Polyarylether resin, preparation method thereof and gas separation membrane

Abstract

The invention provides polyarylether resin, a preparation method thereof and a gas separation membrane, and relates to the technical field of polymer synthesis. According to the polyarylether resin, starting from the molecular design of a membrane material, an amino group having acid-base interaction and hydrogen bond interaction with carbon dioxide molecules and a non-planar aromatic macromolecular fluorenyl group capable of promoting the reduction of the stacking density of the molecular chain are introduced into the molecular chain; the polyarylether resin containing amino and fluorenyl structures and having a specific structure is obtained, and the polyarylether resin has excellent heat resistance, solubility and good gas separation performance for carbon dioxide and nitrogen, and can be used as a gas separation membrane material. The invention also provides a preparation method of the polyarylether resin and a gas separation membrane prepared from the polyarylether resin. The gas separation membrane has high carbon dioxide permeability coefficient and carbon dioxide / nitrogen selectivity.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer synthesis, and particularly relates to a polyarylether resin, a preparation method thereof, and a gas separation membrane. Background Art

[0002] Since industrialization, the sharp increase in CO2 emissions has been one of the main reasons for global warming. The capture and separation of CO2 is one of the important topics in the current energy and environmental fields. Compared with traditional separation technologies such as cryogenic distillation, absorption, and adsorption, membrane separation has the advantages of low cost, low energy consumption, simple operation, and clean energy conservation, and has great development potential in capturing carbon dioxide from flue gas. At present, the most widely studied gas separation membrane materials mainly include organic polymer membrane materials, inorganic membrane materials, and mixed matrix membrane materials. Compared with the poor processability and high manufacturing cost of inorganic membranes, and the poor compatibility between the polymer matrix and fillers of mixed matrix membranes, which are difficult to prepare, organic polymer membranes are increasingly in demand as high-performance gas separation membrane materials due to their low manufacturing cost and simple production process.

[0003] Due to the presence of a rigid aromatic ring structure in the main chain, polyarylethers have excellent thermal stability and mechanical properties; while the presence of ether bonds in the main chain gives them good processability, and they are one of the most important industrial polymer membrane materials at present. The polyarylethers used in gas separation membrane technology are mainly aromatic polyarylethers synthesized from bisphenols and dihalides. Due to the rigidity of the molecular chain and the strong intermolecular interaction, the molecular chains are closely packed, resulting in the inability to simultaneously meet the separation requirements of the membrane permeability and selectivity, which hinders their application in industry.

[0004] In view of this, the present invention is specifically proposed. Summary of the Invention

[0005] Aiming at the deficiencies and defects existing in the prior art, the present invention aims to provide a polyarylether resin, a preparation method thereof, and a gas separation membrane. Specifically, the present invention provides a polyarylether resin having a polar amino structure, a larger free volume fraction, higher heat resistance, and a higher permeability coefficient, and uses it to prepare a separation membrane material to obtain a gas separation membrane (high-temperature homogeneous membrane) with a higher permeability coefficient and better dimensional stability.

[0006] In order to achieve the above object, the following technical solutions are adopted:

[0007] The first object of the present invention is to provide a polyarylether resin having the structural formula shown in Formula I:

[0008]

[0009] In Formula I, the M1 structure is one of the following structures (a) to (h):

[0010]

[0011] The M2 structure is one of the following structures (i) to (m):

[0012]

[0013] Further, on the basis of the above technical solution of the present invention, in Formula I, the molar ratio m:n of the repeating unit containing an amino group, a fluorene group and an M2 structure to the repeating unit containing M1 and M2 structures is (0.1 - 1):(0 - 0.9), and m + n = 1.

[0014] The second object of the present invention is to provide a preparation method of the polyarylether resin provided by the first object of the present invention, comprising the following steps:

[0015] Taking 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene, the bisphenol monomer corresponding to the M1 structure and the dihalogen monomer corresponding to the M2 structure as reaction monomers, mixing them with a catalyst, a water-carrying agent and a solvent, and carrying out a stepwise polymerization reaction under a protective atmosphere to obtain a polyarylether resin.

[0016] Further, on the basis of the above technical solution of the present invention, the bisphenol monomer corresponding to the M1 structure is selected from at least one of bisphenol AF, bisphenol A, bisphenol S, bisphenol M, bisphenol fluorene, 1,3-bis(4-hydroxyphenyl)adamantane, truxene bisphenol or 4-(4-hydroxyphenyl)-2,3-diazanaphthalen-1-one;

[0017] and / or, the dihalogen monomer corresponding to the M2 structure includes at least one of 4,4'-difluorobenzophenone, 4,4'-difluorodiphenyl sulfone, 2,6-difluorobenzonitrile, 2,2-difluorobenzil or 2,4-bis(4-fluorophenyl)-6-phenyl-1,3,5-triazine.

[0018] Further, on the basis of the above technical solution of the present invention, the molar ratio of 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene to the bisphenol monomer corresponding to the M1 structure is (0.1 - 1):(0 - 0.9), and the total molar amount of 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene and the bisphenol monomer corresponding to the M1 structure is equal to the molar amount of the dihalogen monomer corresponding to the M2 structure.

[0019] Further, on the basis of the above technical solution of the present invention, the catalyst includes one or more of potassium carbonate, sodium carbonate, lithium carbonate, cesium carbonate, calcium carbonate, sodium bicarbonate or potassium bicarbonate;

[0020] and / or, the water-carrying agent includes one or more of toluene, n-hexane, cyclohexane, benzene or xylene;

[0021] And / or, the solvent includes one or more of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane or dimethyl sulfoxide;

[0022] And / or, the protective atmosphere includes a mixture of one or more of nitrogen, argon or helium.

[0023] Further, based on the above technical solution of the present invention, the molar total amount of 9,9-bis(4-aminophenyl)-2,7-dihydroxyfluorene and the bisphenol monomer corresponding to the M1 structure is in a ratio of 1:(1-3) to the molar amount of the catalyst;

[0024] And / or, the total mass of 9,9-bis(4-aminophenyl)-2,7-dihydroxyfluorene and the bisphenol monomer corresponding to the M1 structure is in a ratio of 1:(1-10) g / ml to the volume of the solvent;

[0025] And / or, the volume ratio of the solvent to the water-carrying agent is 1:(0.1-2).

