CN114870638B - Polyaniline/polyaryletherketone composite membrane with electrochemical response, preparation method and application thereof - Google Patents
Polyaniline/polyaryletherketone composite membrane with electrochemical response, preparation method and application thereof Download PDFInfo
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Abstract
An electrochemical-response polyaniline/polyaryletherketone composite membrane, a preparation method and application thereof belong to the technical field of surface modification and preparation of polymer membranes. The PANI/PAEK porous membrane is prepared integrally, and the PANI in-situ growth realizes the regulation and control of the PAEK surface micro-nano structure. The preparation process is simple and efficient, and the regulation and control of the PANI micro-nano structure on the surface of the membrane are realized. The invention fully utilizes the oxidability and surface aggregation of inorganic particles, and realizes the enrichment and uniform growth of PANI on the surface of the inorganic particles. Meanwhile, the surface PANI realizes that the bottom PAEK is uniformly covered on the surface micro-nano structure and the hydrophilicity of the membrane is increased. The method fully integrates the characteristics of PANI conductivity and surface enrichment, and has potential development space and application in the fields of membrane separation, oil-water separation, photocatalytic separation, electrified separation materials, pH response, electrified response and the like.
Description
Technical Field
The invention belongs to the technical field of surface modification and preparation of polymer films, and particularly relates to a polyaniline/polyaryletherketone composite film with electrochemical response, a preparation method and application thereof.
Background
The membrane separation technology is a high-efficiency and energy-saving separation method and has wide application in the fields of water treatment, food, medicine, environmental protection, chemical industry, metallurgy and the like. With the development of industry, the separation membrane needs to have the advantages of hydrophilicity, solvent resistance, simple preparation and the like. As a typical special engineering plastic, the Polyaryletherketone (PAEK) material has excellent thermal stability and good mechanical properties. Meanwhile, the membrane has good solvent resistance, and is widely applied to the field of membrane separation. However, PAEK materials are difficult to process in solution, and therefore, the properties of the PAEK materials in the field of separation membranes are limited, and the surfaces of the PAEK materials are difficult to attach to other materials due to the problems of low surface hydrophobicity, low functional group activity and the like.
Polyaniline (PANI) as a hydrophilic polymer rich in N has remarkable application in the field of membrane separation, and has remarkable influence effect on reducing membrane pollution. The unique doping and dedoping properties of polyaniline provide a new opportunity for the improvement of permselective properties of separation membranes. The pore structure of the polyaniline film can be changed by different doping degrees, so that the separation performance is changed. The former generally employs physical blending or polymerization of aniline monomer addition to prepare PANI-based separation membranes. But PANI has high rigidity and is easy to agglomerate, and can not be modified on the surfaces of other materials. Most of the innovative separation membrane modification researches reported at present increase the preparation steps of the separation membrane and increase the production cost.
The invention provides a simple and efficient one-step method for preparing a polyaniline/polyaryletherketone (PANI/PAEK) membrane by taking a polyaryletheramine membrane as a template. The invention breaks through the physical blending and chemical post-addition modification modes by adopting a post-treatment mode, and regulates and controls the microscopic morphology of the membrane surface by adopting a brand new PANI in-situ growth mode. The PANI/PAEK membrane prepared by the invention has obvious application prospect in the fields of membrane separation, electrification separation, pH response, electrification response and the like.
Disclosure of Invention
The invention aims at providing a polyaniline/polyaryletherketone composite membrane with electrochemical response, a preparation method and application thereof, aiming at overcoming the defects of the prior art.
