CN115414805A - Preparation method of high-flux polyaryletherketone-based carbon membrane - Google Patents
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Abstract
The invention relates to a preparation method of a high-flux polyaryletherketone-based carbon membrane, belonging to the field of membrane separation and the field of new materials. A preparation method of a high-flux polyaryletherketone-based carbon membrane is characterized in that large-volume side groups are introduced into a polyaryletherketone polymer structure to obtain functionalized polyaryletherketone; preparing a polyaryletherketone-based porous polymer film by using the functionalized polyaryletherketone; pre-filling a pore structure of the polyaryletherketone-based porous polymer membrane in a pore filler solution; under the action of an initiator, grafting and polymerizing a densifying monomer on the surface of the porous polymer film; and drying and carbonizing the porous polymer film with the surface controlled to be densified to obtain the high-flux polyaryletherketone-based carbon film. The carbon film of the invention shows high gas permeation flux because the porous structure of the polymer film stage is well maintained, the polymer film framework is converted into an amorphous carbon structure in the pyrolysis carbonization process, and the controlled densification of the film surface ensures that the prepared porous carbon film maintains higher selectivity.
Description
Technical Field
The invention relates to a preparation method of a high-flux polyaryletherketone-based carbon membrane, belonging to the field of membrane separation and the field of new materials.
Background
The membrane separation technology is a novel separation technology with the functions of separation, concentration, purification and the like, has the characteristics of high efficiency, energy conservation, environmental protection, simple operation process, easy control and the like, and is widely applied to various fields. Among them, carbon molecular sieve membranes (carbon membranes for short) have received much attention from researchers because of their developed, highly selective, nanoscale, ultrafine pore structures, high thermal and chemical stability, corrosion resistance, and gas separation performance exceeding the upper limit of Robeson. Compared with the defects of faster flux attenuation and low permeability of the traditional carbon film in the using process, the high-flux carbon film prepared by pyrolyzing and carbonizing the porous polymer film has higher research value and application prospect.
The selection of an excellent precursor polymer material is the key to preparing the carbon film with excellent performance. Most carbon film precursor polymer materials are thermosetting polymers, have a limited selection range and low performance, and the precursor polymer materials are high in preparation cost. The polyaryletherketone is a thermoplastic polymer with excellent performance, has the advantages of good thermal and chemical stability, high mechanical performance and good film forming property, and can be used as a precursor material for preparing a carbon film with excellent performance. However, in the process of heat treatment, the polyaryletherketone as a thermoplastic material melts when reaching the melting point, so that the porosity of the porous polymer film is greatly reduced, and the structure of the polymer film and the carbon film is densified, thereby greatly reducing the flux. The polyaryletherketone-based porous carbon membrane with high flux can not be prepared by the conventional polymer membrane pyrolysis method.
Therefore, how to solve the problems of pore structure fusion and integral densification of the polyaryletherketone-based porous polymer film in the high-temperature heat treatment process becomes the key for preparing the polyaryletherketone-based carbon film with high flux and high selectivity.
Disclosure of Invention
The invention aims to solve the problems of pore structure fusion and integral densification of a polyaryletherketone-based porous polymer film in a high-temperature heat treatment process, and prepare the polyaryletherketone-based high-flux carbon film with high flux, high selectivity and good pore structure maintenance. The invention provides a preparation method of a high-flux polyaryletherketone-based carbon membrane. The technical scheme of the invention is as follows:
a preparation method of a high-flux polyaryletherketone-based carbon membrane is characterized in that large-volume side groups are introduced into a polyaryletherketone polymer structure to obtain functionalized polyaryletherketone; preparing a polyaryletherketone-based porous polymer membrane by using the functionalized polyaryletherketone; pre-filling the pore structure of the polyaryletherketone porous polymer membrane in a pore filler solution; under the action of an initiator, grafting and polymerizing a densifying monomer on the surface of the porous polymer film; drying and carbonizing the porous polymer film with the surface controlled densification to obtain the high-flux polyaryletherketone-based carbon film,
wherein, the bulky side group is one of hydroxyl, carboxyl, sulfonic group, chloromethyl, allyl, pyridyl and quaternary ammonium salt group.
In the technical scheme, the densification monomer is one of 2-methacryloyloxyethyl phosphorylcholine, methyl methacrylate, butyl acrylate, acrylic acid and dimethylamino ethyl methacrylate.
Preferably, the method for introducing bulky side groups into the polyaryletherketone polymer structure is as follows: mixing polyaryletherketone with one of 98% concentrated sulfuric acid, sulfur trioxide, chlorosulfonic acid, sulfur trioxide, triethyl phosphate complex and hydroxysulfonic acid at room temperature, firstly carrying out ultrasonic reaction for 1-5 h at the ultrasonic frequency of 100-300 kHz, heating to 40-100 ℃, then continuing the ultrasonic reaction for 3-24 h to obtain polyaryletherketone with sulfonic acid side groups, precipitating and drying to obtain the polyaryletherketone with sulfonic acid side groups,
wherein, the polyaryletherketone: the proportion of the liquid substance containing sulfonic acid group is 1g/5 ml-1 g/100ml; polyaryletherketone: the proportion of the solid substance containing sulfonic acid groups is 1g/5 g-1 g/100g.