[0026] Further, based on the above technical solution of the present invention, during the polymerization reaction process, first carry out water reflux at 80-160°C for 2-5 hours, drain the water-carrying agent, then raise the temperature to 100-170°C to distill off the remaining water-carrying agent, and then raise the temperature to 120-250°C to react for 5-15 hours.

[0027] The third object of the present invention is to provide a gas separation membrane made of the polyarylether resin provided by the first object of the present invention or the polyarylether resin prepared by the preparation method provided by the second object of the present invention.

[0028] Further, based on the above technical solution of the present invention, the gas separation membrane is used to separate carbon dioxide, the carbon dioxide permeability coefficient of the gas separation membrane is 7.0-14.0 Barrer, and / or the selectivity of the gas separation membrane for carbon dioxide and nitrogen is 29.4-40.4.

[0029] Compared with the prior art, the technical solution of the present invention has at least the following technical effects:

[0030] (1) The present invention provides a polyarylether resin, which is modified by introducing amino and fluorene groups into the main chain structure; wherein, there are acid-base interaction and hydrogen bond interaction between the amino group on the main chain and carbon dioxide molecules, and they can reversibly bind to carbon dioxide molecules. When this polyarylether resin is used as a membrane material to make a gas separation membrane, the dissolution selectivity of carbon dioxide in the separation membrane can be improved; the fluorene group on the main chain is a non-planar aromatic macromolecular group, which can effectively hinder the molecular chain packing, reduce the molecular chain packing density, so that the polymer has a relatively high free volume, and improves the gas permeation selectivity of the polyarylether. Moreover, the amino group in the polyarylether resin of the present invention is connected to the fluorene group. The fluorene group is a non-planar aromatic macromolecular group with a distorted structure, which can endow the amino group connected to it with a larger activity space, thereby promoting the effective contact between the amino group and CO2 to improve the dissolution selectivity for CO2.

[0031] (2) The polyarylether resin provided by the present invention introduces amino, fluorene and ether bonds into the same molecular chain simultaneously to obtain a defect-free polyarylether resin with amino and fluorene structures. The above specific structure endows the polyarylether resin with characteristics such as low cost, high heat resistance, high permeability coefficient and good dimensional stability.

[0032] (3) The present invention provides a preparation method of a polyarylether resin, which is mainly obtained by the polymerization reaction between 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene (also used as a bisphenol monomer) and bisphenol monomers and dihalogen monomers with other structures. This preparation method has strong universality, is applicable to the preparation of polyarylether resins with various forms of bisphenol monomers and dihalogen monomers, has good repeatability, and the prepared polyarylether resin has excellent carbon dioxide permeability coefficient and separation selectivity for carbon dioxide and nitrogen.

[0033] (4) The present invention also provides a gas separation membrane made of the polyarylether resin provided by the present invention. Due to the specific structure and properties of the polyarylether resin itself, the gas separation membrane (polyarylether homogeneous membrane) made from it also has excellent carbon dioxide permeability coefficient and separation selectivity for carbon dioxide and nitrogen. Description of the Drawings

[0034] Figure 1 The infrared spectrum of the polyarylether resin prepared in Example 3 of the present invention;

[0035] Figure 2 The differential scanning calorimetry analysis chart of the polyarylether resins prepared in Examples 1-3 and Examples 5-7 of the present invention;

[0036] Figure 3 The thermogravimetric analysis chart of the polyarylether resins prepared in Examples 1-5 of the present invention;

[0037] Figure 4 The NMR spectrum of the polyarylether resin prepared in Example 3 of the present invention. Detailed implementation mode

[0038] To make the objectives, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention. The process parameters without specific conditions noted in the following embodiments are usually in accordance with conventional conditions.

[0039] In the ranges disclosed in the present invention, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values and individual point values of each range, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in the present invention.

[0040] According to the first aspect of the present invention, a polyarylether resin is provided, which has the structural formula shown in Formula I:

[0041]

[0042] In Formula I, the M1 structure is generated by the reaction of the corresponding bisphenol monomer and is determined by the structure of the selected bisphenol monomer. The M1 structure is one of the following structures (a) to (h):

[0043]

[0044] It should be noted that in the above structures (a) to (h), the “—” on the benzene ring or phthalazinone indicates that this position is connected to the main chain of the structure of Formula I.

[0045] The structure of M2 is generated by the reaction of the corresponding dihalo monomer (such as a fluorine-containing dihalo monomer) and is determined by the structure of the selected dihalo monomer. The M2 structure is one of the following structures (i) to (m):

[0046]

[0047] It should be noted that in the above structures (i) to (m), the “—” on the benzene ring indicates that this position is connected to the main chain of the structure of Formula I.

[0048] The present invention provides a polyarylether resin, which is modified by introducing amino and fluorene groups into the main chain structure. Among them, there are acid-base interaction and hydrogen bond interaction between the amino group on the main chain and carbon dioxide molecules, and they can reversibly bind to carbon dioxide molecules. When this polyarylether resin is used as a membrane material to make a gas separation membrane, the dissolution selectivity of carbon dioxide in the separation membrane can be improved; the fluorene group on the main chain is a non-planar aromatic macromolecular group, which can effectively hinder the stacking of molecular chains, resulting in a decrease in the stacking density of molecular chains, so that the polymer has a higher free volume and improves the gas permeation selectivity of the polyarylether. Moreover, the amino group in the polyarylether resin of the present invention is connected to the fluorene group. As a non-planar aromatic macromolecular group, the structure of the fluorene group is distorted, which can endow the amino group connected to it with a larger activity space, thereby promoting the effective contact between the amino group and CO2 to improve the dissolution selectivity for CO2.

[0049] There are also specific limitations on the connection site of the amino group on the fluorene group. If the amino group is in the ortho position of the phenolic hydroxyl group, it is easily affected by the steric hindrance of the main chain and interacts with the adjacent main chain ether bond, thus hindering the effective contact between the amino group and CO2. In the present invention, the amino group is far from both the main chain and the phenolic hydroxyl group, and the activity space is significantly increased, which is more beneficial to improving the gas permeation selectivity of the polymer for CO2 gas.

[0050] The polyarylether resin of the present invention introduces amino, fluorene and ether bonds into the same molecular chain at the same time to obtain a polyarylether resin with a defect-free structure containing amino and fluorene groups. This polyarylether resin has the characteristics of low cost, high heat resistance, high permeability coefficient and good dimensional stability.