The invention relates to a preparation method of a polyaniline/polyaryletherketone composite membrane with electrochemical response, which comprises the following specific steps:
1) A preparation method of polyaniline/polyaryletherketone composite membrane with electrochemical response adopts a one-step method to convert polyaryletheramine (PAEKt) membrane into PANI/PAEK membrane, the structure of the special polyaryletheramine resin is shown as the following formula,
n is a positive integer representing the degree of polymerization, wherein a, b, X, Y is a positive integer and Y is greater than or equal to 1;
adding polyaryletheramine (PAEKt), a pore-forming agent and inorganic nano particles into an organic solution, and stirring until the PAEKt is completely dissolved to prepare PAEKt casting solution; in the PAEKt casting solution, the mass fraction of the PAEKt resin is 10% -25%; the pore-forming agent is one or more of polyvinylpyrrolidone, polyethylene glycol and acetone, and the mass fraction is 1% -15%; the inorganic nanoparticle is graphene oxide, metal Organic Framework (MOF) and TiO 2 One or more of covalent organic framework materials (COF) with mass fraction of 0-4%; the organic solvent is one or more of N-methyl pyrrolidone, dimethylformamide, dimethylacetamide, chloroform and tetrahydrofuran;
2) Preparing a PAEK t porous membrane: pouring the PEAKt casting solution obtained in the step 1) on a clean glass plate by using a solution phase separation method, scraping a film by using a scraper with the thickness of 100-300 mu m, volatilizing for 5-60 s, and then placing the film into a coagulating bath, wherein the coagulating bath is one or more of ultrapure water, ethanol and hydrochloric acid, and preparing the PAEKt porous film on the glass plate; or using electrostatic spinning technology to spin PEAKt casting solution obtained in step 1) in a syringe, the distance from the spinneret of the syringe to the bottom plate is 10-20 cm, the spinning voltage is 10-25 KV, and the flow rate of the casting solution is 0.3-1.0 mL.h -1 Spinning for 20-120 min to prepare PAEKt nanofiber membrane on the bottom plate;
3) The PANI/PAEK porous composite membrane is prepared by adopting a heterogeneous hydrolysis and oxidative coupling synergistic method: preparing acid solutions of different oxidants, wherein the oxidants are one or more of hydrogen peroxide, ammonium persulfate, potassium dichromate and ferric chloride, the acids are one or more of hydrochloric acid, sulfuric acid, phytic acid, sulfosalicylic acid, benzenesulfonic acid, acetic acid and p-toluenesulfonic acid, the acid concentration is 0.1-6.0M, and the oxidant concentration is 0.037-0.6M; adding the PAEKt porous membrane or PAEKt nanofiber membrane obtained in the step 2) into an acid solution containing an oxidant, and putting the acid solution into a reaction kettle to react at 20-80 ℃ for 1-10 h, wherein the dosage ratio of the PAEKt porous membrane (PAEKt) or PAEKt nanofiber membrane to the acid solution containing the oxidant is 0.1g: 5-160 mL; and finally, respectively cleaning the obtained membrane with ethanol and water for 3-5 times, and drying at 50-80 ℃ to obtain the polyaniline/polyaryletherketone composite membrane with electrochemical response.
Compared with the prior art, the invention has the following innovation and advantages:
the PANI/PAEK composite membrane is prepared integrally, and the PANI in-situ growth realizes the regulation and control of the PAEK surface micro-nano structure. The PANI/PAEK composite membrane is integrally prepared by using the PAEKt porous membrane or the PAEKt nanofiber membrane as a template, and compared with other surface modification treatment technologies, the preparation process is simple and efficient, and the regulation and control of the PANI micro-nano structure on the surface of the membrane are realized. The PANI/PAEK composite membrane prepared in situ in an integrated and non-additive mode increases the interfacial compatibility of the membrane, and meanwhile, the PANI on the surface realizes uniform coverage of the PAEK on the bottom layer, and the hydrophilicity of the membrane is increased while the micro-nano structure on the surface is regulated. The invention fully utilizes the oxidability and surface aggregation of inorganic nano particles, and realizes the enrichment of PANI on the surface and the good fusion of the surface PANI and the bottom PAEK. The invention obtains the membrane material with better separation performance by optimizing the type, acid concentration, oxidant concentration, temperature, time and the like of the acid in the treatment process, and the membrane flux reaches 311L m -2 h -1 bar -1 The retention rate of bovine serum albumin reaches 97%. In the technical exploration process, the increase of the pore-forming agent has a remarkable effect on the increase of porosity and pore size, but in the preparation process, the dosage of the pore-forming agent is regulated and controlled for further preparing the high-performance film material. Surface enrichment of PANI increases the surface hydrophilicity of the membrane and increases the resistance to contamination. The PANI/PAEK composite membrane prepared by the method realizes uniform coverage of PANI on the surface of the membrane, is not easy to agglomerate and has higher content. The method of the invention fully integrates the hydrophilia of PANIAnd the characteristics of conductivity and surface enrichment, and has remarkable application in membrane separation, oil-water separation, photocatalysis separation and the like. Meanwhile, based on enrichment of PANI on the surface of the membrane and change of PANI in different oxidation-reduction states, the size of the PANI/PAEK composite membrane in acid doping and other aspects can be further used in the fields of power-on separation materials, pH response, power-on response and the like, and potential development space and application are provided.