Preferably, at room temperature, mixing polyaryletherketone with 98% concentrated sulfuric acid and one of chloromethyl ether, chloromethyl ethyl ether, 1, 4-dichloromethoxybutane, trimethylchlorosilane and chloromethyl octyl ether, firstly carrying out ultrasonic reaction for 1-5 h at the ultrasonic frequency of 100-300 kHz, then heating to 40-100 ℃, continuing the ultrasonic reaction for 3-24 h to obtain polyaryletherketone with chloromethyl side group, separating out and drying to obtain the polyaryletherketone with chloromethyl side group,
wherein, the polyaryletherketone: 98% concentrated sulfuric acid: chloromethyl group-containing material =1g/5ml/5g to 1g/100ml/100g.
Preferably, the functionalized polyaryletherketone is dissolved in an organic solvent, and the mixture is uniformly stirred to prepare a homogeneous casting solution; and casting the casting solution on a flat plate to form a liquid film, and then soaking the liquid film in a coagulating bath to obtain the polyaryletherketone-based porous polymer film.
Further, according to the mass fraction of 8-30%, dissolving the functionalized polyaryletherketone in an organic solvent, stirring for 4-12 h at 25-100 ℃, centrifuging by a high-speed centrifuge to remove impurities, wherein the centrifugation speed is 3000-12000 rmp, the centrifugation time is 5-60 min, and then defoaming treatment is carried out at room temperature by using a vacuum drying oven, the vacuum degree is-0.2-0.8 bar, and the defoaming time is 5-60 min; casting the casting solution on a flat plate to form a liquid film with the thickness of 10-800 mu m, dipping the flat plate with the liquid film in a coagulating bath at the temperature of 20-80 ℃ to form a film,
wherein the flat plate is one of a glass plate, a polytetrafluoroethylene flat plate, a nylon flat plate and a polyvinylidene fluoride flat plate; the organic solvent is one of N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF) and N-vinyl pyrrolidone (NVP); the coagulating bath is one of deionized water, methanol, ethanol, glycerol, isopropanol, ethylene glycol, n-butanol, and acetone.
Preferably, the pore filler is uniformly mixed with deionized water to prepare a pore filler solution with the mass fraction of 5-50%; the polyaryletherketone group porous polymer membrane is arranged in a nanofiltration device, a pore filler solution is taken as a circulating liquid, and the circulation is carried out for 1 to 5 hours under 0.1 to 0.6MPa, so that the pore filler fully enters into the pore structure of the membrane.
Wherein the pore filler is one of polyvinylpyrrolidone (PVP-K30, PVP-K60, PVP-K90), polyethylene glycol (PEG-1000, PEG-2000, PEG-3000), polyethyleneimine (PEI), polyvinyl butyral (PVB), tributyl phosphate, ammonium nitrate and ammonium bicarbonate.
Preferably, the filled polyaryletherketone-based porous polymer membrane is ultrasonically cleaned by deionized water; the concentration is 5X 10 -5 ～5×10 -3 mixing the initiator solution in mol/l with the densification monomer to obtain a mixed solution containing the densification monomer with the mass volume fraction of 1-15% w/v, and introducing high-purity argon gas into the mixed solution for 1-60 min; and then putting the cleaned porous polymer film into the mixed solution, stirring and reacting for 1-6 h at 40-100 ℃, introducing high-purity argon for protection all the time in the whole process, and washing the obtained grafted film with deionized water to remove unreacted densification monomers on the surface of the film, thereby obtaining the polyaryletherketone-based porous polymer grafted film.
Further, the obtained polyaryletherketone-based porous polymer grafted membrane is placed in a vacuum drying oven, dried for 1-12 h at the temperature of 40-120 ℃, then placed in a tubular carbonization furnace, heated to 600-1000 ℃ from room temperature at the heating rate of 5-20 ℃/min in high-purity nitrogen at the gas flow rate of 100-1000 ml/min, kept at the constant temperature for 1-10 h, and finally naturally cooled to room temperature to complete carbonization, so that the polyaryletherketone-based porous carbon membrane is obtained.