[0051] As an optional implementation manner of the technical solution of the present invention, in formula I, the molar ratio m:n of the repeating unit containing amino, fluorene and M2 structures to the repeating unit containing M1 and M2 structures is (0.1-1):(0-0.9), and m + n = 1. For example, m:n is 0.1:0.9, 0.2:0.8, 0.25:0.75, 0.3:0.7, 0.4:0.6, 0.5:0.5, 0.6:0.4, 0.7:0.3, 0.8:0.2, 0.9:0.1 or 1:0, etc.

[0052] When the molar ratio m:n of the two repeating units in the polyarylether resin of the present invention is 0.5:0.5, that is, the ratio of the number of the two repeating units is 1:1.

[0053] The polyarylether resin provided by the present invention has good thermal stability and an appropriate molecular weight. As an optional implementation manner of the technical solution of the present invention, the glass transition temperature (Tg) of the polyarylether resin is 170-300 °C, preferably 173-294 °C;

[0054] and / or, the 5% weight loss temperature (Td,5％ ) is 460 - 520 °C, preferably 464 - 517 °C.

[0055] As an alternative embodiment of the technical solution of the present invention, the number average molecular weight of the polyarylether resin is 4×10 4 ~12×10 4 Da.

[0056] According to the second aspect of the present invention, there is also provided a method for preparing the polyarylether resin provided in the first aspect of the present invention, comprising the following steps:

[0057] Using 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene, a bisphenol monomer corresponding to the M1 structure, and a dihalogen monomer corresponding to the M2 structure as reaction monomers, mixing them with a catalyst, a water-carrying agent, and a solvent, and performing a stepwise polymerization reaction under a protective gas atmosphere to obtain the polyarylether resin.

[0058] The method for preparing the polyarylether resin provided by the present invention is mainly obtained by a polymerization reaction between 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene (also used as a bisphenol monomer) and other bisphenol monomers and dihalogen monomers. This preparation method has strong universality, is applicable to the preparation of polyarylether resins with various forms of bisphenol monomers and dihalogen monomers, and has good repeatability.

[0059] As an alternative embodiment of the technical solution of the present invention, the bisphenol monomer corresponding to the M1 structure is selected from at least one of bisphenol AF (structure (a) corresponding to the M1 structure), bisphenol A (structure (b) corresponding to the M1 structure), bisphenol S (structure (c) corresponding to the M1 structure), bisphenol M (structure (d) corresponding to the M1 structure), bisphenol fluorene (structure (e) corresponding to the M1 structure), 1,3-bis(4-hydroxyphenyl)adamantane (structure (f) corresponding to the M1 structure), truxene bisphenol (structure (g) corresponding to the M1 structure), or 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one (DHPZ, structure (h) corresponding to the M1 structure). Among them, bisphenol AF, bisphenol A, bisphenol S, bisphenol M, bisphenol fluorene, and 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one can all be obtained by commercial purchase.

[0060] 1,3-Bis(4-hydroxyphenyl)adamantane can be prepared by self-preparation. The specific preparation method includes the following steps: Under nitrogen protection, add 25.00 g of 1,3-adamantanediol (purity 99%, purchased from Shanghai Macklin Biochemical Co., Ltd.) and 110.66 g of phenol (purity 99%, purchased from Shanghai Macklin Biochemical Co., Ltd.) into a 250 ml three-necked flask, and heat to 80 °C to melt it; Subsequently, during continuous stirring, slowly add 14.38 g of methanesulfonic acid and react at 90 °C for 7 hours. After the reaction is completed, pour the reaction mixture in the three-necked flask into 600 mL of deionized water to obtain a crude product. Filter the crude product and dissolve it in 400 mL of ethyl acetate, then add 600 mL of n-heptane, and obtain a precipitate after ultrasonic treatment for 30 minutes. Filter the precipitated solid and vacuum dry it at 60 °C for 5 hours to obtain the white solid product 1,3-bis(4-hydroxyphenyl)adamantane.

[0061] Triptycene bisphenol can be prepared by self-preparation. The specific preparation method includes the following steps:

[0062] (1) Under nitrogen protection, dissolve 7.10 g of anthracene (purity 99%, purchased from Shanghai Macklin Biochemical Co., Ltd.) and 4.39 g of 1,4-benzoquinone (purity 99%, purchased from Shanghai Macklin Biochemical Co., Ltd.) in 50 mL of xylene, place it in a 250 mL three-necked flask and heat to reflux for 3 hours. After the reaction is completed, cool to room temperature. Then filter the mixture, wash the filter cake with ethanol and dry it in a 60 °C vacuum oven to obtain 10.40 g of a light yellow solid product intermediate.

[0063] (2) Under nitrogen protection, dissolve 8.52 g of the light yellow solid product intermediate in 70 mL of glacial acetic acid, place it in a 250 mL three-necked flask, slowly drop two drops of 40% hydrobromic acid, and then heat to reflux for 2 hours. After the reaction is completed, cool to room temperature. Filter the mixed solution to obtain a white powder, and then vacuum dry it at 80 °C for 8 hours to obtain the white solid triptycene bisphenol.

[0064] As an alternative embodiment of the technical solution of the present invention, the dihalogen monomers corresponding to the M2 structure include at least one of 4,4'-difluorobenzophenone (structure (i) corresponding to the M2 structure), 4,4'-difluorodiphenyl sulfone (structure (j) corresponding to the M2 structure), 2,6-difluorobenzonitrile (structure (k) corresponding to the M2 structure), 2,2-difluorobenzil (structure (l) corresponding to the M2 structure), or 2,4-bis(4-fluorophenyl)-6-phenyl-1,3,5-triazine (BFPT, structure (m) corresponding to the M2 structure). Among them, 4,4'-difluorobenzophenone, 4,4'-difluorodiphenyl sulfone, 2,6-difluorobenzonitrile, and 2,2-difluorobenzil can all be obtained by commercial purchase. 2,4-bis(4-fluorophenyl)-6-phenyl-1,3,5-triazine can be obtained by commercial purchase or can be prepared by oneself.