Drawings
FIG. 1 is an infrared spectrum of the PANI/PEEK porous composite film prepared in example 1. The PANI/PEEK porous composite film shown in the figure is 1650cm -1 The C=O bond vibration peak appears at the position of 1306cm -1 Characteristic peaks of C-N bonds of N-Ph-N appear, which prove that the PANI/PEEK porous composite membrane is successfully prepared.
Fig. 2 is a scanning electron microscope image of the surfaces of the PEEKt porous membrane prepared in example 1 and the PANI/PEEK porous composite membrane prepared in example 1, fig. a is a PANI/PEEK porous composite membrane, and fig. b is a PEEKt porous membrane. From the graph, white particles exist on the surface of the synthesized PANI/PEEK porous composite membrane, so that the synthesized PANI is successfully modified on the surface of the membrane, and the material is uniformly dispersed and is not easy to agglomerate.
Fig. 3 is a scanning electron microscope image of the surfaces of the PEEKt nanofiber membrane prepared in example 7 and the PANI/PEEK nanofiber membrane prepared in example 7, fig. a is a PEEKt nanofiber membrane and fig. b is a PANI/PEEK nanofiber membrane. From the graph, the surface of the synthesized PANI/PEEK nanofiber membrane is coarser than that of PEEKt filaments, so that the synthesized PANI is successfully modified on the surface of the membrane, and the material is uniformly dispersed and is not easy to agglomerate.
FIG. 4 is a graph of pure water flux and bovine serum albumin cutoff versus temperature for PANI/PEEK porous composite membranes prepared at different temperatures (example 1-example 3). The PANI/PEEK porous membrane prepared by the method has obvious application in the field of membrane separation.
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings, in which embodiments are shown, by way of illustration, only, and not as a whole. All falling within the scope of the invention are embodiments based on the invention.
Example 1: synthesis of PANI/PEEK porous composite film at room temperature (20 ℃)
(1) Preparing a PEEKt porous membrane: the structural formula of the polyaryletheramine (PEEKt) is shown as (I), wherein a=b=x=y=1. Adding polyaryletheramine (PEEKt) and pore-forming agent polyvinylpyrrolidone into an organic solvent N-methylpyrrolidone, and stirring until the mixture is completely dissolved to prepare PEEKt casting solution; in PEEKt casting solution, the mass fraction of PEEKt is 12%, and the mass fraction of polyvinylpyrrolidone is 12%; pouring the obtained PEEKt casting solution on a clean glass plate, scraping the film by using a scraper with the thickness of 200 mu m, volatilizing for 30 seconds, and then placing the film into a coagulating bath which is ultrapure water to prepare a PEEKt porous film;
(2) Adding the PEEKt porous membrane into a hydrochloric acid solution of ammonium persulfate (the concentration of the hydrochloric acid solution is 2.5M, and the concentration of ammonium persulfate in the hydrochloric acid solution is 0.037M), and reacting for 6 hours in a reaction kettle at 20 ℃; the dosage ratio of the porous membrane of polyaryletheramine (PEEKt) to the hydrochloric acid solution of ammonium persulfate is 0.1g:30mL;
(3) Washing the product obtained in the step (2) with ethanol and water for 3 times respectively, and drying in a vacuum oven at 80 ℃ to obtain the PANI/PEEK porous composite membrane;
(4) Based on enrichment of PANI on the surface and increase of surface hydrophilicity, pure water flux and bovine serum albumin interception test are carried out on the PANI/PEEK porous composite membrane synthesized at 20 ℃, and the membrane flux reaches 311L m -2 h -1 bar -1 The rejection rate of bovine serum albumin reaches 97 percent (cross-flow test), the flux recovery rate is 80 percent, and the PANI/PEEK porous membrane prepared by the invention has obvious application in the fields of membrane separation, size screening, membrane pollution resistance and the like. Meanwhile, based on enrichment of PANI on the surface of the membrane and change of PANI in different oxidation-reduction states, the size of the PANI/PEEK porous membrane can be regulated and controlled in aspects of acid doping and the like, and the prepared PANI/PEEK porous membrane can be further used in the fields of pH response and electrifying response.
