CN110106703B - Preparation method of ion exchange fabric membrane - Google Patents

Preparation method of ion exchange fabric membrane Download PDF

Info

Publication number
CN110106703B
CN110106703B CN201910230134.5A CN201910230134A CN110106703B CN 110106703 B CN110106703 B CN 110106703B CN 201910230134 A CN201910230134 A CN 201910230134A CN 110106703 B CN110106703 B CN 110106703B
Authority
CN
China
Prior art keywords
fabric
ion exchange
membrane
irradiation
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910230134.5A
Other languages
Chinese (zh)
Other versions
CN110106703A (en
Inventor
朱新生
陶然
高德贵
徐涛
杨振北
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Priority to CN201910230134.5A priority Critical patent/CN110106703B/en
Publication of CN110106703A publication Critical patent/CN110106703A/en
Application granted granted Critical
Publication of CN110106703B publication Critical patent/CN110106703B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/36—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated carboxylic acids or unsaturated organic esters as the major constituent
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/08—Organic compounds
    • D06M10/10—Macromolecular compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/11—Compounds containing epoxy groups or precursors thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12—Aldehydes; Ketones
    • D06M13/123—Polyaldehydes; Polyketones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/08—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin
    • D06M14/12—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M14/16—Polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

The invention discloses a preparation method of an ion exchange fabric membrane, and belongs to the field of membrane material preparation. The invention uses free radical solution polymerization to prepare the copolymer containing ion exchange group, and then uses electrostatic spinning technology to spin the electric spinning solution on the surface of the fabric which is processed by pre-grafting polymerization, and then uses cross-linking agent to cross-link to obtain the homogeneous phase ion exchange fabric membrane. The obtained ion exchange membrane has high mechanical strength, large ion exchange capacity, no environmental pollution in the preparation process and wide application prospect.