Compared with the prior art, the invention has the beneficial effects that:
in the preparation process of the high-flux polyaryletherketone-based carbon membrane, large-volume side groups are introduced into the polyaryletherketone structure, and the porous polyaryletherketone-based polymer membrane is pre-filled with a pore structure, so that the problems of pore structure fusion and integral densification of the porous polyaryletherketone-based polymer membrane in a high-temperature heat treatment process are effectively solved, and the polyaryletherketone-based high-flux carbon membrane with high flux and good pore structure maintenance is prepared. The polyaryletherketone-based high-flux carbon membrane shows high gas permeation flux because the polyaryletherketone-based high-flux carbon membrane well maintains a porous structure of a polymer membrane stage, a polymer membrane framework is converted into an amorphous carbon structure in a pyrolysis carbonization process, and the controlled densification of the membrane surface ensures that the prepared porous carbon membrane maintains higher selectivity. The method is simple, easy to control and amplify, and has wide application prospect and commercial value.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but will not limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
A preparation method of a high-flux polyaryletherketone-based carbon membrane comprises the following steps:
s1, preparing functionalized polyaryletherketone
(1) Preparing sulfonic acid side group polyaryletherketone: mixing polyaryletherketone and a substance containing sulfonic acid groups for reaction, inserting an ultrasonic vibration rod into a reaction solution at room temperature for ultrasonic reaction for a period of time, heating to a certain temperature, and continuing the ultrasonic reaction for a period of time to obtain a reaction solution. And then adding the reaction solution into deionized water for precipitation, soaking the precipitate in the deionized water for a period of time, washing to neutrality, putting the precipitate into a vacuum drying oven, and drying at a certain temperature for a period of time to obtain the polyaryletherketone containing the sulfonic acid side group.
(2) Preparing chloromethyl side group polyaryletherketone: mixing polyaryletherketone with 98% concentrated sulfuric acid and a substance containing chloromethyl groups for reaction, inserting an ultrasonic vibration rod into the reaction solution at room temperature for ultrasonic reaction for a period of time, heating to a certain temperature, and continuing the ultrasonic reaction for a period of time to obtain a reaction solution. And then adding the reaction solution into deionized water for precipitation, putting the precipitate into the deionized water again for soaking for a period of time, washing to be neutral, putting into a vacuum drying oven, and drying for a period of time at a certain temperature to obtain the polyaryletherketone containing chloromethyl side groups.
S2, preparing a homogeneous phase casting solution
And (2) adding the functionalized polyaryletherketone obtained in the step (S1) into an organic solvent according to a certain mass ratio, and heating and stirring for a certain time to obtain a membrane casting solution. And (3) placing the membrane casting solution into a centrifuge for centrifuging to remove impurities and insoluble substances, then placing the membrane casting solution into a vacuum drying oven, and defoaming the membrane casting solution at room temperature for a period of time to obtain the homogeneous membrane casting solution.
S3, preparing the polyaryletherketone-based porous polymer membrane
And (3) casting the casting solution obtained in the step (S2) on a flat plate to form a liquid film with a certain thickness, dipping the flat plate with the liquid film in a coagulating bath at a certain temperature, and after the liquid film is coagulated, removing the coagulated porous polymer film from the flat plate to obtain the polyaryletherketone-based porous polymer film.
S4, pre-filling treatment of polyaryletherketone group porous polymer membrane pore structure
And uniformly mixing the pore filler with deionized water according to a certain mass ratio to prepare a pore filler solution. And (3) installing the polyaryletherketone-based porous polymer membrane obtained in the step (S3) in a nanofiltration device, and circulating for a period of time under a certain pressure by taking a pore filler solution as a circulating liquid so that the pore filler fully enters a pore structure of the membrane.
S5, controlled densification of polyaryletherketone-based porous polymer film surface
Ultrasonically cleaning the filled polyaryletherketone porous polymer film with deionized water for a period of time; simultaneously preparing an initiator solution with a certain molar concentration, adding a certain amount of densification monomers into the initiator solution to obtain a mixed solution containing densification monomers with a certain mass volume fraction, and introducing high-purity argon gas into the mixed solution for a period of time; and then, putting the cleaned porous polymer film into the mixed solution, stirring and reacting for a period of time at a certain temperature, introducing high-purity argon gas for protection all the time in the whole process, and washing the obtained grafted film with deionized water to remove unreacted densified monomers on the surface of the film, thereby obtaining the polyaryletherketone-based porous polymer grafted film.
S6, drying and carbonizing the polyaryletherketone group porous polymer grafted film
And (4) placing the polyaryletherketone group porous polymer grafted membrane obtained in the step (S5) in a vacuum drying oven, drying for a period of time at a certain temperature, then placing in a tubular carbonization furnace, carbonizing in high-purity nitrogen at a certain gas flow by adopting a certain temperature rise program, and naturally cooling to room temperature after the reaction is finished to obtain the polyaryletherketone group porous carbon membrane.
In the above technical solution, in the step S1 (1), the polyaryletherketone and the substance containing sulfonic acid group are mixed and reacted, and the substance containing sulfonic acid group is one of 98% concentrated sulfuric acid, sulfur trioxide, chlorosulfonic acid, a complex of sulfur trioxide and triethyl phosphate, and hydroxysulfonic acid.
In the technical scheme, an ultrasonic vibrating bar is inserted into the reaction liquid at room temperature in the step S1 (1) for ultrasonic reaction for a period of time, the ultrasonic frequency is 100-300 kHz, and the reaction time is 1-5 h.