Example 2: synthesis of PANI/PEEK porous composite film at 40 DEG C
(1) Preparing a PEEKt porous membrane: the structural formula of the polyaryletheramine (PEEKt) is shown as (I), wherein a=b=x=y=1. Adding polyaryletheramine (PEEKt) and pore-forming agent polyvinylpyrrolidone into an organic solvent N-methylpyrrolidone, and stirring until the mixture is completely dissolved to prepare PEEKt casting solution; in PEEKt casting solution, the mass fraction of PEEKt is 12%, and the mass fraction of polyvinylpyrrolidone is 12%; pouring the obtained PEEKt casting solution on a clean glass plate, scraping the film by using a scraper with the thickness of 200 mu m, volatilizing for 30 seconds, and then placing the film into a coagulating bath which is ultrapure water to prepare a PEEKt porous film;
(2) Adding the PEEKt porous membrane into a hydrochloric acid solution of ammonium persulfate (the concentration of the hydrochloric acid solution is 2.5M, and the concentration of ammonium persulfate in the hydrochloric acid solution is 0.037M), and reacting for 6 hours in a reaction kettle at 40 ℃; the dosage ratio of the porous membrane of polyaryletheramine (PEEKt) to the hydrochloric acid solution of ammonium persulfate is 0.1g:30mL;
(3) Washing the product obtained in the step (2) with ethanol and water for 3 times respectively, and drying in a vacuum oven at 80 ℃ to obtain the PANI/PEEK porous composite membrane;
(4) Based on enrichment of PANI on the surface and increase of surface hydrophilicity, pure water flux and bovine serum albumin interception test are carried out on the PANI/PEEK porous composite membrane synthesized at 40 ℃, and the membrane flux reaches 185L m -2 h -1 bar -1 The retention rate of bovine serum albumin reaches 95 percent (cross flow test).
Example 3: synthetic PANI/PEEK porous composite film
(1) Preparing a PEEKt porous membrane: the structural formula of the polyaryletheramine (PEEKt) is shown as (I), wherein a=b=x=y=1. Adding polyaryletheramine (PEEKt) and pore-forming agent polyvinylpyrrolidone into an organic solvent N-methylpyrrolidone, and stirring until the mixture is completely dissolved to prepare PEEKt casting solution; in PEEKt casting solution, the mass fraction of PEEKt is 12%, and the mass fraction of polyvinylpyrrolidone is 12%; pouring the obtained PEEKt casting solution on a clean glass plate, scraping the film by using a scraper with the thickness of 200 mu m, volatilizing for 30 seconds, and then placing the film into a coagulating bath which is ultrapure water to prepare a PEEKt porous film;
(2) Adding the PEEKt porous membrane into a hydrochloric acid solution of hydrogen peroxide (the concentration of the hydrochloric acid solution is 2.5M, and the concentration of the hydrogen peroxide in the hydrochloric acid solution is 0.037M), and reacting for 6 hours in a reaction kettle at 80 ℃; the dosage ratio of the porous membrane of polyaryletheramine (PEEKt) to the hydrochloric acid solution of hydrogen peroxide is 0.1g:30mL;
(3) Washing the product obtained in the step (2) with ethanol and water for 3 times respectively, and drying in a vacuum oven at 80 ℃ to obtain the PANI/PEEK porous composite membrane;
(4) Pure water flux and bovine serum albumin cutoff tests are carried out on the PANI/PEEK porous composite membrane synthesized at 80 ℃, and the membrane flux reaches 110Lm -2 h -1 bar -1 The rejection rate of bovine serum albumin reaches 95% (cross-flow test), the flux recovery rate is 80%, and the PANI/PEEK porous membrane prepared by the invention has remarkable application in the fields of membrane separation, size screening, membrane pollution resistance and the like.