Description

Preparation method of ion exchange fabric membrane
Technical Field
The invention relates to the field of polymer membranes, in particular to a homogeneous phase ion exchange fabric membrane prepared by pre-irradiation graft polymerization and electrostatic spinning.
Background
Ion exchange membranes are a class of polymeric membranes containing ionizable groups. It is divided into cation exchange membrane and anion exchange membrane according to the different charge properties of the fixed group. They are further classified into heterogeneous membranes and homogeneous membranes according to the degree of uniformity of chemical properties. The preparation method of the homogeneous membrane mainly comprises the following steps: film formation after polymer functionalization or introduction of active functional groups on a polymer base film. The method for introducing the active group comprises a solution polymerization method, an impregnation polymerization method, a slurry coating polymerization method and a base film grafting method. The heterogeneous membrane is formed by mixing ion exchange resin powder and a high molecular adhesive, pulling a sheet, reinforcing mesh cloth, hot pressing and the like.
As early as the 50 s of the 20 th century, Ionics and Rohm, usa, have led to the development of well-performing heterogeneous ion exchange membranes, and electrodialysis processes based on such membranes are rapidly applied to desalination and concentration of industrial electrolyte solutions. However, due to the defects of poor structural stability and high membrane surface resistance of the heterogeneous membrane, the heterogeneous membrane is mainly used for primary water treatment and some simple chemical separation at present and cannot be used in the fields of comprehensive utilization of seawater, chemical separation and the like.
The early Ningbo environmental protection equipment factory in China produces S by chloromethylation of chloromethyl ether by taking polysulfone as a matrix2O3Homogeneous negative film, the Hangzhou water treatment center develops homogeneous positive film of sulfonic acid type styrene-divinyl benzene, and the radiation grafting method adopted by Shanghai atoms can produce polyethylene grafted homogeneous negative and positive film. Wherein S is2O3Homogeneous negative films were forced to stop production at the end of 1997 due to the contamination problem with chloromethyl ether.
In recent years, the Shandong Hai chemical industry academy utilizes methyl bromination of polymer instead of chloromethylation of chloromethyl ether, avoids the use of chloromethyl ether which is a highly toxic substance, and can control the performance of the membrane through bromination position and bromine content.
According to the report, a film formed by blending polyethylene and an ethylene-octene copolymer elastomer is used as a raw material, then the film is soaked in a solution composed of styrene, divinylbenzene and an initiator dibenzoyl peroxide, then the film is taken out for superposition, pressurized and heated for polymerization to obtain a base film, and then the base film is soaked in concentrated sulfuric acid for sulfonation reaction at 70-80 ℃, so that the cation exchange membrane is obtained. Similarly, soaking the base membrane in a solution composed of chloromethyl ether and anhydrous stannic chloride, reacting at 35-50 ℃ to obtain a chloromethyl membrane, soaking the chloromethyl membrane in 25-30% trimethylamine aqueous solution, and reacting at 30-35 ℃ to obtain the strong quaternary ammonium type anion exchange membrane.
However, in the production according to the above process, if the crystallinity of the base membrane (e.g., polyethylene) is high, the graft monomer is difficult to permeate into the inside of the membrane, and the graft ratio is low, i.e., the ion exchange amount is low. Even if the crystallinity of the base film (e.g., ethylene-octene copolymer elastomer) is low, the non-polar and highly cross-linked polymer composite membrane prevents permeation of strongly polar concentrated sulfuric acid and trimethylamine aqueous solution, resulting in a low ion exchange amount.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a homogeneous phase ion exchange fabric membrane prepared by pre-grafting and electrostatic spinning, which is used for solving the problems of low ion exchange amount and poor mechanical property in the prior art.
A method of making a homogeneous ion exchange fabric membrane, the method comprising the steps of:
dipping the electric treated fabric into a grafting solution, and grafting to obtain a pre-grafted polymerization treated fabric;
spinning the electrospinning solution to the surface of the pre-grafted and polymerized fabric through an electrostatic spinning process to form an electrospun fiber fabric membrane;