[0065] By introducing adamantane, trifluoromethyl, asymmetric or non-coplanar structures into the polyarylether containing amino and fluorene structures, the present invention can reduce the packing degree of polymer molecular chains, reduce the interaction between molecular chains, and endow the polymer with good solubility and processing properties, and it can be dissolved in conventional organic solvents (such as N,N-dimethylacetamide (DMAC), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), etc.) at room temperature; as a gas separation membrane material, this polymer has excellent heat resistance, solubility, and good gas separation performance for carbon dioxide and nitrogen.

[0066] As an alternative embodiment of the technical solution of the present invention, the molar ratio of 9,9-bis(4-aminophenyl)-2,7-dihydroxyfluorene to the bisphenol monomer corresponding to the M1 structure is (0.1 - 1):(0 - 0.9), for example, 0.1:0.9, 0.2:0.8, 0.3:0.7, 0.4:0.5, 0.5:0.5, 0.6:0.4, 0.7:0.3, 0.8:0.2, 0.9:0.1, or 1.0:0, etc. The total molar amount of 9,9-bis(4-aminophenyl)-2,7-dihydroxyfluorene and the bisphenol monomer corresponding to the M1 structure is equal to the molar amount of the dihalogen monomer corresponding to the M2 structure.

[0067] As an alternative embodiment of the technical solution of the present invention, the catalyst includes one or several of potassium carbonate, sodium carbonate, lithium carbonate, cesium carbonate, calcium carbonate, sodium bicarbonate, or potassium bicarbonate.

[0068] As an alternative embodiment of the technical solution of the present invention, the solvent includes one or several of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane, or dimethyl sulfoxide.

[0069] As an alternative embodiment of the technical solution of the present invention, the water-carrying agent includes one or more of toluene, n-hexane, cyclohexane, benzene or xylene.

[0070] As an alternative embodiment of the technical solution of the present invention, the inert protective atmosphere includes one or a mixture of two or more of nitrogen, argon or helium, preferably nitrogen.

[0071] As an alternative embodiment of the technical solution of the present invention, the molar ratio of the total molar amount of the bisphenol monomer (i.e., the total molar amount of 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene and the bisphenol monomer corresponding to the M1 structure) to the molar amount of the catalyst is 1:(1-3), for example, 1:1, 1:1.5, 1:2, 1:2.5 or 1:3, etc.

[0072] As an alternative embodiment of the technical solution of the present invention, the ratio of the total mass of the bisphenol monomer to the volume of the solvent is 1:(1-10) g / ml, for example, 1 g / ml, 2 g / ml, 3 g / ml, 4 / ml, 5 g / ml, 6 g / ml, 7 g / ml, 8 / ml, 9 g / ml or 10 g / ml, etc.

[0073] As an alternative embodiment of the technical solution of the present invention, the volume ratio of the solvent to the water-carrying agent is 1:(0.1-2), for example, 1:0.1, 1:0.5, 1:1, 1:1.5 or 1:2, etc.

[0074] As an alternative embodiment of the technical solution of the present invention, during the polymerization reaction, first carry out water reflux at 80-160 °C (for example, 80 °C, 100 °C, 120 °C, 140 °C, 150 °C or 160 °C, etc.) for 2-5 h (for example, 2 h, 3 h, 4 h or 5 h, etc.), drain the water-carrying agent, then raise the temperature to 100-170 °C (for example, 100 °C, 120 °C, 140 °C, 150 °C, 160 °C or 170 °C, etc.) to distill off the remaining water-carrying agent, and then raise the temperature to 120-250 °C (for example, 120 °C, 140 °C, 150 °C, 160 °C, 180 °C, 200 °C, 220 °C, 240 °C or 250 °C, etc.) and react for 5-15 h (for example, 5 h, 8 h, 10 h, 12 h, 14 h or 15 h, etc.).

[0075] According to the third aspect of the present invention, there is also provided a gas separation membrane made of the polyarylether resin provided in the first aspect of the present invention or the polyarylether resin prepared by the preparation method provided in the second aspect of the present invention.

[0076] Due to the specific structure and properties of the polyarylether resin itself, the gas separation membrane (polyarylether homogeneous membrane) prepared therefrom has excellent carbon dioxide permeability coefficient (for example, it can be as high as 14.0 Barrer) and separation selectivity for carbon dioxide and nitrogen (for example, it can reach 40.4).

[0077] As an alternative embodiment of the technical solution of the present invention, the polyarylether resin prepared by the present invention is formulated into a solution, and then a homogeneous membrane is prepared on a polytetrafluoroethylene petri dish by the solvent evaporation method to obtain a gas separation membrane.

[0078] As an alternative embodiment of the technical solution of the present invention, the gas separation membrane is used to separate carbon dioxide. The thickness of the gas separation membrane is 25 - 300 μm (for example, 25 μm, 30 μm, 50 μm, 60 μm, 63 μm, 65 μm, 70 μm, 73 μm, 75 μm, 80 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, etc.), and preferably 50 - 100 μm.

[0079] As an alternative embodiment of the technical solution of the present invention, the carbon dioxide permeability coefficient of the gas separation membrane is 7.0 - 14.0 Barrer, and the selectivity for carbon dioxide and nitrogen is 29.4 - 40.4.

[0080] The present invention will be further described in detail below with specific examples and comparative examples, and the raw materials involved in each example and comparative example are described as follows:

[0081] The purities of bisphenol AF, bisphenol A, and bisphenol fluorene are all 99%, and they are purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; the purities of 4,4'-difluorobenzophenone, 4,4'-difluorodiphenyl sulfone, and 9,9-bis(3-amino-4-hydroxyphenyl)fluorene are all 99%, and they are purchased from Shanghai Macklin Biochemical Co., Ltd.; 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one, with a purity of 99%, is purchased from Dalian Baolimo New Materials Co., Ltd.

[0082] The synthesis steps of 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene are as follows: Under an ice bath environment and nitrogen protection, 2.28 g of 2,7-dihydroxy-9-fluorenone (99%, purchased from Shanghai Macklin Biochemical Co., Ltd.) and 8.01 g of aniline (purity 99%, purchased from Shanghai Macklin Biochemical Co., Ltd.) were added to a three-necked flask, and 0.81 g of trifluoromethanesulfonic acid was slowly added dropwise through a constant pressure dropping funnel. Stir continuously in the ice bath for 20 min, then raise the temperature to 150 °C and react at a constant temperature for 10 h. After the reaction is completed, lower the temperature to 80 °C, add absolute ethanol to the reaction solution and stir for 20 min. After the system cools to room temperature, filter by suction, and then place the obtained solid product in a vacuum oven at 80 °C for drying for 10 hours to finally obtain 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene in the form of a pale yellow powder.