Example 4: synthetic PANI/PEEK porous composite film
(1) Preparing a PEEKt porous membrane: the structural formula of the polyaryletheramine (PEEKt) is shown as (I), wherein a=b=x=y=1. Adding polyaryletheramine (PEEKt) and pore-forming agent polyvinylpyrrolidone into an organic solvent N-methylpyrrolidone, and stirring until the mixture is completely dissolved to prepare PEEKt casting solution; in PEEKt casting solution, the mass fraction of PEEKt is 12%, and the mass fraction of polyvinylpyrrolidone is 12%; pouring the obtained PEEKt casting solution on a clean glass plate, scraping the film by using a scraper with the thickness of 200 mu m, volatilizing for 30 seconds, and then placing the film into a coagulating bath which is ultrapure water to prepare a PEEKt porous film;
(2) Adding the PEEKt porous membrane into a hydrochloric acid solution of ammonium persulfate (the concentration of the hydrochloric acid solution is 2.5M, and the concentration of ammonium persulfate in the hydrochloric acid solution is 0.6M), and reacting for 6 hours in a reaction kettle at 20 ℃; the dosage ratio of the porous membrane of polyaryletheramine (PEEKt) to the hydrochloric acid solution of ammonium persulfate is 0.1g:160mL;
(3) Washing the product obtained in the step (2) with ethanol and water for 3 times respectively, and drying in a vacuum oven at 80 ℃ to obtain the PANI/PEEK porous composite membrane;
(4) The PANI/PEEK porous composite membrane synthesized under the conditions was subjected to a pure water flux and bovine serum albumin cutoff test based on the enrichment of PANI on the surface and the increase of the hydrophilicity of the surface, and the result was similar to example 3.
Example 5: synthesis of PANI/PEEK porous composite membrane under low hydrochloric acid concentration condition
(1) Preparing a PEEKt porous membrane: the structural formula of the polyaryletheramine (PEEKt) is shown as (I), wherein a=b=x=y=1. Adding polyaryletheramine (PEEKt) and pore-forming agent polyvinylpyrrolidone into an organic solvent N-methylpyrrolidone, and stirring until the mixture is completely dissolved to prepare PEEKt casting solution; in PEEKt casting solution, the mass fraction of PEEKt is 12%, and the mass fraction of polyvinylpyrrolidone is 12%; pouring the obtained PEEKt casting solution on a clean glass plate, scraping the film by using a scraper with the thickness of 200 mu m, volatilizing for 30 seconds, and then placing the film into a coagulating bath which is ultrapure water to prepare a PEEKt porous film;
(2) Adding the PEEKt porous membrane into a hydrochloric acid solution of ammonium persulfate (the concentration of the hydrochloric acid solution is 1.0M, and the concentration of ammonium persulfate in the hydrochloric acid solution is 0.037M), and reacting for 6 hours in a reaction kettle at 20 ℃; the dosage ratio of the porous polyaryletheramine (PEEKt) to the ammonium persulfate hydrochloric acid solution is 0.1g:30mL;
(3) Washing the product obtained in the step (2) with ethanol and water for 3 times respectively, and drying in a vacuum oven at 80 ℃ to obtain the PANI/PEEK porous composite membrane;
(4) The synthesized PANI/PEEK porous composite membrane is subjected to pure water flux and bovine serum albumin cutoff test, and the membrane flux reaches 183Lm -2 h -1 bar -1 The retention rate of bovine serum albumin reaches 95 percent (cross flow test).
