-bis (3-aminophenoxy) benzene (1, 3, 3-APB), 2, 5-dimethyl-1, 4-phenylenediamine (DPD), 1, 5-Naphthalenediamine (NPD), 2, 8-diamino-4, 10-dimethyl-6H, 12H-5, 11-methylbenzyl [ b, f ] [1, 5] diazocine (TBDA-1), 3, 9-diamino-4, 10-dimethyl-6H, 12H-5, 11-methylbenzhydr [ b, f ] [1, 5] diazocine (TBDA-2), 9-bis (4-aminophenyl) fluorene (BMF), 2 '-diamino-9, 9' -Spirobifluorene (SBF), 4 '-diamino-3, 3' -dimethylbinaphthyl (AMMA), 9-bis (4-amino-3-tolyl) fluorene (BAMF), 2 '-diamino-3, 3' -dibromo-9, 9 '-spirobifluorene (BSBF), 2' -diamino-3, 3 '-dimethyl-9, 9' -spirobifluorene (CSBF), 2, 6-Diaminotriptycene (DAT), 3, 7-dimethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobuta [1, 2-b ] biphenyl-2, 8-diamine/3, 8-dimethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobuta [1, 2-b ] biphenyl-2, 7-diamine (CANAL-1), 1, 3, 7, 9-tetramethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobuta [1, 2-b ] biphenyl-2, 8-diamine/1, 3, 6, 8-tetramethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, any one or a combination of two or more of 10-methylbenzo [3, 4] cyclobutane [1, 2-b ] biphenyl-2, 7-diamine (CANAL-2), 4, 6-dimethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobutane [1, 2-b ] biphenyl-2, 8-diamine/4, 9-dimethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobutane [1, 2-b ] biphenyl-2, 7-diamine (CANAL-3), and is not limited thereto.
Further, the catalyst includes a basic catalyst and/or an acidic catalyst, and is not limited thereto.
Further, the basic catalyst includes isoquinoline and/or triethylamine, and is not limited thereto.
Further, the acid catalyst includes benzoic acid and/or p-hydroxybenzoic acid, and is not limited thereto.
Further, the solvent includes any one or a combination of two or more of m-cresol, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone, and is not limited thereto.
Further, the protective atmosphere includes a nitrogen atmosphere and/or an inert gas atmosphere.
Further, the inert gas atmosphere includes argon and/or helium, and is not limited thereto.
Further, the purification process is selected from any one of the following methods: performing Soxhlet extraction and reflux on the precipitate in a Soxhlet extractor with ethanol as solvent for 12-24 h; or dissolving the precipitate again, adding into mixed solution of ethanol and water, precipitating again, filtering, and repeating for 2-3 times.
Further, the organic solvent is selected from one or more of tetrahydrofuran, dichloromethane, trichloromethane, m-cresol, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and the like; the film-forming method is preferably a tape casting method.
In another aspect of the embodiments of the present invention, there is also provided a semi-alicyclic polyimide film made of the aforementioned semi-alicyclic polyimide. The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
In this example, a semi-alicyclic polyimide has the following structural formula:
Figure BDA0003110861900000091
the preparation method of the semi-alicyclic polyimide film comprises the following steps:
under nitrogen protection, norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6, 6 "-tetracarboxylic dianhydride (CpODA) (0.9610g, 2.5mmol), 6-amino-1- (4-aminophenyl) -1, 3, 3-trimethylindenediamine (DAPI) (0.6660g, 2.5mmol), benzoic acid (0.1527g, 1.25mmol), and m-cresol (6.51g) were added to the flask to control the solid content of the system to 20 wt%. Mechanically stirring at 80 deg.C for 1 hr until the reactants are completely dissolved, heating to 180 deg.C, and continuing to react for 8 hr until the polymer is completely imidized. M-cresol (24.40g) was added to dilute the solid content to 5 wt%, the heating was stopped and the temperature was naturally lowered to room temperature. The reaction mixture was poured into a mixed solution of ethanol and water (300ml, 1: 1 v/v) with magnetic stirring, to precipitate a filamentous white fibrous solid, which was then filtered. And (3) putting the filamentous fiber solid into a Soxhlet extractor, heating and refluxing ethanol for 18h, removing redundant m-cresol, and drying at 120 ℃ after the completion to obtain the semi-alicyclic polyimide.