[0083] The synthesis steps of 2,4-bis(4-fluorophenyl)-6-phenyl-1,3,5-triazine are as follows: At ice bath temperature, 100 mL of chlorobenzene (analytical pure, purchased from Shanghai Macklin Biochemical Co., Ltd.), 12.111 g of 4-fluorobenzonitrile (99%, purchased from Shanghai Macklin Biochemical Co., Ltd.), 5.1 mL of benzaldehyde (analytical pure, purchased from Shanghai Macklin Biochemical Co., Ltd.) and 2.675 g of ammonium chloride were added to a three-necked flask, and then 6.667 g of aluminum chloride was gradually added. Thereafter, raise the temperature to 130 °C and react for 8 - 12 h. Slowly pour the reaction mixture into a 5% hydrochloric acid aqueous solution for precipitation. Remove the chlorobenzene in the mixture by steam distillation, and then filter. Wash the product with deionized water until neutral, then add 200 mL of methanol to the obtained white solid, stir and filter. The crude product is dried in vacuo at 100 °C for 24 h, and finally the crude product is recrystallized from toluene and then placed in a vacuum oven at 80 °C for drying for 10 hours to finally obtain the white solid product 2,4-bis(4-fluorophenyl)-6-phenyl-1,3,5-triazine.

[0084] Example 1

[0085] This example provides a polyarylether resin, and the specific structural formula is as follows:

[0086]

[0087] In the formula, the value of m is 0.1 and the value of n is 0.9.

[0088] The preparation method of the polyarylether resin in this example includes the following steps:

[0089] (1) Under nitrogen protection, add the reaction monomers 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene (0.5 mmol, 0.190 g), bisphenol AF (4.5 mmol, 1.513 g), 4,4'-difluorobenzophenone (5 mmol, 1.091 g), the catalyst potassium carbonate (0.91 g), the solvent N-methylpyrrolidone (10 ml), and the water-carrying agent toluene (15 ml) into a 100 mL three-necked flask connected to a mechanical stirrer, a water separator, an inlet tube, and a condenser tube;

[0090] Under a nitrogen atmosphere, gradually raise the temperature of the system to 80 °C, and carry water at this temperature for 2 h to ensure that there is no residual water in the system, and then drain the water-carrying agent. Remove the residual toluene in the system by heating to 100 °C. Then, heat the reaction to 120 °C for about 15 h until the reaction ends.

[0091] (2) After the reaction ends, dilute the mixture in the three-necked flask with NMP, and then precipitate it in boiling deionized water to precipitate a strip-shaped polymer crude product. Then, boil the polymer crude product with deionized water until it is clear to remove the residual solvent in the polymer, then filter it by suction, dry it in an ordinary pressure oven for 10 h, and then dry it in a vacuum oven to obtain the polyarylether resin.

[0092] Example 2

[0093] This example provides a polyarylether resin, and its specific structural formula is as follows:

[0094]

[0095] In the formula, the value of m is 0.25, and the value of n is 0.75.

[0096] The preparation method of the polyarylether resin in this example includes the following steps:

[0097] (1) Under nitrogen protection, add the reaction monomers 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene (1.25 mmol, 0.476 g), bisphenol AF (3.75 mmol, 1.261 g), 4,4'-difluorobenzophenone (5 mmol, 1.091 g), the catalyst potassium carbonate (0.91 g), the solvent N-methylpyrrolidone (10 ml), and the water-carrying agent toluene (15 ml) into a 100 mL three-necked flask connected to a mechanical stirrer, a water separator, an inlet tube, and a condenser tube;

[0098] Under a nitrogen atmosphere, gradually raise the temperature of the system to 100 °C, and carry water at this temperature for 3 h to ensure that there is no residual water in the system, and then drain the water-carrying agent. Remove the residual toluene in the system by heating to 120 °C. Then, heat the reaction to 150 °C for about 13 h until the reaction ends.

[0099] (2) After the reaction is completed, the mixture in the three-necked flask is diluted with NMP and then precipitated in boiling deionized water to precipitate a strip-shaped polymer crude product. Then, the polymer crude product is boiled with deionized water until it becomes clear to remove the residual solvent in the polymer. Then, it is filtered by suction and dried in an ordinary pressure oven for 10 h, and then dried in a vacuum oven to obtain the polyarylether resin.

[0100] Example 3

[0101] This example provides a polyarylether resin, and its specific structural formula is as follows:

[0102]

[0103] In the formula, the value of m is 0.5 and the value of n is 0.5.

[0104] The preparation method of the polyarylether resin in this example includes the following steps:

[0105] (1) Under the protection of nitrogen, 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene (2.5 mmol, 0.951 g), bisphenol AF (2.5 mmol, 0.841 g), 4,4'-difluorobenzophenone (5 mmol, 1.091 g), catalyst potassium carbonate (0.91 g), solvent N-methylpyrrolidone (10 ml) and water-carrying agent toluene (15 ml) are added to a 100 mL three-necked flask connected with a mechanical stirrer, a water separator, an inlet pipe and a condenser.

[0106] Under a nitrogen atmosphere, the temperature of the system is gradually raised to 120 °C, and water is carried at this temperature for 3 h to ensure that there is no residual water in the system. Then, the water-carrying agent is drained off. By heating to 140 °C, the residual toluene in the system is removed. Then, the reaction is heated to 170 °C for about 10 h until the reaction is completed.

[0107] (2) After the reaction is completed, the mixture in the three-necked flask is diluted with NMP and then precipitated in boiling deionized water to precipitate a strip-shaped polymer crude product. Then, the polymer crude product is boiled with deionized water until it becomes clear to remove the residual solvent in the polymer. Then, it is filtered by suction and dried in an ordinary pressure oven for 10 h, and then dried in a vacuum oven to obtain the polyarylether resin.

[0108] Example 4

[0109] This example provides a polyarylether resin, and its specific structural formula is as follows:

[0110]

[0111] In the formula, the value of m is 0.75 and the value of n is 0.25.