Example 6: synthesis of PANI/PEEK porous composite membrane under high hydrochloric acid concentration condition
(1) Preparing a PEEKt porous membrane: the structural formula of the polyaryletheramine (PEEKt) is shown as (I), wherein a=b=x=y=1. Adding polyaryletheramine (PEEKt) and pore-forming agent polyvinylpyrrolidone into an organic solvent N-methylpyrrolidone, and stirring until the mixture is completely dissolved to prepare PEEKt casting solution; in PEEKt casting solution, the mass fraction of PEEKt is 12%, and the mass fraction of polyvinylpyrrolidone is 12%; pouring the obtained PEEKt casting solution on a clean glass plate, scraping the film by using a scraper with the thickness of 200 mu m, volatilizing for 30 seconds, and then placing the film into a coagulating bath which is ultrapure water to prepare a PEEKt porous film;
(2) Adding the PEEKt porous membrane into a hydrochloric acid solution of ammonium persulfate (the concentration of the hydrochloric acid solution is 6.0M, and the concentration of ammonium persulfate in the hydrochloric acid solution is 0.037M), and reacting for 6 hours in a reaction kettle at 20 ℃; the dosage ratio of the porous membrane of polyaryletheramine (PEEKt) to the hydrochloric acid solution of ammonium persulfate is 0.1g:30mL;
(3) Washing the product obtained in the step (2) with ethanol and water for 3 times respectively, and drying in a vacuum oven at 80 ℃ to obtain the PANI/PEEK porous composite membrane;
(4) The synthesized PANI/PEEK porous composite membrane is subjected to pure water flux and bovine serum albumin cutoff test, and the membrane flux reaches 165Lm -2 h -1 bar -1 The retention rate of bovine serum albumin reaches 96 percent (cross flow test).
Example 7: PANI/PEEK porous composite membrane synthesized under p-toluenesulfonic acid condition
(1) Preparing a PEEKt porous membrane: the structural formula of the polyaryletheramine (PEEKt) is shown as (I), wherein a=b=x=y=1. Adding polyaryletheramine (PEEKt) and pore-forming agent polyvinylpyrrolidone into an organic solvent N-methylpyrrolidone, and stirring until the mixture is completely dissolved to prepare PEEKt casting solution; in PEEKt casting solution, the mass fraction of PEEKt is 12%, and the mass fraction of polyvinylpyrrolidone is 12%; pouring the obtained PEEKt casting solution on a clean glass plate, scraping the film by using a scraper with the thickness of 200 mu m, volatilizing for 30 seconds, and then placing the film into a coagulating bath which is ultrapure water to prepare a PEEKt porous film;
(2) Adding the PEEKt porous membrane into p-toluenesulfonic acid and hydrochloric acid solution of ammonium persulfate (the concentration of the p-toluenesulfonic acid solution is 2.0M, the solubility of the hydrochloric acid solution is 1M, and the concentration of ammonium persulfate in the p-toluenesulfonic acid and hydrochloric acid solution is 0.037M), and reacting for 6 hours in a reaction kettle at 60 ℃; the dosage ratio of the porous membrane of polyaryletheramine (PEEKt) to the p-toluenesulfonic acid and hydrochloric acid solution of ammonium persulfate is 0.1g:30mL;
(3) Washing the product obtained in the step (2) with ethanol and water for 3 times respectively, and drying in a vacuum oven at 80 ℃ to obtain the PANI/PEEK porous composite membrane;
(4) The porous composite membrane prepared in this example has flux and shut-off properties similar to those of example 3.