Dissolving semi-alicyclic polyimide in N-methyl pyrrolidone to prepare a solution with the solid content of 5 wt%, filtering to remove insoluble substances and impurities, vacuumizing to eliminate bubbles, and slowly coating the polyimide solution on a flat, smooth and dry glass plate by adopting a tape casting method. And (3) putting the glass plate into a film-spreading oven, drying for 12h at 80 ℃, cooling, putting into a vacuum oven, and sequentially drying for 4h at 100, 150 and 200 ℃. And (3) cooling to room temperature, completely soaking the glass plate in distilled water until the film naturally falls off, and thus obtaining the semi-alicyclic polyimide film (marked as CpODA-DAPI).
Structural characterization:
FIG. 1a shows the integral assignment of the peak in the NMR spectrum of CpODA-DAPI prepared in this example; 1780, 1720, 1380cm in the IR spectrum-1The peak of absorption of the imide ring is shown in FIG. 2.
The specific surface area of the material is 92m by nitrogen adsorption and desorption test2g-1(ii) a The gas separation test shows that the nitrogen permeability coefficient is 3.5Barrer, the oxygen permeability coefficient is 20.8Barrer, the methane permeability coefficient is 2.9Barrer, the carbon dioxide permeability coefficient is 54.2Barrer, the hydrogen permeability coefficient is 166Barrer, the hydrogen/methane selectivity coefficient is 57.3, and the hydrogen/nitrogen selectivity coefficient is 47.5.
Example 2
In this example, a semi-alicyclic polyimide has the following structural formula:
Figure BDA0003110861900000101
the preparation method of the semi-alicyclic polyimide film comprises the following steps:
under the protection of nitrogen, norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6, 6 "-tetracarboxylic dianhydride (CpODA) (0.9610g, 2.5mmol), 2, 8-diamino-4, 10-dimethyl-6H, 12H-5, 11-methylbenzhydr [ b, f ] [1, 5] diazocine diamine (TBDA-1) (0.7009g, 2.5mmol), benzoic acid (0.1527g, 1.25mmol), m-cresol (6.65g) were added to the flask, and the solid content of the system was controlled to 20 wt%. Mechanically stirring at 60 deg.C for 2 hr until the reactants are completely dissolved, heating to 150 deg.C, and continuously reacting for 12 hr until the polymer is completely imidized. M-cresol (24.93g) was added to dilute the solid content to 5 wt%, the heating was stopped and the temperature was naturally lowered to room temperature. The reaction mixture was poured into a mixed solution of ethanol and water (300ml, 1: 1 v/v) with magnetic stirring, to precipitate a filamentous white fibrous solid, which was then filtered. And (3) putting the filamentous fiber solid into a Soxhlet extractor, heating and refluxing ethanol for 12h, removing redundant m-cresol, and drying at 120 ℃ after the completion to obtain the semi-alicyclic polyimide.
Dissolving semi-alicyclic polyimide in N-methyl pyrrolidone to prepare a solution with the solid content of 5 wt%, filtering to remove insoluble substances and impurities, vacuumizing to eliminate bubbles, and slowly coating the polyimide solution on a flat, smooth and dry glass plate by adopting a tape casting method. And (3) putting the glass plate into a film-spreading oven, drying for 12h at 80 ℃, cooling, putting into a vacuum oven, and sequentially drying for 4h at 100, 150 and 200 ℃. And (3) cooling to room temperature, completely soaking the glass plate in distilled water until the film naturally falls off, thus obtaining the semi-alicyclic polyimide film (marked as CpODA-TBDA-1).
Structural characterization:
the integral assignment of the peak in the nuclear magnetic resonance hydrogen spectrum of the semi-alicyclic polyimide film prepared in this example is shown in fig. 1 b; 1780, 1720, 1380cm in the IR spectrum-1The peak of absorption of the imide ring is shown in FIG. 2.