and chemically crosslinking, cleaning and drying the electrospun fiber fabric membrane to obtain the ion exchange fabric membrane.
Further, the preparation method of the electric treatment fabric comprises the step of irradiating the fabric to obtain the electric treatment fabric.
Further, the fabric includes woven fabrics, knitted fabrics and non-woven fabrics;
the fiber of the fabric comprises terylene, chinlon, acrylon, polypropylene fiber, vinylon and modacrylic chloride;
the fabric graft polymerization treatment means that the surface and the internal air of the fabric are extruded or exhausted by inert gas, so that the monomer in the grafting liquid is better graft polymerized onto the fabric.
Further, the irradiation includes high-energy gamma ray irradiation, electron beam irradiation, plasma irradiation and ultraviolet irradiation; when ultraviolet irradiation is carried out, the photosensitizer benzophenone and benzoin dimethyl ether are needed.
Further, the electrostatic spinning voltage is 7-20 kilovolts, the distance is 10-20 centimeters, and the spinning speed is 1.0-35.0 milliliters per hour.
Furthermore, the crosslinking curing temperature is 50-120 ℃, and the crosslinking curing time is 0.5-5.0 hours.
Further, the crosslinking agent for crosslinking and curing comprises bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glutaraldehyde, hexamethylenetetramine, trimethylolmelamine, hexamethylolmelamine, dimethylol dihydroxyethylene urea, butanetetracarboxylic acid, adipic acid, succinic acid, maleic anhydride, triethyltetramine, diethyltriamine and ethylenediamine.
The method for transferring the cross-linking agent in the cross-linking curing reaction comprises two methods, wherein one method is that the cross-linking agent is dissolved in an organic solvent or a mixed solvent of the organic solvent and water, the fabric covered with the electro-spun fiber layer is placed in the cross-linking agent solution for dipping and taken out, and the cross-linking reaction is carried out at a certain temperature and pressure; the other method is to steam the fabric covered with the electrospun fiber layer in a closed container containing a crosslinking agent, so that the crosslinking agent permeates the graft and the surface and the inside of the fiber, and the crosslinking reaction is carried out at certain temperature and pressure.
Further, the comonomers in the grafting liquid and the electrospinning liquid comprise acrylic acid, methacrylic acid, styrene sulfonic acid, sodium styrene sulfonate, sodium acrylate, sodium methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, butyl acrylate, butyl methacrylate, methacrylamidopropyltrimethylammonium chloride, dimethyldiallylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, acrylamide, trimethylolpropane triacrylate, pentaerythritol triacrylate, and N, N-methylene bisacrylamide (the latter three monomers are free radical crosslinking monomers).
Further, the preparation method of the electrospinning liquid comprises the following steps: and (3) dropwise adding an initiator into a comonomer dissolved in a solvent, carrying out polymerization reaction at 50-95 ℃ under the protection of nitrogen to obtain a polymer solution, and adjusting the viscosity to obtain the electrospinning solution.
Further, the solvent is an organic solvent, water, and a mixed solvent of the organic solvent and the water;
the organic solvent comprises methanol, ethanol, acetone, butanone, tetrahydrofuran, ethyl acetate and butyl acetate.
For the preparation of bipolar ion exchange fabric membranes, the grafted unsaturated monomers include acrylic acid, methacrylic acid, hydroxyethyl acrylate, glycidyl acrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate. After the graft polymerization reaction is completed, under the action of a dibutyltin dilaurate catalyst, an epoxy ring-opening reaction is carried out based on 2, 3-epoxypropyltrimethylammonium chloride, so as to introduce an anion exchange group.
For the preparation of bipolar ion exchange fabric membranes, the electrospinning solution copolymer unsaturated monomer is close to the grafting solution monomer, but does not contain a free radical crosslinking monomer. After electrospinning coating, polyacrylic acid in the electrospun fiber is subjected to esterification and crosslinking reaction with hydroxyl and epoxy groups in the electrospun fiber under the action of a carbodiimide activating agent. And under the action of a dibutyltin dilaurate catalyst, performing ring opening reaction based on 2, 3-epoxypropyltrimethylammonium chloride, so as to insert an anion exchange group into the electrospun fiber.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
compared with the prior art, the invention has the following beneficial effects:
(1) a certain amount of polymer is grafted on the surface of the fabric substrate in advance, so that covalent bonding is formed between the grafted polymer and the fiber surface of the fabric, and the transmembrane flow of free water is limited;
(2) the mechanical property of an 'electro-spinning coating layer' of the fabric is improved by an electrostatic spinning technology;
(3) the cross-linking treatment substantially improves the binding force between the electrospun fibers and between the fabrics and the electrospun fibers so as to improve the mechanical property of the ion exchange fabric membrane;
(4) the amount of ion exchange can be adjusted by selecting the fabric, adjusting the fabric grafting rate and the thickness of the electrospun fiber layer.
Detailed Description
The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1 homogeneous cation exchange Membrane preparation
1.1 grafting pretreatment:
(1) polyamide monofilament fabric (surface density 45 g/m) by corona discharge technology2) Performing irradiation treatment, wherein the voltage is 130V, the current is 0.5A, and the fabric is moved back and forth to discharge for 10 times to obtain the electric treatment fabric;
(2) uniformly dissolving a grafting monomer comprising acrylic acid/butyl acrylate/hydroxyethyl acrylate/pentaerythritol triacrylate (the molar ratio is 4:1.5:1.5:1) in methanol, dissolving ammonium persulfate in water, uniformly mixing the two solutions, soaking the electrically-treated fabric in a grafting solution to ensure that the grafting solution permeates into the interior of the fabric and uniformly distributes the surface of the fabric, and removing the redundant grafting solution by using filter paper;
(3) fixing the electrically treated fabric impregnated with the grafting liquid in a metal frame, placing between two metal plates, fastening (removing air on the inner and outer surfaces of the fabric by squeezing), placing the whole in an oven, performing thermal polymerization at 60 deg.C for 4 hr, cooling, and obtaining radiation graft polymerization
The fabric is treated.
1.2 electrostatic spinning:
(1) uniformly dissolving unsaturated monomers including acrylic acid/butyl acrylate/hydroxyethyl acrylate (the molar ratio is 2:1:1) in a methanol/water (the volume ratio is 3:1) mixed solvent, dissolving initiator ammonium persulfate in deionized water, dropwise adding the initiator into the unsaturated monomer solution by using a peristaltic pump, polymerizing at 50 ℃ under the protection of nitrogen, and controlling the polymerization degree and the conversion rate of a polyacrylate copolymer;
(2) adding a mixed solvent into the copolymer, and adjusting the viscosity of the polymer solution to prepare uniform electrospinning solution;
(3) placing the pre-grafted polymerization treated fabric in a metal frame to form a receiving screen, connecting a negative electrode of a high-voltage direct-current power supply to the receiving screen, enabling the receiving screen to rotate, connecting a positive electrode of the high-voltage direct-current power supply to a spinning nozzle to carry out electrostatic spinning treatment on the pre-grafted polymerization treated fabric, wherein the spinning voltage is 7-9 kilovolts, the spinning distance is 10 centimeters, and the spinning speed is 1 milliliter/hour;
(4) and when a certain amount of electrospinning liquid is spun on the surface of the pre-grafted fabric, stopping spinning, and taking down the electrospinning fiber fabric membrane from the receiving screen.
1.3 post-crosslinking and drying treatment:
(1) placing a certain amount of glutaraldehyde aqueous solution at the bottom of a dryer, placing an electrospun fiber fabric membrane on a ceramic pore plate in drying, sealing the dryer, placing in a constant-temperature water bath for steaming, and taking out after steaming;
(2) placing the processed electrospun fiber fabric membrane in a metal frame, tensioning and flattening, clamping between two Teflon plates, and reacting in an oven at 50 ℃ for 5 hours for crosslinking and curing;
(3) and washing and vacuum drying the crosslinked and solidified electrospun fiber fabric membrane to obtain the ion exchange fiber fabric membrane.
The performance of the obtained ion exchange fabric membrane is as follows: tensile mechanical strength: 10MPa, elongation at break of 15%, ion exchange amount of 1.5mmol/g (dry film), sheet resistance of 40. omega. cm2Resistance to hydrostatic pressure of 500mmH2The height of the O water column is 1 h.
Example 2 homogeneous anion exchange Membrane
2.1 grafting pretreatment:
(1) terylene monofilament fabric (surface density 55 g/m)2) Placing the polyester fabric in the ethanol of benzophenoneAnd (5) carrying out middle dipping treatment, taking out and airing, and then carrying out irradiation treatment. Irradiating by using an ultraviolet irradiation technology, wherein an ultraviolet light source is a mercury lamp, the irradiation power is 300 watts, and the irradiation time is 10 minutes, so that the electric treatment fabric is obtained.