Example 8: synthetic PANI/GO/PEEK porous composite membrane
(1) Preparing a PEEKt porous membrane: the structural formula of the polyaryletheramine (PEEKt) is shown as (I), wherein a=b=x=y=1. Adding polyaryletheramine (PEEKt), pore-forming agent polyvinylpyrrolidone and inorganic nanoparticle graphene oxide into an organic solvent N-methylpyrrolidone, and stirring until the mixture is completely dissolved to prepare PEEKt casting solution; in PEEKt casting solution, the mass fraction of PEEKt is 12%, the mass fraction of polyvinylpyrrolidone is 12%, and the mass fraction of graphene oxide is 2%; pouring the obtained PEEKt casting solution on a clean glass plate, scraping the film by using a scraper with the thickness of 200 mu m, volatilizing for 30 seconds, and then placing the film into a coagulating bath which is ultrapure water to prepare a PEEKt porous film;
(2) Adding the PEEKt film into a hydrochloric acid solution of ammonium persulfate (the solubility of the hydrochloric acid solution is 4M, and the concentration of ammonium persulfate in the hydrochloric acid solution is 0.037M), and treating the PEEKt film in a reaction kettle at 60 ℃ for 6 hours; the dosage ratio of the porous polyaryletheramine (PEEKt) to the mixed solution is 0.1g:30mL;
(3) Washing the product obtained in the step (2) with ethanol and water for 3 times respectively, and drying in a vacuum oven at 80 ℃ to obtain the PANI/GO/PEEK porous composite membrane;
(4) The porous composite membrane prepared in this example has flux and shut-off properties similar to those of example 2.
Example 9: synthetic PANI/PEEK nanofiber composite membrane
(1) Preparing a PEEKt porous membrane: the structural formula of the polyaryletheramine (PEEKt) is shown as (I), wherein a=b=x=y=1. Adding polyaryletheramine (PEEKt) into an organic solvent N-methylpyrrolidone, and stirring until the polyaryletheramine (PEEKt) is completely dissolved to prepare PEEKt casting solution; the PEEKt casting solution comprises 23% of PEEKt by mass. Placing PEAKt casting solution into a syringe by using electrostatic spinning technology, controlling the distance from a spinneret to a bottom plate to be 15cm, the voltage to be 15KV and the flow velocity to be 0.5 mL.h -1 The spinning time is 60min, and the PAEKt nanofiber membrane is prepared;
(2) Adding the PEEKt nanofiber membrane into a hydrochloric acid solution of ammonium persulfate (the concentration of the hydrochloric acid solution is 2.5M, and the concentration of ammonium persulfate in the hydrochloric acid solution is 0.037M), and treating the mixture in a reaction kettle at 25 ℃ for 6 hours; polyaryletheramine nanocomposite mold (dosage ratio to ammonium persulfate hydrochloric acid solution is 0.1g:30ml;
(3) Washing the product obtained in the step (2) with ethanol and water for 3 times respectively, and drying in a vacuum oven at 80 ℃ to obtain the PANI/PEEK nanofiber composite membrane;
(4) Based on the hydrophilicity of the PANI surface, the PANI/PEEK nanofiber membrane can realize the efficient separation of oil and water by testing the oil-water separation performance.