The specific surface area is 289m by nitrogen absorption and desorption test2g-1(ii) a The gas separation test shows that the nitrogen permeability coefficient is 13.2Barrer, the oxygen permeability coefficient is 66.5Barrer, the methane permeability coefficient is 9.4Barrer, the carbon dioxide permeability coefficient is 240Barrer, the hydrogen permeability coefficient is 360Barrer, the hydrogen/methane selectivity coefficient is 38.2, and the hydrogen/nitrogen selectivity coefficient is 27.3.
Example 3
In this example, a semi-alicyclic polyimide has the following structural formula:
Figure BDA0003110861900000111
the preparation method of the semi-alicyclic polyimide film comprises the following steps:
under the protection of nitrogen, norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6, 6 "-tetracarboxylic dianhydride (CpODA) (0.9610g, 2.5mmol), 3, 9-diamino-4, 10-dimethyl-6H, 12H-5, 11-methylbenzhydr [ b, f ] [1, 5] diazocine diamine (TBDA-2) (0.7009g, 2.5mmol), benzoic acid (0.1527g, 1.25mmol), m-cresol (6.65g) were added to the flask, and the solid content of the system was controlled to 20 wt%. Mechanically stirring at 70 deg.C for 1.5 hr until the reactant is completely dissolved, heating to 200 deg.C, and continuously reacting for 6 hr until the polymer is completely imidized. M-cresol (24.93g) was added to dilute the solid content to 5 wt%, the heating was stopped and the temperature was naturally lowered to room temperature. The reaction mixture was poured into a mixed solution of ethanol and water (300ml, 1: 1 v/v) with magnetic stirring, to precipitate a filamentous white fibrous solid, which was then filtered. And (3) putting the filamentous fiber solid into a Soxhlet extractor, heating and refluxing the ethanol for 24h, removing the redundant m-cresol, and drying at the temperature of 120 ℃ after the removal of the redundant m-cresol to obtain the semi-alicyclic polyimide.
Dissolving semi-alicyclic polyimide in N-methyl pyrrolidone to prepare a solution with the solid content of 5 wt%, filtering to remove insoluble substances and impurities, vacuumizing to eliminate bubbles, and slowly coating the polyimide solution on a flat, smooth and dry glass plate by adopting a tape casting method. And (3) putting the glass plate into a film-spreading oven, drying for 12h at 80 ℃, cooling, putting into a vacuum oven, and sequentially drying for 4h at 100, 150 and 200 ℃. And (3) cooling to room temperature, completely soaking the glass plate in distilled water until the film naturally falls off, thus obtaining the semi-alicyclic polyimide film (marked as CpODA-TBDA-2).
Structural characterization:
the integral assignment of the peak in the nuclear magnetic resonance hydrogen spectrum of the semi-alicyclic polyimide film prepared in this example is shown in fig. 1 c; 1780, 1720, 1380cm in the IR spectrum-1The peak of absorption of the imide ring is shown in FIG. 2.
The specific surface area of the material is 387m according to a nitrogen absorption and desorption test2g-1(ii) a The gas separation test shows that the nitrogen permeability coefficient is 26.3Barrer, the oxygen permeability coefficient is 121Barrer, the methane permeability coefficient is 26.8Barrer, the carbon dioxide permeability coefficient is 498Barrer, the hydrogen permeability coefficient is 685Barrer, the hydrogen/methane selectivity coefficient is 24.5, and the hydrogen/nitrogen selectivity coefficient is 26.1.
Example 4
In this example, a semi-alicyclic polyimide has the following structural formula:
Figure BDA0003110861900000112
the preparation method of the semi-alicyclic polyimide film comprises the following steps:
under nitrogen protection, norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6, 6 "-tetracarboxylic dianhydride (CpODA) (0.9610g, 2.5mmol), 2, 6-Diaminotriptycenediamine (DAT) (0.7109g, 2.5mmol), benzoic acid (0.1527g, 1.25mmol), and m-cresol (6.69g) were added to the flask, and the solid content of the system was controlled to 20 wt%. Mechanically stirring at 80 deg.C until the reactant is completely dissolved, heating to 180 deg.C, and continuously reacting for 6-12h until the polymer is completely imidized. M-cresol (25.08g) was added to dilute the solid content to 5 wt%, the heating was stopped and the temperature was naturally lowered to room temperature. The reaction mixture was poured into a mixed solution of ethanol and water (300ml, 1: 1 v/v) with magnetic stirring, to precipitate a filamentous white fibrous solid, which was then filtered. Putting the filamentous fiber solid into a Soxhlet extractor, heating and refluxing the ethanol for 12-24h, removing the redundant m-cresol, and drying at 120 ℃ after the completion to obtain the semi-alicyclic polyimide.
Dissolving semi-alicyclic polyimide in N-methyl pyrrolidone to prepare a solution with the solid content of 5 wt%, filtering to remove insoluble substances and impurities, vacuumizing to eliminate bubbles, and slowly coating the polyimide solution on a flat, smooth and dry glass plate by adopting a tape casting method. And (3) putting the glass plate into a film-spreading oven, drying for 12h at 80 ℃, cooling, putting into a vacuum oven, and sequentially drying for 4h at 100, 150 and 200 ℃. And (3) after the temperature is reduced to room temperature, completely soaking the glass plate in distilled water until the film naturally falls off, thus obtaining the semi-alicyclic polyimide film (marked as CpODA-DAT).
Structural characterization:
the integral assignment of the peak in the nuclear magnetic resonance hydrogen spectrum of the semi-alicyclic polyimide film prepared in this example is shown in fig. 1 d; 1780, 1720, 1380cm in the IR spectrum-1The peak of absorption of the imide ring is shown in FIG. 2.
The specific surface area of the material is 500m by nitrogen adsorption and desorption test2g-1(ii) a The gas separation test showed a nitrogen permeability of 19.8Barrer, an oxygen permeability of 88.3Barrer, a methane permeability of 17.8Barrer, a carbon dioxide permeability of 263Barrer, a hydrogen permeability of 608Barrer, a hydrogen/methane selectivity of 34.2, and a hydrogen/nitrogen selectivity of 30.7.
Example 5
In this example, a semi-alicyclic polyimide has the following structural formula:
Figure BDA0003110861900000121
the preparation method of the semi-alicyclic polyimide film comprises the following steps:
norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6, 6 "-tetracarboxylic dianhydride (CpODA) (0.9610g, 2.5mmol), 1, 3, 7, 9-tetramethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobutane [1, 2-b ] biphenyl-2, 8-diamine/1, 3, 6, 8-tetramethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobutane [1, 2-b ] biphenyl-2, 7-diamine (CANAL-2) (0.8262g, 2.5mmol), under nitrogen protection, Benzoic acid (0.1527g, 1.25mmol) was added, and m-cresol (7.15g) was added to control the solids content of the system at 20 wt%. Mechanically stirring at 80 deg.C until the reactant is completely dissolved, heating to 180 deg.C, and continuously reacting for 6-12h until the polymer is completely imidized. M-cresol (26.81g) was added to dilute the solid content to 5 wt%, the heating was stopped and the temperature was naturally lowered to room temperature. The reaction mixture was poured into a mixed solution of ethanol and water (300ml, 1: 1 v/v) with magnetic stirring, to precipitate a filamentous white fibrous solid, which was then filtered. Putting the filamentous fiber solid into a Soxhlet extractor, heating and refluxing the ethanol for 12-24h, removing the redundant m-cresol, and drying at 120 ℃ after the completion to obtain the semi-alicyclic polyimide.
Dissolving semi-alicyclic polyimide in N-methyl pyrrolidone to prepare a solution with the solid content of 5 wt%, filtering to remove insoluble substances and impurities, vacuumizing to eliminate bubbles, and slowly coating the polyimide solution on a flat, smooth and dry glass plate by adopting a tape casting method. And (3) putting the glass plate into a film-spreading oven, drying for 12h at 80 ℃, cooling, putting into a vacuum oven, and sequentially drying for 4h at 100, 150 and 200 ℃. And (3) after the temperature is reduced to room temperature, completely soaking the glass plate in distilled water until the film naturally falls off, thus obtaining the semi-alicyclic polyimide film (marked as CpODA-CANAL-2).
Structural characterization:
the integral assignment of the peak in the nuclear magnetic resonance hydrogen spectrum of the semi-alicyclic polyimide film prepared in this example is shown in fig. 1 e; the infrared spectrum is as shown in FIG. 2, 1780, 1720, 1380cm in infrared spectrum-1The absorption peak of the imide ring is shown.
The specific surface area of the sample is 567m by nitrogen adsorption and desorption test2g-1(ii) a According to a gas separation test, the nitrogen permeability coefficient is 95.1Barrer, the oxygen permeability coefficient is 334Barrer, the methane permeability coefficient is 121Barrer, the carbon dioxide permeability coefficient is 1110Barrer, the hydrogen permeability coefficient is 1285Barrer, the hydrogen/methane selectivity coefficient is 10.6, and the hydrogen/nitrogen selectivity coefficient is 13.5.
FIGS. 3 a-3 b are semi-alicyclic polyimide films according to examples 1-5 of the present invention and a pair of hexafluorodianhydride and seven commercial gas separation membranes according to the prior art H2/CH4、H2/N2Gas separation performance diagram of (1).
The performance test methods referred to in the examples are as follows:
(1) structural characterization:
nuclear magnetic resonance of the semi-alicyclic polyimide film is tested by using a Brookfield nuclear magnetic resonance spectrometer;
the infrared of the semi-alicyclic polyimide film is tested by using a Fourier transform attenuated total reflection infrared spectrometer.
(2) And (3) testing physical properties:
the specific surface area of the semi-alicyclic polyimide film was tested by grinding polyimide into powder using a mack ASAP2640 full-automatic specific surface and porosity analyzer.
(3) Testing the gas separation performance:
the semi-alicyclic polyimide film is used for treating five single gases (H)2、O2、N2、CH4、CO2) The permeability coefficient of (a) was measured at 35 ℃ and 1Barrer using a gas permeameter.
Performance discussion:
table 1 lists the gas permeability coefficients and selectivity coefficients of typical examples 3-5 of the present invention, and the reported hexafluorodianhydrides, seven commercial gas separation membranes, as can be seen from the table: examples 3-5 for five single gases (H)2、O2、N2、CH4、CO2) Are higher than the corresponding hexafluorodianhydride polyimide polymer (reference: polymer 2019, 161, 16-26; polymer 2017, 130, 182-190; macromolecular Rapid Communications 2011, 32(7), 579-86; chemistry of Materials 2019, 31(5), 1767-: journal of Membrane Science 2008, 314(1-2), 123-; journal of Applied Polymer Science 2010, 101(6), 3800-; progress in Polymer Science 1988, 13(4), 339-; journal of Polymer Science Part B: polymer Physics 1987, 25(9), 1999-2026; the permeability coefficient of Journal of Membrane Science 1998, 138(2), 143-152) greatly improves the gas separation efficiency; in addition, in the examples 3-5, the permeability coefficient is improved, and meanwhile, a proper selection coefficient is kept, so that the overall separation performance is improved, wherein the hydrogen/methane and hydrogen/nitrogen performances of some examples are close to or break through the Robeson upper line limit in 2008, and the method has better application in the aspects of industrial hydrogen purification and recoveryAnd 4, application prospect.
TABLE 2 gas permeability coefficient and selection coefficient data
Figure BDA0003110861900000141
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the protection scope of the claims.

Claims (10)

1. The application of the semi-alicyclic polyimide film in gas separation is characterized in that: the semi-alicyclic polyimide film is prepared from semi-alicyclic polyimide, and the semi-alicyclic polyimide has a structure shown in a formula (I):
Figure FDA0003110861890000011
wherein n is more than 10 and less than 500, and R is selected from the structures shown by any one or the combination of more than two of the following formulas:
Figure FDA0003110861890000012
wherein the dashed line represents the position of the amino group access.
2. The use according to claim 1, wherein the semi-alicyclic polyimide film is prepared by a method comprising:
reacting a mixed reaction system containing norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride, diamine, a catalyst and a solvent at the temperature of 60-80 ℃ for 1-2 hours under a protective atmosphere to obtain a prepolymer;
heating the prepolymer to 150-200 ℃, and continuously reacting for 6-12 hours to obtain semi-alicyclic polyimide;
and performing film formation treatment on the semi-alicyclic polyimide to obtain the semi-alicyclic polyimide film.
3. Use according to claim 2, characterized in that: the diamine includes 2, 2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl, 3, 3 ', 5, 5' -tetramethylbiphenyldiamine, 6-amino-1- (4-aminophenyl) -1, 3, 3-trimethylindene, 1, 3-bis (3-aminophenoxy) benzene, 2, 5-dimethyl-1, 4-phenylenediamine, 1, 5-naphthalenediamine, 2, 8-diamino-4, 10-dimethyl-6H, 12H-5, 11-methylbenzo [ b, f ] [1, 5] diazocine, 3, 9-diamino-4, 10-dimethyl-6H, 12H-5, 11-methylbenzo [ b, f ] [1, 5] diazocine, 9, 9-bis (4-aminophenyl) fluorene, 2 '-diamino-9, 9' -spirobifluorene, 4 '-diamino-3, 3' -dimethylbinaphthyl, 9-bis (4-amino-3-methylphenyl) fluorene, 2 '-diamino-3, 3' -dibromo-9, 9 '-spirobifluorene, 2' -diamino-3, 3 '-dimethyl-9, 9' -spirobifluorene, 2, 6-diaminotriptycene, 3, 7-dimethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobut [1, 2-b ] biphenyl-2, 8-diamine/3, 8-dimethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobuta [1, 2-b ] biphenyl-2, 7-diamine, 1, 3, 7, 9-tetramethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobuta [1, 2-b ] biphenyl-2, 8-diamine/1, 3, 6, 8-tetramethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobuta [1, 2-b ] biphenyl-2, 7-diamine, 4, 6-dimethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobutane [1, 2-b ] biphenyl-2, 8-diamine/4, 9-dimethyl-4 b, 5, 5a, 9b, 10, 10 a-hexahydro-5, 10-methylbenzo [3, 4] cyclobutane [1, 2-b ] biphenyl-2, 7-diamine or a combination of more than two of the above.
4. Use according to claim 2, characterized in that: the catalyst comprises a basic catalyst and/or an acidic catalyst; preferably, the basic catalyst comprises isoquinoline and/or triethylamine; preferably, the acidic catalyst comprises benzoic acid and/or p-hydroxybenzoic acid;
and/or the solvent comprises one or the combination of more than two of m-cresol, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
and/or, the protective atmosphere comprises a nitrogen atmosphere and/or an inert gas atmosphere; preferably, the inert gas atmosphere comprises argon and/or helium.
5. The use according to claim 2, wherein the method of preparing the semi-alicyclic polyimide film further comprises: after the reaction for preparing the semi-alicyclic polyimide is finished, purifying and drying the obtained mixture, and then performing film forming treatment;
preferably, the purification treatment comprises: performing Soxhlet extraction on the obtained mixture for 12-24 h; more preferably, the solvent used for Soxhlet extraction comprises ethanol;
preferably, the purification treatment comprises: dissolving the obtained mixture in an organic solvent, and then carrying out precipitation and filtration treatment by using a mixed solution of ethanol and water; more preferably, the organic solvent includes one or a combination of two or more of tetrahydrofuran, dichloromethane, chloroform, m-cresol, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.
6. Use according to claim 2, wherein the film forming process comprises: dissolving the semi-alicyclic polyimide in an organic solvent, and then carrying out film forming treatment by adopting a tape casting method to obtain a semi-alicyclic polyimide film; preferably, the organic solvent includes one or a combination of two or more of tetrahydrofuran, dichloromethane, chloroform, m-cresol, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
7. The application according to claim 1, wherein the application comprises: separating hydrogen gas with the semi-alicyclic polyimide film; preferably, the application specifically includes: the semi-alicyclic polyimide film is used for separating hydrogen from hydrogen/methane mixed gas or hydrogen/nitrogen mixed gas.
8. Use according to claim 1, characterized in that: the thickness of the semi-alicyclic polyimide film is 60-80 mu m;
and/or the specific surface area of the semi-alicyclic polyimide film is more than 90m2/g。
9. A semi-alicyclic polyimide having a structure represented by formula (I):
Figure FDA0003110861890000031
wherein n is more than 10 and less than 500, and R is selected from the structures shown by any one or the combination of more than two of the following formulas:
Figure FDA0003110861890000032
Figure FDA0003110861890000041
wherein the dashed line represents the position of the amino group access.
10. A semi-alicyclic polyimide film characterized by: which is made of the semi-alicyclic polyimide according to claim 9.
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