(2) Uniformly dissolving a grafting monomer comprising methacrylamide propyl trimethyl ammonium chloride/N, N-methylene bisacrylamide/hydroxyethyl acrylate (the molar ratio is 4:1.5:2) in an ethanol/water (the volume ratio is 1:1) mixed solvent, dissolving ammonium persulfate in water, uniformly mixing the two solutions, dipping the fabric subjected to ultraviolet irradiation treatment in a grafting solution, ensuring that the grafting solution permeates into the interior of the fabric and uniformly distributes the surface of the fabric, and removing the redundant grafting solution by using filter paper;
(3) and (3) placing the electric treated fabric soaked with the grafting liquid in a closed pressure container, replacing air in the container with nitrogen to form an inert atmosphere, then placing the closed pressure container in an oven, carrying out thermal polymerization reaction at 70 ℃ for 4 hours, taking out and cooling to obtain the pre-grafted polymerization treated fabric.
2.2 electrostatic spinning:
(1) dissolving unsaturated monomers including methacrylamide propyl trimethyl ammonium chloride/acrylamide/hydroxyethyl acrylate (the molar ratio is 4:1:3) in a mixed solvent of ethanol/water (the volume ratio is 1:1), dissolving initiator ammonium persulfate in deionized water, dropwise adding the initiator into the unsaturated monomer solution by using a peristaltic pump, carrying out polymerization reaction at 65 ℃ under the protection of nitrogen, and controlling the polymerization degree and the conversion rate of the copolymer by using the polymer viscosity;
(2) adding a mixed solvent into the copolymer, and adjusting the viscosity of the polymer solution to prepare uniform electrospinning solution;
(3) placing the pre-grafted fabric in a metal frame to serve as a receiving screen, connecting a negative electrode of a high-voltage direct-current power supply to the metal frame, rotating the receiving screen, connecting a spinning nozzle with a positive electrode of the high-voltage direct-current power supply, and carrying out electrostatic spinning on the pre-grafted fabric, wherein the spinning voltage is 10-11 kilovolts, the spinning distance is 15 centimeters, and the spinning speed is 5.0 milliliters per hour;
(4) and when a certain amount of the electrospinning liquid is spun on the surface of the receiving fabric, stopping spinning, and removing the electrospinning fiber fabric membrane from the receiving screen.
2.3 post-crosslinking and drying treatment:
(1) dissolving a certain amount of bisphenol A diglycidyl ether and dibutyl tin dilaurate in tetrahydrofuran, placing the electrospun fiber fabric membrane in the tetrahydrofuran solution, and taking out after soaking for a certain time;
(2) placing the processed electrospun fiber fabric membrane in a metal frame, tensioning and flattening, clamping between two Teflon plates, and performing crosslinking curing reaction in an oven at 95 ℃ for 2 hours;
(3) and washing and vacuum drying the cross-linking treated fabric membrane, and finally, spinning the fiber fabric membrane.
The performance of the obtained ion exchange fabric membrane is as follows: tensile mechanical strength: 14MPa, elongation at break of 10%, ion exchange amount of 1.2mmol/g (dry film), sheet resistance of 50. omega. cm2Resistance to hydrostatic pressure of 530mmH2The height of the O water column is 1 h.
Example 3 homogeneous Bipolar ion exchange Membrane
3.1 grafting pretreatment:
(1) for polypropylene monofilament fabric (surface density 80 g/m)2) Carrying out electron beam irradiation treatment, wherein the total irradiation dose in the air is 60kGy, and obtaining the electric treatment fabric;
(2) uniformly dissolving a grafting monomer comprising acrylic acid/hydroxyethyl acrylate/pentaerythritol triacrylate (the molar ratio is 2:3.75:0.75) in an ethanol solvent, dissolving ammonium persulfate in deionized water, uniformly mixing the two solutions, soaking the discharge-treated fabric in a grafting solution to ensure that the grafting solution permeates into the interior of the fabric and uniformly distributes the surface of the fabric, and removing the redundant grafting solution by using filter paper;
(3) fixing the fabric of the electric treatment fabric soaked with the grafting liquid in a metal frame, then placing the metal frame between two layers of metal plates, fastening the metal frame, placing the metal frame in an oven, carrying out thermal polymerization reaction at 75 ℃ for 3 hours, taking out the metal frame and cooling the metal frame to obtain a pre-grafted polymerization treatment fabric;
(4) and (3) soaking the pre-grafted fabric in an ethyl acetate solution of dibutyl tin dilaurate, and then performing functionalization reaction in a 2, 3-epoxypropyltrimethylammonium chloride aqueous solution.