Claims (4)
1. A preparation method of polyaniline/polyaryletherketone composite membrane with electrochemical response comprises the following steps:
1) Adding polyaryletheramine with the structural formula shown in the specification, a pore-forming agent and nano particles into an organic solution, and stirring until the polyaryletheramine, the pore-forming agent and the nano particles are completely dissolved to prepare polyaryletheramine casting solution; in the polyaryletheramine casting solution, the mass fraction of the polyaryletheramine is 10% -25%; the pore-forming agent is one or more of polyvinylpyrrolidone, polyethylene glycol and acetone, and the mass fraction is 1% -15%; the nano particles are one or more of graphene oxide, metal organic frame materials and covalent organic frame materials, the mass fraction of the nano particles is 0% -4%, the mass fraction of the nano particles is not 0%, and the addition of the nano particles realizes the enrichment of polyaniline on the surface of the membrane;
n is a positive integer representing the degree of polymerization, wherein a, b, X, Y is a positive integer and Y is greater than or equal to 1;
2) Preparing a polyaryletheramine porous membrane: pouring the polyaryletheramine casting solution obtained in the step 1) on a clean glass plate, scraping the film by using a scraper with the thickness of 100-300 mu m, volatilizing for 5-60 s, and then placing the film into a coagulating bath, wherein the coagulating bath is one or more of ultrapure water, ethanol and hydrochloric acid, and preparing the polyaryletheramine porous film on the glass plate; or placing the polyaryletheramine casting solution obtained in the step 1) in an injector for electrostatic spinning, wherein the distance from a spinning nozzle of the injector to a bottom plate is 10-20 cm, the spinning voltage is 10-25 KV, the flow rate of the casting solution is 0.3-1.0 mL & h < -1 >, and the spinning time is 20-120 min, so that the polyaryletheramine nanofiber membrane is obtained;
3) Preparing an acid solution of an oxidant, wherein the acid concentration is 0.1-6.0M, and the oxidant concentration is 0.037-0.6M; adding the polyaryletheramine porous membrane or the polyaryletheramine nanofiber membrane obtained in the step 2) into an acid solution containing an oxidant, and putting the acid solution into a reaction kettle to react at 20-80 ℃ for 1-10 h, wherein the dosage ratio of the polyaryletheramine porous membrane or the polyaryletheramine nanofiber membrane to the acid solution containing the oxidant is 0.1g: 5-160 mL; the oxidant is one or more of hydrogen peroxide, ammonium persulfate, potassium dichromate and ferric chloride; the acid is one or more of hydrochloric acid, sulfuric acid, phytic acid, sulfosalicylic acid, benzenesulfonic acid, acetic acid and p-toluenesulfonic acid; and finally, respectively cleaning the obtained membrane with ethanol and water for 3-5 times, and drying at 50-80 ℃ to obtain the polyaniline/polyaryletherketone composite membrane with electrochemical response.
2. The method for preparing the polyaniline/polyaryletherketone composite membrane with electrochemical response according to claim 1, wherein the method comprises the following steps: the organic solvent in the step 1) is one or more of N-methyl pyrrolidone, dimethylformamide, dimethylacetamide, chloroform and tetrahydrofuran.
3. A polyaniline/polyaryletherketone composite membrane having electrochemical response, characterized in that: is prepared by the method of any one of claims 1-2.
4. Use of a polyaniline/polyaryletherketone composite membrane having electrochemical response according to claim 3 in the field of membrane separation.
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| CN102068925A (en) * | 2010-12-08 | 2011-05-25 | 天津大学 | Preparation method of polyaniline nano composite film |
| CN112726192A (en) * | 2020-12-18 | 2021-04-30 | 江苏大学 | Preparation method of electrospun carbon nanofiber/reduced graphene oxide/polyaniline/basic nickel carbonate composite electrode material |
| WO2021258701A1 (en) * | 2020-06-23 | 2021-12-30 | 三达膜科技（厦门）有限公司 | Preparation method of sustainable hydrophilic modified polyvinylidene fluoride hollow membrane |
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| CN110841493B (en) * | 2019-11-25 | 2021-08-03 | 吉林大学 | Polyaryletherketone separation membrane or sulfonated polyaryletherketone separation membrane with adjustable pore diameter and preparation method thereof |
| CN113509840B (en) * | 2020-04-09 | 2023-01-03 | 中国石油化工股份有限公司 | Composite nanofiltration membrane and preparation method and application thereof |
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| CN102068925A (en) * | 2010-12-08 | 2011-05-25 | 天津大学 | Preparation method of polyaniline nano composite film |
| WO2021258701A1 (en) * | 2020-06-23 | 2021-12-30 | 三达膜科技（厦门）有限公司 | Preparation method of sustainable hydrophilic modified polyvinylidene fluoride hollow membrane |
| CN112726192A (en) * | 2020-12-18 | 2021-04-30 | 江苏大学 | Preparation method of electrospun carbon nanofiber/reduced graphene oxide/polyaniline/basic nickel carbonate composite electrode material |
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