In the technical scheme, after the heating in the step S1 (1) is carried out to a certain temperature, the ultrasonic reaction is continued for a period of time, the temperature is 40-100 ℃, and the reaction time is 3-24 hours.
In the above technical solution, the reaction solution in step S1 (1) is polyaryletherketone: liquid sulfonic group-containing substance =1g/5ml to 1g/100ml, polyaryletherketone: the solid sulfonic acid group-containing substance =1g/5g to 1g/100g.
In the technical scheme, the precipitate in the step S1 (1) is soaked in deionized water for a period of time of 12-24 hours.
In the technical scheme, the polyaryletherketone polymer containing the sulfonic acid side group in the step S1 (1) is dried in a vacuum drying oven at the drying temperature of 40-120 ℃ for 12-24 h.
In the above technical solution, in the step S1 (2), the polyaryletherketone, 98% concentrated sulfuric acid and a material containing chloromethyl group are mixed and reacted, and the material containing chloromethyl group is one of chloromethyl ether, chloromethyl ethyl ether, 1, 4-dichloromethoxybutane, trimethylchlorosilane and chloromethyl octyl ether.
In the technical scheme, an ultrasonic vibrating bar is inserted into the reaction liquid at room temperature in the step S1 (2) for ultrasonic reaction for a period of time, the ultrasonic frequency is 100-300 kHz, and the reaction time is 1-5 h.
In the technical scheme, after the heating in the step S1 (2) is carried out to a certain temperature, the ultrasonic reaction is continued for a period of time, the temperature is 40-100 ℃, and the reaction time is 3-24 hours.
In the above technical scheme, the reaction solution in step S1 (2) is polyaryletherketone: 98% concentrated sulfuric acid: chloromethyl group-containing material =1g/5ml/5g to 1g/100ml/100g.
In the technical scheme, the precipitate in the step S1 (2) is soaked in deionized water for a period of time of 12-24 hours.
In the technical scheme, the polyaryletherketone containing chloromethyl side groups in step S1 (2) is dried in a vacuum drying oven at 40-120 ℃ for 12-24 h.
In the above technical scheme, the casting solution in step S2 is mixed by mass ratio, and the mass fraction of the functionalized polyaryletherketone is 8-30%.
In the above technical solution, the organic solvent in step S2 is one of N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), and N-vinyl pyrrolidone (NVP).
In the above technical scheme, the homogeneous casting solution is obtained by heating and stirring for a certain time in step S2, the heating temperature is 25-100 ℃, and the stirring time is 4-12 hours.
In the technical scheme, the homogeneous casting solution in the step S2 can be used after impurities are removed by centrifugation through a high-speed centrifuge, the centrifugation speed is 3000-12000 rmp, and the centrifugation time is 5-60 min.
In the above technical scheme, the homogeneous casting solution in step S2 is subjected to defoaming treatment in a vacuum drying oven at room temperature before use, wherein the vacuum degree is-0.2 to-0.8 bar, and the defoaming time is 5 to 60min.
In the above technical solution, the casting solution obtained in step S2 is cast on a flat plate to form a liquid film with a certain thickness in step S3, the flat plate is one of a glass plate, a polytetrafluoroethylene flat plate, a nylon flat plate and a polyvinylidene fluoride flat plate, and the thickness of the liquid film is 10-800 μm.
In the above technical scheme, the flat plate with the liquid film in step S3 is dipped in a coagulation bath at a certain temperature to form a film, the coagulation bath is one of deionized water, methanol, ethanol, glycerol, isopropanol, ethylene glycol, n-butanol and acetone, and the temperature of the coagulation bath is 20-80 ℃.
In the above technical solution, the pore filler solution described in step S4 is obtained by uniformly mixing a pore filler with deionized water according to a certain mass ratio, the pore filler used is one of polyvinylpyrrolidone (PVP-K30, PVP-K60, PVP-K90), polyethylene glycol (PEG-1000, PEG-2000, PEG-3000), polyethyleneimine (PEI), polyvinyl butyral (PVB), tributyl phosphate, ammonium nitrate, and ammonium bicarbonate, and the mass fraction of the pore filler in the pore filler solution is 5 to 50%.
In the technical scheme, the polyaryletherketone group porous polymer membrane in the step S4 is arranged in a nanofiltration device, and a pore filler solution is used as a circulating liquid to circulate for a period of time under a certain pressure, wherein the pressure is 0.1-0.6 MPa, and the circulating time is 1-5 h.
In the above technical solution, the polyaryletherketone based porous polymer film filled in step S5 is ultrasonically cleaned with deionized water for a period of time, the ultrasonic frequency is 100-500 kHz, and the cleaning time is 1-60 min.
In the above technical solution, the initiator solution with a certain molar concentration prepared in step S5 is added with a certain amount of densification monomer to obtain a mixed solution, the initiator used is one of cerium ammonium nitrate, azobisisobutyronitrile, benzoyl peroxide and ammonium persulfate, and the densification monomer used is one of 2-methacryloyloxyethyl phosphorylcholine, methyl methacrylate, butyl acrylate, acrylic acid and dimethylamino ethyl methacrylate.