[0112] The preparation method of the polyarylether resin in this example includes the following steps:

[0113] (1) Under nitrogen protection, add the reaction monomers 9,9-bis(4-aminophenyl)-2,7-dihydroxyfluorene (3.75 mmol, 1.427 g), bisphenol AF (1.25 mmol, 0.420 g), 4,4'-difluorobenzophenone (5 mmol, 1.091 g), the catalyst potassium carbonate (0.91 g), the solvent N-methylpyrrolidone (10 ml), and the water-carrying agent toluene (15 ml) into a 100 mL three-necked flask connected with a mechanical stirrer, a water separator, an inlet pipe, and a condenser.

[0114] Under a nitrogen atmosphere, the temperature of the system is gradually raised to 135 °C, and water is carried for 3 h at this temperature to ensure that there is no residual water in the system, and then the water-carrying agent is drained off. Residual toluene in the system is removed by heating to 155 °C. Then, the reaction is heated to 180 °C for about 8 h until the reaction ends.

[0115] (2) After the reaction ends, dilute the mixture in the three-necked flask with NMP, and then precipitate it in boiling deionized water to precipitate a strip-shaped polymer crude product. Then, boil the polymer crude product with deionized water until it is clear to remove the residual solvent in the polymer, then filter by suction, dry it in an ordinary pressure oven for 10 h, and then dry it in a vacuum oven to obtain the polyarylether resin.

[0116] Example 5

[0117] This example provides a polyarylether resin, and the specific structural formula is as follows:

[0118]

[0119] In the formula, the value of m is 1, and the value of n is 0.

[0120] The preparation method of the polyarylether resin in this example includes the following steps:

[0121] (1) Under nitrogen protection, add the reaction monomers 9,9-bis(4-aminophenyl)-2,7-dihydroxyfluorene (5 mmol, 1.902 g), 4,4'-difluorobenzophenone (5 mmol, 1.091 g), the catalyst potassium carbonate (0.91 g), the solvent N-methylpyrrolidone (10 ml), and the water-carrying agent toluene (15 ml) into a 100 mL three-necked flask connected with a mechanical stirrer, a water separator, an inlet pipe, and a condenser.

[0122] Under a nitrogen atmosphere, the temperature of the system was gradually raised to 150 °C, and water was carried at this temperature for 3 h to ensure that there was no residual water in the system, and then the water-carrying agent was drained off. The residual toluene in the system was removed by heating to 160 °C. Then, the reaction was heated to 200 °C for about 6 h until the reaction was completed.

[0123] (2) After the reaction was completed, the mixture in the three-necked flask was diluted with NMP and then precipitated in boiling deionized water to precipitate a strip-shaped polymer crude product. Then, the polymer crude product was boiled with deionized water until it was clear to remove the residual solvent in the polymer. Then, it was filtered by suction, dried in an ordinary pressure oven for 10 h, and then dried in a vacuum oven to obtain a polyarylether resin.

[0124] Example 6

[0125] This example provides a polyarylether resin, and the specific structural formula is as follows:

[0126]

[0127] In the formula, the value of m is 0.2 and the value of n is 0.8.

[0128] The preparation method of the polyarylether resin in this example includes the following steps:

[0129] Under nitrogen protection, 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene (1 mmol, 0.380 g), 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one (4 mmol, 0.953 g), 4,4'-difluorodiphenyl sulfone (5 mmol, 1.271 g), catalyst potassium carbonate (0.91 g), solvent dimethyl sulfoxide (10 ml) and water-carrying agent toluene (15 ml) were added to a 100 mL three-necked flask connected with a mechanical stirrer, a water-carrying device, an inlet pipe and a condenser tube;

[0130] Under a nitrogen atmosphere, the temperature of the system was gradually raised to 160 °C, and water was carried at this temperature for 5 h to ensure that there was no residual water in the system, and then the water-carrying agent was drained off. The residual toluene in the system was removed by heating to 170 °C. Then, the reaction was heated to 250 °C for about 5 h until the reaction was completed.

[0131] After the reaction was completed, the mixture in the three-necked flask was diluted with NMP and then precipitated in boiling deionized water to precipitate a strip-shaped polymer crude product. Then, the polymer crude product was boiled with deionized water until it was clear to remove the residual solvent in the polymer. Then, it was filtered by suction, dried in an ordinary pressure oven for 10 h, and then dried in a vacuum oven to obtain a polyarylether resin.

[0132] Example 7

[0133] This embodiment provides a polyarylether resin, and its specific structural formula is as follows:

[0134]

[0135] In the formula, the value of m is 0.4, and the value of n is 0.6.

[0136] The preparation method of the polyarylether resin in this embodiment includes the following steps:

[0137] (1) Under nitrogen protection, add the reaction monomers 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene (2 mmol, 0.760 g), bisphenol A (3 mmol, 0.685 g), 2,4-bis(4-fluorophenyl)-6-phenyl-1,3,5-triazine (5 mmol, 1.727 g), the catalyst potassium carbonate (0.91 g), the solvent dimethyl sulfoxide (10 ml), and the water-carrying agent toluene (15 ml) into a 100 mL three-necked flask connected with a mechanical stirrer, a water separator, an inlet pipe, and a condenser tube;

[0138] Under a nitrogen atmosphere, the temperature of the system is gradually raised to 150 °C, and water is carried for 5 h at this temperature to ensure that there is no residual water in the system, and then the water-carrying agent is drained. By heating to 170 °C, the residual toluene in the system is removed. Then, the reaction is heated to 230 °C for about 5 h until the reaction ends.

[0139] (2) After the reaction ends, dilute the mixture in the three-necked flask with NMP, and then precipitate it in boiling deionized water to precipitate a strip-shaped polymer crude product. Then, boil the polymer crude product with deionized water until it is clear to remove the residual solvent in the polymer, then filter it by suction, dry it in an ordinary pressure oven for 10 h, and then dry it in a vacuum oven to obtain the polyarylether resin.

[0140] Comparative Example 1

[0141] This comparative example provides a polyarylether resin, and its specific structural formula is as follows:

[0142]

[0143] In the formula, the value of m is 0.5, and the value of n is 0.5.

[0144] The preparation method of the polyarylether resin in this comparative example is the same as that in Example 3, except that the reaction monomer 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene (2.5 mmol, 0.951 g) in Example 3 is replaced by bisphenol fluorene (2.5 mmol, 0.876 g).

[0145] Comparative Example 2

[0146] This comparative example provides a polyarylether resin, and its specific structural formula is as follows:

[0147]

[0148] In the formula, the value of m is 0.5 and the value of n is 0.5.

[0149] The preparation method of the polyarylether resin of this comparative example is the same as that of Example 3 except that the reaction monomer 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene (2.5 mmol, 0.951 g) in Example 3 is replaced by 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (2.5 mmol, 0.951 g).

[0150] In order to compare the technical effects of each example and comparative example, the following experimental examples are specially set up.

[0151] Experimental Example 1

[0152] (1) Taking Example 3 as an example, the prepared polyarylether resin was tested by infrared spectroscopy (FT-IR) on a Thermo Nicolet IS50 infrared spectrometer, using reflection spectroscopy. Before the sample test, the test sample needs to be placed in a vacuum oven at 100 °C and dried for more than 12 hours to exclude the interference of solvents such as water on the test.

[0153] From Figure 1 it can be seen that stretching vibration characteristic peaks of primary amine (N-H) appear near 3460 cm -1 and 3365 cm -1 , stretching vibration characteristic peaks of carbonyl (C=O) appear near 1593 cm -1 , and 1231 cm -1 is the stretching vibration characteristic peak of ether bond (C-O-C), thus proving the synthesis of Example 3.

[0154] (2) The polyarylether resin prepared in Example 3 was tested by nuclear magnetic resonance spectroscopy on an AVANCE NEO 600M nuclear magnetic resonance spectrometer. The solvent was deuterated dimethyl sulfoxide (DMSO-d6), and tetramethylsilane (TMS) was used as the internal standard at room temperature. The test sample needs to be placed in a vacuum oven at 100 °C and dried for more than 12 hours to exclude the interference of solvents such as water on the test. When preparing the sample, 5-10 mg of the sample to be tested was put into a nuclear magnetic tube, 0.5 ml of deuterated solvent was added, and after shaking and dissolving fully, the test was carried out.

[0155] For Figure 4 all hydrogen atoms of the nuclear magnetic resonance hydrogen spectrum of Example 3, accurate attribution was carried out, and it was confirmed that the molar ratio of the two bisphenol monomers in the obtained polymer was consistent with the feeding ratio of the monomers, proving the successful synthesis of Example 3.

[0156] (3) The glass transition temperature (Tg) of the polyarylether resins prepared in the examples and comparative examples of the present invention was measured. Specifically, a METTLER DSC822 differential scanning calorimeter was used for the test. Among them, the nitrogen flow rate was 50 ml / min, the heating rate was 10 °C / min, the test range was 50 - 350 °C, and the test samples needed to be dried in a vacuum oven at 100 °C for more than 12 hours to exclude the interference of solvents such as water on the test. See Table 1 and Figure 2 。

[0157] From Figure 2 and Table 1, it can be seen that the glass transition temperature (Tg) of the polymer is between 173 °C and 294 °C, showing excellent thermal properties. The glass transition temperature of the polymer increases significantly with the increase in the amino group content. This is because the 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene monomer contains an amino group and a non-planar aromatic bulky side group fluorene group. The benzene ring structure of the fluorene group endows the polymer with high rigidity, and the hydrogen atom in the amino group can form intermolecular hydrogen bonds with the oxygen atom in the main chain, which can effectively enhance the interaction between polymer chains, thereby increasing the glass transition temperature of the polymer.

[0158] (4) Thermogravimetric analysis was carried out on the polyarylether resins prepared in the examples and comparative examples of the present invention. The thermogravimetric analysis was carried out on a METTLER TGA / SDTA851, and the test was carried out in a nitrogen atmosphere (gas flow rate was 50 mL / min), and the heating rate was 10 °C / min. The test samples needed to be dried in a vacuum oven at 100 °C for more than 12 hours to exclude the interference of solvents such as water on the test. See Table 1 and Figure 3 。

[0159] From Figure 3 and Table 1, it can be seen that the polymers of Examples 1 - 5 all have only one thermogravimetric platform, which corresponds to the degradation process of the polymer main chain. The 5% weight loss temperature of the polymer is between 497 °C and 517 °C, indicating that the synthesized polymer has good thermal stability. As the amino group content increases from 10% to 50% (i.e., Examples 1, 2, and 3), the 5% weight loss temperature shows an obvious downward trend. This phenomenon is due to the poor stability of the amino group. However, when the amino group content continues to increase from 50% to 100% (i.e., Examples 3, 4, 5), the 5% weight loss temperature hardly changes. This may be because the high proportion of polar amino groups form an ordered structure, improving the thermal stability of the polymer. The result of the competition between the two makes the 5% weight loss temperatures of Examples 3, 4, and 5 very close and does not decrease significantly with the increase in the amino group content.

[0160] (5) The molecular weights of the polyarylether resins prepared in the examples and comparative examples of the present invention were measured by gel permeation chromatography (GPC). The specific test was carried out on an Agilent PL-GPC 50 instrument, with NMP as the solvent. The specific results are shown in Table 1.

[0161] Table 1

[0162]

[0163]

[0164] (6) The dissolution properties of the polyarylether resins prepared in the examples and comparative examples of the present invention were detected. Specifically, 0.04 g of the polyarylether resin was respectively placed in 1 mL of the following solvents. The specific results are shown in Table 2.

[0165] Table 2

[0166] Experimental group NMP DMAc DMF THF DMSO Chloroform Dichloromethane Example 1 ++ ++ ++ ++ +- ++ ++ Example 2 ++ ++ ++ ++ ++ ++ ++ Example 3 ++ ++ ++ ++ ++ ++ ++ Example 4 ++ ++ ++ ++ ++ +- - Example 5 ++ ++ ++ ++ ++ - - Example 6 ++ ++ ++ - + + +- Example 7 ++ ++ ++ ++ + +- - Comparative Example 1 ++ ++ ++ ++ +- ++ ++ Comparative Example 2 ++ ++ ++ ++ ++ ++ ++

[0167] Note: ++ means dissolution at room temperature; + means dissolution by heating; +- means partial dissolution by heating; - means no dissolution.

[0168] As can be seen from Table 2, this type of polymer has good solubility in N-methylpyrrolidone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and tetrahydrofuran (THF). Moreover, as the amino group content in the polymer increases, the solubility of the polymer in polar solvents such as dimethyl sulfoxide (DMSO) improves, while the solubility in non-polar solvents such as chloroform and dichloromethane is relatively small, which is consistent with the principle of like dissolves like. By comparing Example 3 with Comparative Example 1, it was found that the presence of polar amino groups improved the solubility of the polymer in polar solvents such as dimethyl sulfoxide (DMSO).

[0169] Experimental Example 2

[0170] The polyarylether resins prepared in the examples and comparative examples of the present invention were respectively dissolved in NMP to prepare solutions, and polyarylether homogeneous membranes with a certain film thickness were prepared on a polytetrafluoroethylene petri dish by the solvent evaporation method. The gas separation properties of the above-prepared polyarylether homogeneous membranes were detected in accordance with the test method for gas permeability of polymer membrane materials GBT40260-2021. The gas permeability test was carried out on a GTR-721 type gas permeability tester produced by Jinan Sike Testing Technology Co., Ltd. The test pressure was 0.1 MPa, and the test temperature was 35 °C. The specific results are shown in Table 3.

[0171] Table 3

[0172]

[0173] Through the performance comparison of Examples 1-5 in Table 3, it is found that as the content of polar amino groups increases, the permeability coefficient of CO2 decreases, and the CO2 / N2 selectivity first increases and then decreases. This is because there are hydrogen bond interactions and acid-base interactions between the hydrogen atoms of amino groups and the oxygen atoms of CO2, which promote the dissolution of CO2 in the polymer, resulting in an increase in the CO2 / N2 selectivity of the polymer. However, as the amino group content of the polymer increases, the intermolecular hydrogen bond density increases, hindering the movement of chain segments and reducing the permeation rate of gas molecules, resulting in a decrease in the permeability coefficient of CO2 and a decrease in the CO2 / N2 selectivity. Examples 3 and Comparative Example 1 illustrate that amino groups are beneficial to the permeation selectivity of the polymer for CO2 gas. Compared with Comparative Example 2, the amino groups of the polymer in Example 3 are farther away from both the main chain and the phenolic hydroxyl group, and the activity space is significantly increased, which is obviously more beneficial to improving the permeation selectivity of the polymer for CO2 gas.

[0174] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention are within the scope of the claims of the present invention pending approval.

Claims

1. A polyarylether resin, characterized in that, The polyarylether resin has a structural formula shown in Formula I: In Formula I, the structure of M1 is one of the following structures (a) to (h): The structure of M2 is one of the following structures (i) to (m):

2. The polyarylether resin according to claim 1, characterized in that, In Formula I, the molar ratio m:n of the repeating unit containing an amino group, a fluorene group, and the M2 structure to the repeating unit containing the M1 and M2 structures is (0.1 - 1):(0 - 0.9), and m + n = 1.

3. The preparation method of the polyarylether resin according to claim 1 or 2, characterized in that, It includes the following steps: Using 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene, the bisphenol monomer corresponding to the M1 structure, and the dihalogen monomer corresponding to the M2 structure as reaction monomers, mixing them with a catalyst, a water-carrying agent, and a solvent, and carrying out a stepwise polymerization reaction under a protective atmosphere to obtain the polyarylether resin.

4. The preparation method of the polyarylether resin according to claim 3, characterized in that, The bisphenol monomer corresponding to the M1 structure is selected from at least one of bisphenol AF, bisphenol A, bisphenol S, bisphenol M, bisphenol fluorene, 1,3-bis(4-hydroxyphenyl)adamantane, truxene bisphenol, or 4-(4-hydroxyphenyl)-2,3-diazanaphthalen-1-one; And / or, the dihalogen monomer corresponding to the M2 structure includes at least one of 4,4'-difluorobenzophenone, 4,4'-difluorodiphenyl sulfone, 2,6-difluorobenzonitrile, 2,2-difluorobenzil, or 2,4-bis(4-fluorophenyl)-6-phenyl-1,3,5-triazine.

5. The preparation method of the polyarylether resin according to claim 4, wherein The molar ratio of 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene to the bisphenol monomer corresponding to the M1 structure is (0.1 - 1):(0 - 0.9), and the total molar amount of 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene and the bisphenol monomer corresponding to the M1 structure is equal to the molar amount of the dihalogen monomer corresponding to the M2 structure.

6. The preparation method of the polyarylether resin according to claim 3, characterized in that The catalyst includes one or several of potassium carbonate, sodium carbonate, lithium carbonate, cesium carbonate, calcium carbonate, sodium bicarbonate, or potassium bicarbonate; And / or, the water-carrying agent includes one or several of toluene, n-hexane, cyclohexane, benzene, or xylene; And / or, the solvent includes one or several of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane, or dimethyl sulfoxide; And / or, the protective atmosphere includes one or a mixture of two or more of nitrogen, argon, or helium.

7. The preparation method of the polyarylether resin according to claim 6, wherein The molar ratio of the total molar amount of 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene and the bisphenol monomer corresponding to the M1 structure to the molar amount of the catalyst is 1:(1 - 3); And / or, the ratio of the total mass of 9,9-bis-(4-aminophenyl)-2,7-dihydroxyfluorene and the bisphenol monomer corresponding to the M1 structure to the volume of the solvent is 1:(1 - 10) g / ml; And / or, the volume ratio of the solvent to the water-carrying agent is 1:(0.1 - 2).

8. The preparation method of the polyarylether resin according to claim 3, characterized in that, During the polymerization reaction process, first carry out water reflux at 80 - 160 °C for 2 - 5 hours, drain the water-carrying agent, then raise the temperature to 100 - 170 °C to distill off the remaining water-carrying agent, and then raise the temperature to 120 - 250 °C and react for 5 - 15 hours.

9. A gas separation membrane, characterized in that, It is made of the polyarylether resin described in Claim 1 or 2 or the polyarylether resin prepared by the preparation method according to any one of Claims 3 - 8.

10. The gas separation membrane according to claim 9, characterized in that, The gas separation membrane is used for separating carbon dioxide. The carbon dioxide permeability coefficient of the gas separation membrane is 7.0 - 14.0 Barrer, and / or the selectivity of the gas separation membrane for carbon dioxide and nitrogen is 29.4 - 40.4.

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