3.2 electrostatic spinning:
(1) uniformly dissolving unsaturated monomers including acrylic acid/hydroxyethyl acrylate (the molar ratio is 2:4) in deionized water, dissolving an initiator potassium persulfate in the deionized water, dropwise adding the initiator into the unsaturated monomer solution by using a peristaltic pump, polymerizing at 95 ℃ under the protection of nitrogen, and controlling the polymerization degree and the conversion rate of the copolymer by using the polymer viscosity;
(2) adding a mixed solvent into the copolymer, and adjusting the viscosity of the polymer solution to prepare uniform electrospinning solution;
(3) placing the pre-grafted fabric after the functionalization reaction in a metal frame to serve as a receiving screen, connecting a negative electrode of a high-voltage direct-current power supply to the metal frame, wherein the receiving screen can rotate, connecting a spinning nozzle with a positive electrode of the high-voltage direct-current power supply to perform electrostatic spinning treatment on the pre-grafted fabric, wherein the spinning voltage is 15-20 kilovolts, the spinning distance is 20 cm, and the spinning speed is 35 ml/h;
(3) stopping spinning after a certain amount of electrospinning liquid is spun on the surface of the pre-grafted fabric, and taking down the electrospinning fiber fabric membrane from the receiving screen;
(4) in the presence of ethyl acetate solvent of dicyclohexylcarbodiimide and 4-dimethylaminopyridine, polyacrylic acid in the electrospun fiber is subjected to esterification crosslinking reaction with hydroxyl groups and epoxy groups in the electrospun fiber at room temperature.
(5) And (3) soaking the crosslinked electrospun fiber fabric membrane in a butyl acetate solution of a dibutyl tin dilaurate catalyst for treatment, and then performing a functionalization reaction in a 2, 3-epoxypropyltrimethylammonium chloride aqueous solution.
3.3 post-crosslinking and drying treatment:
(1) dissolving a certain amount of butane tetracarboxylic acid and carbodiimide in deionized water, and then putting the electrospun fiber fabric membrane subjected to the functionalization reaction in the solution for dipping and taking out.
(2) Tensioning and flattening the treated electrospun fiber fabric membrane in a metal frame, clamping the membrane between two Teflon plates, and carrying out cross-linking curing reaction in an oven at 120 ℃ for 0.5 hour;
(3) and washing and vacuum drying the cross-linked fabric membrane to obtain the ion exchange fabric membrane.
The performance of the obtained ion exchange fabric membrane is as follows: tensile mechanical strength: 10MPa, elongation at break of 20%, anion and cation exchange capacities of 0.5 and 0.6mmol/g (dry film), respectively, and sheet resistance of 55. omega. cm2And is resistant to hydrostatic pressure of 550mmH2The height of the O water column is 1 h.
Electrospinning is a special fiber manufacturing process. Under the action of electric field force, the liquid drop in the spinning nozzle changes from semispherical shape to conical shape and further extends from the conical surface and the tip of the conical surface to obtain fiber filament. In this way, ultra-fine and nano-fibers can be produced. The stretching action of the electric field force leads to the orientation of macromolecular chains, so that the tensile strength of the obtained fiber is higher. The whip effect of the electro-spinning fiber in the electric field makes the electro-spinning fiber in a random distribution state on a receiving screen. The characteristics of low diameter, high strength and random deposition of the electrospun fibers can meet the basic requirements of the ion exchange membrane. When the electrospun polymer is a polyelectrolyte, its fiber diameter is smaller. In this way, the ion exchange groups can be distributed more to the surface of the fibers. By controlling the volatility of the solvent in the electrospun fiber and using the cross-linking agent, the bonding effect between fibers can be improved, and the mechanical property of a fiber film layer can be improved. Potential application fields of the electrospun fiber membrane comprise biomedical materials, air filter materials, sensors, ion exchange membranes and the like.
The invention takes the fabric as a reinforced substrate, firstly grafts polyelectrolyte into the fabric and on the surface of the fabric, then electro-spun fibrous membrane is electro-spun and deposited on the surface of the grafted fabric, and the fabric covered with the electro-spun fibrous membrane is cross-linked, so that the bonding force between the fibrous membrane and the fabric and in the fibrous membrane layer is improved, and further the mechanical stability of the ion exchange fabric membrane is improved.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (7)