In the above technical solution, the configuration described in step S5Mixing the solution, introducing high-purity argon gas for a period of time, mixing the solution, and adding 5X 10 -5 ～5×10 -3 mixing the initiator solution in mol/l with the densification monomer to form a mixed solution containing the densification monomer in a mass volume fraction of 1-15% w/v, and introducing high-purity argon gas for a period of 1-60 min.
In the above technical scheme, the polymer film in step S5 is put into the mixed solution, and stirred and reacted for a period of time at a certain temperature, wherein the temperature is 40-100 ℃, and the reaction time is 1-6 h.
In the technical scheme, the polymer grafted membrane in the step S6 is placed in a vacuum drying oven and dried for a period of time at a certain temperature of 40-120 ℃ for 1-12 h.
In the above technical scheme, the dried polymer graft membrane in the step S6 is placed in a tubular carbonization furnace, and high-purity nitrogen gas with a certain gas flow rate is introduced, wherein the gas flow rate is 100-1000 ml/min.
In the above technical solution, the step S6 employs a certain temperature-raising program for carbonization, and the temperature-raising program is: raising the temperature from the room temperature to 600-1000 ℃ at the heating rate of 5-20 ℃/min, keeping the temperature for 1-10 h, and finally naturally cooling to the room temperature.
Example 1
S1, preparing functionalized polyaryletherketone
Preparing sulfonic acid side group polyaryletherketone: mixing polyaryletherketone and chlorosulfonic acid according to a proportion of 1g. And then adding the reaction solution into deionized water for precipitation, soaking the precipitate into the deionized water again for 24 hours, washing to be neutral, then placing the precipitate into a vacuum drying oven, and drying at 120 ℃ for 12 hours to obtain the polyaryletherketone containing the sulfonic acid side group.
S2, preparing a homogeneous phase casting solution
And (2) adding the functionalized polyaryletherketone obtained in the step (S1) into N-vinyl pyrrolidone (NVP) according to a certain mass ratio, and heating and stirring at 50 ℃ for 6 hours to obtain a casting solution with the mass fraction of 30%. And then, putting the membrane casting solution into a centrifuge, centrifuging for 5min at a centrifugal speed of 12000rmp, then putting into a vacuum drying oven, and defoaming for 5min at room temperature in a vacuum degree of-0.8 bar to obtain a homogeneous membrane casting solution.
S3, preparing the polyaryletherketone-based porous polymer membrane
And (3) casting the casting solution obtained in the step (S2) on a glass plate to form a liquid film with the thickness of 800 microns, soaking the glass plate with the liquid film in ethylene glycol at 80 ℃, and after the liquid film is solidified, removing the solidified porous polymer film from the glass plate to obtain the polyaryletherketone-based porous polymer film.
S4, pre-filling treatment of polyaryletherketone group porous polymer membrane pore structure
Uniformly mixing ammonium nitrate and deionized water according to a certain mass ratio to prepare an ammonium nitrate pore filler solution with the mass fraction of 50%. And (3) installing the polyaryletherketone-based porous polymer membrane obtained in the step (S3) in a nanofiltration device, and circulating the solution of ammonium nitrate serving as circulating liquid under the pressure of 0.6MPa for 1 hour to ensure that the ammonium nitrate fully enters the pore structure of the membrane.
S5, controlled densification of polyaryletherketone-based porous polymer film surface
Ultrasonically cleaning the filled polyaryletherketone-based porous polymer film with deionized water, and cleaning for 1min at the ultrasonic frequency of 500 kHz; at the same time, the molar concentration of the mixture is 5 multiplied by 10 -3 Adding methyl methacrylate to a mol/l aqueous benzoyl peroxide solution to obtain a mixed solution containing 15% w/v by mass volume of methyl methacrylate, and introducing high-purity argon gas for 60min into the mixed solution; and then putting the cleaned porous polymer film into the mixed solution, stirring and reacting for 1h at 100 ℃, introducing high-purity argon for protection all the time in the whole process, and washing the obtained grafted film with deionized water to remove unreacted methyl methacrylate on the surface of the film, thereby obtaining the polyaryletherketone-based porous polymer grafted film.
S6, drying and carbonizing the polyaryletherketone group porous polymer grafted film
And (3) placing the porous polymer grafted membrane obtained in the step (S5) in a vacuum drying oven, drying at 120 ℃ for 1h, and then placing in a tubular carbonization furnace, wherein high-purity nitrogen with the gas flow rate of 1000ml/min is used as a pyrolysis atmosphere. And heating the temperature from room temperature to 1000 ℃ at the heating rate of 20 ℃/min, keeping the temperature for 1h, and naturally cooling to room temperature to obtain the polyaryletherketone-based porous carbon membrane. The permeability properties of the membrane are shown in table 1.
Example 2:
s1, preparing functionalized polyaryletherketone
Preparing chloromethyl side group polyaryletherketone: mixing polyaryletherketone, 98% concentrated sulfuric acid and chloromethyl octyl ether according to the proportion of 1g 100ml for reaction, inserting an ultrasonic vibration rod into the reaction solution at room temperature, wherein the ultrasonic frequency is 100kHz, reacting for 5h, heating to 40 ℃, and continuing to perform ultrasonic reaction for 24h to obtain the reaction solution. And then adding the reaction solution into deionized water for precipitation, soaking the precipitate into the deionized water again for 24 hours, washing to be neutral, then placing the precipitate into a vacuum drying oven, and drying at 50 ℃ for 24 hours to obtain the polyaryletherketone containing chloromethyl side groups.
S2, preparing homogeneous casting solution
And (2) adding the functionalized polyaryletherketone obtained in the step (S1) into N, N-Dimethylformamide (DMF) according to a certain mass ratio, and stirring at 25 ℃ for 12 hours to obtain a casting solution with the mass fraction of 8%. And then, putting the casting solution into a centrifuge, centrifuging for 60min at a centrifugal speed of 3000rmp, then putting into a vacuum drying oven, and defoaming for 60min at room temperature under a vacuum degree of-0.8 bar to obtain a homogeneous casting solution.
S3, preparing the polyaryletherketone-based porous polymer membrane
And (3) casting the casting solution obtained in the step (S2) on a glass plate to form a liquid film with the thickness of 100 microns, soaking the glass plate with the liquid film in acetone at the temperature of 20 ℃, and after the liquid film is solidified, removing the solidified porous polymer film from the glass plate to obtain the polyaryletherketone-based porous polymer film.
S4, pre-filling treatment of polyaryletherketone group porous polymer membrane pore structure
Uniformly mixing Polyethyleneimine (PEI) and deionized water according to a certain mass ratio to prepare a Polyethyleneimine (PEI) pore filler solution with the mass fraction of 5%. And (3) installing the polyaryletherketone-based porous polymer membrane obtained in the step (S3) in a nanofiltration device, and circulating for 5 hours under the pressure of 0.1MPa by taking the Polyethyleneimine (PEI) solution as a circulating liquid, so that the Polyethyleneimine (PEI) fully enters into a pore structure of the membrane.
S5, controlled densification of polyaryletherketone-based porous polymer film surface
Ultrasonically cleaning the filled polyaryletherketone-based porous polymer film for 60min by using deionized water, wherein the ultrasonic frequency is 100 kHz; at the same time, the molar concentration of the mixture is 5 multiplied by 10 -3 Adding 2-methacryloyloxyethyl phosphorylcholine to an aqueous solution of ammonium persulfate in mol/l to obtain a mixed solution containing 15% w/v by mass of 2-methacryloyloxyethyl phosphorylcholine, and introducing high-purity argon gas for 60min into the mixed solution; and then, putting the cleaned porous polymer film into the mixed solution, stirring and reacting for 6 hours at 40 ℃, introducing high-purity argon for protection all the time in the whole process, and washing the obtained grafted film with deionized water to remove unreacted 2-methacryloyloxyethyl phosphorylcholine on the surface of the film, thereby obtaining the polyaryletherketone-based porous polymer grafted film.
S6, drying and carbonizing the polyaryletherketone-based porous polymer grafted film
And (3) placing the porous polymer grafted membrane obtained in the step (S5) in a vacuum drying oven, drying at 40 ℃ for 12 hours, and then placing in a tubular carbonization furnace, wherein high-purity nitrogen with the gas flow rate of 100ml/min is used as a pyrolysis atmosphere. And heating the temperature from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 10h, and naturally cooling to room temperature to obtain the polyaryletherketone-based porous carbon membrane. The permeability properties of the membrane are shown in table 1.
Comparative example 1:
the experimental procedure of example 1 was followed, except that the step S1 of functionalizing process and the step S4 of pre-filling the pore structure of the polymer membrane were not performed, to prepare a PAEK-based carbon membrane, unlike example 1. The permeability properties of the membrane are shown in table 1.
Comparative example 2:
the experimental procedure of example 1 was carried out in the same manner as in example 1 except that the polyaryletherketone-based porous carbon film was prepared without the functionalization process of step S1. The permeability properties of the membrane are shown in table 1.
TABLE 1
Examples 3 to 7:
the experimental procedure of example 1 was followed, except that in step S1 of example 1, the functionalized polyaryletherketone was mixed with 98% concentrated sulfuric acid, chlorosulfonic acid, sulfur trioxide and triethyl phosphate complex at a ratio of 1g to 100ml, and mixed with 1g of sulfur trioxide and hydroxysulfonic acid at a ratio of 1g to 100100g, respectively, to react. The permeability of the polyaryletherketone-based porous carbon membrane is shown in Table 2.