1. A method of making an ion exchange fabric membrane, comprising the steps of:
dipping the electric treated fabric into a grafting solution, and carrying out graft polymerization to obtain a pre-grafted polymerization treated fabric;
spinning the electrospinning solution to the surface of the pre-grafted and polymerized fabric through an electrostatic spinning process to form an electrospun fiber fabric membrane;
chemically crosslinking the electrospun fiber fabric membrane to obtain an ion exchange fabric membrane;
the preparation method of the electrospinning liquid comprises the following steps:
dropwise adding an initiator into a comonomer dissolved in a solvent, carrying out polymerization reaction at 50-95 ℃ under the protection of nitrogen to obtain a polymer solution, and adjusting the viscosity to obtain an electrospinning solution;
the comonomers in the grafting liquid and the electrospinning liquid comprise acrylic acid, methacrylic acid, styrene sulfonic acid, sodium styrene sulfonate, sodium acrylate, sodium methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, butyl acrylate, butyl methacrylate, methacrylamide propyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, acrylamide, trimethylolpropane triacrylate, pentaerythritol triacrylate and N, N-methylene bisacrylamide;
the preparation method of the electric treatment fabric comprises the steps of carrying out irradiation pretreatment on the fabric to obtain the electric treatment fabric; the fabric comprises woven fabric, knitted fabric and non-woven fabric; the fiber of the fabric comprises terylene, chinlon, acrylon, polypropylene fiber, vinylon and modacrylic chloride; the irradiation includes high-energy gamma ray irradiation, electron beam irradiation, plasma irradiation, and ultraviolet irradiation.
2. The method for preparing an ion exchange fabric membrane according to claim 1, wherein the treatment method of graft polymerization comprises removing air from the fabric surface and the inside by pressing or inert gas.
3. The method of claim 1, wherein the plasma irradiation comprises corona discharge and dielectric barrier discharge.
4. The method for preparing an ion exchange fabric membrane according to claim 1, wherein the voltage of the electrostatic spinning is 7-20 kilovolts, the distance between a spinneret and a receiving screen is 10-20 centimeters, and the spinning speed is 1.0-35.0 milliliters per hour.
5. The method for preparing an ion exchange fabric membrane according to claim 1, wherein the temperature of the chemical crosslinking is 50-120 ℃, and the curing time is 0.5-5 hours.
6. The method of claim 1, wherein the cross-linking agent comprises bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, glutaraldehyde, hexamethylenetetramine, trimethylolmelamine, hexamethylolmelamine, dimethylol dihydroxyethylene urea, butanetetracarboxylic acid, adipic acid, succinic acid, maleic anhydride, triethyltetramine, diethyltriamine, and ethylenediamine.
7. The method for preparing an ion exchange fabric membrane according to claim 1, wherein the solvent is an organic solvent, water or a mixed solvent of the organic solvent and the water;
the organic solvent comprises methanol, ethanol, acetone, butanone, tetrahydrofuran, ethyl acetate and butyl acetate.
CN201910230134.5A 2019-03-26 2019-03-26 Preparation method of ion exchange fabric membrane Active CN110106703B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910230134.5A CN110106703B (en) 2019-03-26 2019-03-26 Preparation method of ion exchange fabric membrane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910230134.5A CN110106703B (en) 2019-03-26 2019-03-26 Preparation method of ion exchange fabric membrane