Examples 8 to 12:
following the experimental procedure of example 2, the difference from step S1 of example 2 is that functionalized polyaryletherketone, 98% concentrated sulfuric acid were mixed with 1, 4-dichloromethoxybutane, chloromethyl ether, chloromethyl ethyl ether, trimethylchlorosilane, chloromethyl octyl ether in a ratio of 1g:100ml: the reaction was mixed at a ratio of 100g. The permeability of the polyaryletherketone-based porous carbon membrane is shown in Table 2.
TABLE 2
Examples 13 to 15
According to the experimental method of example 1, the difference from step S2 in example 1 is that sulfonic acid side group polyaryletherketone is added to N-methylpyrrolidone (NMP) organic solvent according to different mass ratios, respectively, to obtain homogeneous casting solutions with mass fractions of 10%, 20% and 30%. The permeability of the polyaryletherketone-based porous carbon membrane is shown in Table 3.
Examples 16 to 18
According to the experimental method of example 2, the difference from step S2 of example 2 is that chloromethyl side group polyaryletherketone is added to N-methylpyrrolidone (NMP) organic solvent according to different mass ratios, respectively, to obtain homogeneous casting solution with mass fractions of 10%, 20% and 30%. The permeability of the polyaryletherketone-based porous carbon membrane is shown in Table 3.
TABLE 3
Examples 19 to 22:
according to the experimental method of the example 1, the difference from the step S2 in the example 1 is that sulfonic acid side group polyaryletherketone is added into N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF) and N-vinylpyrrolidone (NVP) according to a certain mass ratio to obtain a homogeneous casting solution with a mass fraction of 30%. The permeability of the polyaryletherketone-based porous carbon membrane is shown in Table 4.
Examples 23 to 26
According to the experimental method of example 2, the difference from step S2 in example 2 is that chloromethyl side group polyaryletherketone is added to N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), and N-vinylpyrrolidone (NVP) at a certain mass ratio, respectively, to obtain a homogeneous casting solution with a mass fraction of 30%. The permeability of the polyaryletherketone-based porous carbon membrane is shown in Table 4.
TABLE 4
Comparative example 3
The experimental procedure of example 1 was followed, except that no pre-filling treatment of the pore structure of the polymer membrane of step S4 was performed, to prepare a polyaryletherketone-based porous carbon membrane, unlike example 1. The permeability properties of the membrane are shown in table 5.
Examples 27 to 33:
according to the experimental method of example 1, the difference from step S4 in example 1 is that polyethylene glycol (PEG-1000), polyvinylpyrrolidone (PVP-K60), polyethyleneimine (PEI), polyvinyl butyral (PVB), tributyl phosphate (TBP) and deionized water are mixed according to a certain mass ratio, so as to prepare a pore filler solution with a mass fraction of 5%; respectively mixing ammonium nitrate, ammonium bicarbonate and deionized water according to a certain mass ratio to prepare a pore filler solution with the mass fraction of 50%. The permeability of the polyaryletherketone-based porous carbon membrane is shown in Table 5.
TABLE 5
Comparative example 4
The experimental procedure of example 2 was followed, except that the step S4 of pre-filling the pore structure of the polymer membrane was not performed, to prepare a PAEK-based porous carbon membrane, in contrast to example 2. The permeability properties of the membrane are shown in table 6.
Examples 34 to 40:
according to the experimental method of the embodiment 2, the difference from the step S4 in the embodiment 2 is that polyethylene glycol (PEG-1000), polyvinylpyrrolidone (PVP-K60), polyethyleneimine (PEI), polyvinyl butyral (PVB), tributyl phosphate (TBP) and deionized water are mixed according to a certain mass ratio, so as to prepare a pore filler solution with a mass fraction of 5%; respectively mixing ammonium nitrate, ammonium bicarbonate and deionized water according to a certain mass ratio to prepare a pore filler solution with the mass fraction of 50%. The permeability of the polyaryletherketone-based porous carbon membrane is shown in Table 6.
TABLE 6
Claims (9)
1. A preparation method of a high-flux polyaryletherketone-based carbon membrane is characterized by comprising the following steps: introducing a bulky side group into a polyaryletherketone polymer structure to obtain functionalized polyaryletherketone; preparing a polyaryletherketone-based porous polymer film by using the obtained functionalized polyaryletherketone; pre-filling a pore structure of the polyaryletherketone-based porous polymer membrane in a pore filler solution; under the action of an initiator, grafting and polymerizing a densifying monomer on the surface of the porous polymer film; drying and carbonizing the porous polymer film with the surface controlled to be densified to obtain the high-flux polyaryletherketone-based carbon film,
wherein, the bulky side group is one of hydroxyl, carboxyl, sulfonic group, chloromethyl, allyl, pyridyl and quaternary ammonium salt group.
2. The method of claim 1, wherein: the densification monomer is one of 2-methacryloyloxyethyl phosphorylcholine, methyl methacrylate, butyl acrylate, acrylic acid and dimethylamino ethyl methacrylate.
3. The method of claim 1, wherein: the method for introducing the bulky side group into the polyaryletherketone polymer structure comprises the following steps: mixing polyaryletherketone with one of 98% concentrated sulfuric acid, sulfur trioxide, chlorosulfonic acid, sulfur trioxide, triethyl phosphate complex and hydroxysulfonic acid at room temperature, firstly carrying out ultrasonic reaction for 1-5 h at the ultrasonic frequency of 100-300 kHz, heating to 40-100 ℃, then continuing the ultrasonic reaction for 3-24 h to obtain polyaryletherketone with sulfonic acid side groups, precipitating and drying to obtain the polyaryletherketone with sulfonic acid side groups,
wherein, the polyaryletherketone: the proportion of the liquid substance containing sulfonic acid group is 1g/5 ml-1 g/100ml; polyaryletherketone: the proportion of the solid substance containing sulfonic acid groups is 1g/5 g-1 g/100g.
4. The method of claim 1, wherein: mixing polyaryletherketone with 98 percent concentrated sulfuric acid and one of chloromethyl ether, chloromethyl ethyl ether, 1, 4-dichloromethoxybutane, trimethylchlorosilane and chloromethyl octyl ether at room temperature, carrying out ultrasonic reaction for 1-5 h at the ultrasonic frequency of 100-300 kHz, heating to 40-100 ℃, continuing the ultrasonic reaction for 3-24 h to obtain chloromethyl side group polyaryletherketone, separating out and drying to obtain the polyaryletherketone,
wherein, the polyaryletherketone: 98% concentrated sulfuric acid: chloromethyl group-containing material =1g/5ml/5g to 1g/100ml/100g.
5. The method of claim 1, wherein: dissolving functional polyaryletherketone into an organic solvent, and uniformly stirring to prepare a homogeneous membrane casting solution; and casting the casting solution on a flat plate to form a liquid film, and then soaking the liquid film in a coagulating bath to obtain the polyaryletherketone-based porous polymer film.
6. The method of claim 5, wherein: dissolving the functionalized polyaryletherketone in an organic solvent according to the mass fraction of 8-30%, stirring for 4-12 h at 25-100 ℃, centrifuging by a high-speed centrifuge to remove impurities, wherein the centrifugation speed is 3000-12000 rmp, and the centrifugation time is 5-60 min; then, defoaming at room temperature by using a vacuum drying oven, wherein the vacuum degree is-0.2 to-0.8 bar, and the defoaming time is 5 to 60min; casting the casting solution on a flat plate to form a liquid film with the thickness of 10-800 mu m, dipping the flat plate with the liquid film in a coagulating bath at the temperature of 20-80 ℃ to form a film,
wherein the flat plate is one of a glass plate, a polytetrafluoroethylene flat plate, a nylon flat plate and a polyvinylidene fluoride flat plate; the organic solvent is one of N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF) and N-vinyl pyrrolidone (NVP); the coagulating bath is one of deionized water, methanol, ethanol, glycerol, isopropanol, ethylene glycol, n-butanol, and acetone.
7. The method of claim 1, wherein: uniformly mixing the pore filler with deionized water to prepare a pore filler solution with the mass fraction of 5-50%; installing the polyaryletherketone-based porous polymer membrane in a nanofiltration device, taking a pore filler solution as circulating liquid, circulating for 1-5 h under 0.1-0.6 MPa to ensure that the pore filler fully enters into a pore structure of the membrane,
the pore filler is one of polyvinylpyrrolidone (PVP-K30, PVP-K60 and PVP-K90), polyethylene glycol (PEG-1000, PEG-2000 and PEG-3000), polyethyleneimine (PEI), polyvinyl butyral (PVB), tributyl phosphate, ammonium nitrate and ammonium bicarbonate.
8. The method of claim 1, wherein: ultrasonically cleaning the filled polyaryletherketone-based porous polymer film by using deionized water; at a concentration of 5X 10 -5 ～5×10 -3 mixing the initiator solution in mol/l with the densification monomer to obtain a mixed solution containing the densification monomer with the mass volume fraction of 1-15% w/v, and introducing high-purity argon gas into the mixed solution for 1-60 min; and then, putting the cleaned porous polymer film into the mixed solution, stirring and reacting for 1-6 h at 40-100 ℃, introducing high-purity argon for protection all the time in the whole process, and washing the obtained grafted film with deionized water to remove unreacted densification monomers on the surface of the film, thereby obtaining the polyaryletherketone-based porous polymer grafted film.
9. The method of claim 8, wherein: and (3) placing the obtained polyaryletherketone-based porous polymer grafted membrane in a vacuum drying oven, drying at 40-120 ℃ for 1-12 h, then placing in a tubular carbonization furnace, heating from room temperature to 600-1000 ℃ at the heating rate of 5-20 ℃/min in high-purity nitrogen with the gas flow of 100-1000 ml/min, keeping the temperature for 1-10 h, and finally naturally cooling to room temperature to finish carbonization to obtain the polyaryletherketone-based porous carbon membrane.
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