Publications (2)

Publication Number Publication Date
CN110106703A CN110106703A (en) 2019-08-09
CN110106703B true CN110106703B (en) 2021-12-10

Family

ID=67484637

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910230134.5A Active CN110106703B (en) 2019-03-26 2019-03-26 Preparation method of ion exchange fabric membrane

Country Status (1)

Country Link
CN (1) CN110106703B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102965929A (en) * 2012-10-12 2013-03-13 苏州大学 Preparation method and application of modified polypropylene non-woven fabric
CN103924445A (en) * 2014-04-17 2014-07-16 苏州大学 Polypropylene industrial yarn cloth grafting modification method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102965929A (en) * 2012-10-12 2013-03-13 苏州大学 Preparation method and application of modified polypropylene non-woven fabric
CN103924445A (en) * 2014-04-17 2014-07-16 苏州大学 Polypropylene industrial yarn cloth grafting modification method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Co60预辐照接枝共聚制备PET离子交换纤维的研究;陈德峻 等;《华南理工大学学报（自然科学版）》;19941215;第22卷(第6期);摘要和第20页1.3接枝反应，第21-23页2.2接枝织物的离子交换性能，第21页2.1.3氧气对接枝反应的影响 *
Fabrication of electrospun polyacrylonitrile ion-exchange membranes for application in lysozym;Chiu H T 等;《express polymer letters》;20110430;第5卷(第4期);摘要和第309页2.2 Electrospinning of polyacrylonitrile *
涤纶纤维制品自由基接枝聚合改性及其应用性能研究;石小丽;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20080415(第4期);第20页2.2.2.2等离子处理，第21页2.2.2.3接枝聚合反应，第31页2.3.8接枝率对涤纶织物力学性能的影响 *

Also Published As

Publication number Publication date
CN110106703A (en) 2019-08-09

Similar Documents

Publication Publication Date Title
JP7379587B2 (en) Chemically modified base material
CN107587268A (en) A kind of preparation method of environment-friendly solvent type Static Spinning waterproof humidity-permeant film
FR2543354A1 (en) ION EXCHANGE MEMBRANES REINFORCED WITH NON-WOVEN CARBON FIBERS
CN103924384B (en) Preparation method of constant-hydrophilic graft-modified chlorinated polymer micro/nano fiber film
CN112973653B (en) Preparation method of Mxene membrane adsorbing material based on polyamidoxime and uranium extraction method
CN114425243B (en) Metal-organic framework material separation membrane and preparation method and application thereof
JPH09194609A (en) Ion-exchange membrane and its preparation
CN100335702C (en) Non-woven fabric treatment
CN110106703B (en) Preparation method of ion exchange fabric membrane
JP4035106B2 (en) Method for preparing a graft copolymer membrane
KR100992557B1 (en) Preparation Method of Ion Selective Fibrous Nano-form using Hyperbranched Polystyrene with Reactive Acrylic Resin
CN101683639B (en) Sizing device and sizing method for preparing polyethylene fibre reinforced composite material
CN110201552A (en) With micropore/meso-hole structure nano-porous fiber film and preparation method thereof
CN101736436B (en) Composite electrostatic spinning integrated by initiator and preparation method thereof
CN101748603A (en) Method for modifying surface of composite electrostatic spun filament integrated by initiator
KR100783802B1 (en) Manufacturing method of surface-modified yarn by uv and apparatus thereof
KR20180017518A (en) Oxy-PAN nanofibrous web as adsorbent for heavy metal ions and manufacturing method thereof
CN117798042A (en) Filter screen with antibacterial function, preparation method thereof and filter
CN110026160A (en) A kind of preparation method of weak base type ion exchange fiber
CN112677577B (en) Waterproof and moisture permeable composite fabric material with high tensile strength and preparation process thereof
RU2795192C1 (en) Layered base of electrode for capacitive deionization and method for its manufacture
CN114246980B (en) Partially absorbable hernia repair patch and preparation method thereof
JP2010001392A (en) Anion exchanger and method for producing it
Ghafoor et al. Synthesis of cation exchange membrane from polypropylene fabric using simultaneous radiation grafting
CN115874356A (en) Lithium ion sieve nano fiber felt and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant