CN111793235A - Preparation method of cation exchange membrane with IPN structure - Google Patents

Preparation method of cation exchange membrane with IPN structure Download PDF

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CN111793235A
CN111793235A CN202010512068.3A CN202010512068A CN111793235A CN 111793235 A CN111793235 A CN 111793235A CN 202010512068 A CN202010512068 A CN 202010512068A CN 111793235 A CN111793235 A CN 111793235A
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cation exchange
exchange membrane
ipn structure
preparing
membrane
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王彬
潘礼德
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Jinhua Jin Qiu Environmental Protection Water Treatment Co ltd
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Jinhua Jin Qiu Environmental Protection Water Treatment Co ltd
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/422—Electrodialysis
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D67/0002—Organic membrane manufacture
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
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    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
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    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
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    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/42—Ion-exchange membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
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    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
    • C—CHEMISTRY; METALLURGY
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    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes

Abstract

The invention belongs to the technical field of ion exchange membranes, and particularly relates to a preparation method of a cation exchange membrane with an IPN structure. The invention comprises taking two different aromatic polymers as main materials, mixing the two polymers according to the mass ratio of 1:0.5-1.5 to obtain a premix; adding the prepared premix into an extruder, adding a crosslinking initiator, heating to 150-; and sulfonating the prepared base membrane by using a sulfonating device to obtain the cation exchange membrane. The invention takes two different aromatic polymers as main materials, and the cation exchange membrane with the IPN structure is obtained after cross-linking polymerization, thereby eliminating the structural defect that the cation exchange resin powder and the macromolecular binder in the traditional heterogeneous cation exchange membrane are incompatible, and having lower membrane resistance and higher exchange capacity.

Description

Preparation method of cation exchange membrane with IPN structure
Technical Field
The invention belongs to the technical field of ion exchange membranes, and particularly relates to a preparation method of a cation exchange membrane with an IPN structure.
Background
Ion exchange membranes are one of the key components in electrodialysis devices. The electrodialysis device is widely used for desalting seawater and brackish water to prepare drinking water, desalting and purifying organic compounds, preparing high-purity water and ultrapure water for semiconductor industry, electronic industry and power plant pressure boilers, treating and recycling industrial wastewater and the like. The cation exchange membrane as a key ionic membrane has important application value in the fields of electrodialysis, water treatment, fuel cells and the like. At present, part of cation exchange membranes are commercialized, but the prior art also has the problems of high membrane resistance and small exchange capacity.
For example, chinese invention patent application discloses a cation exchange membrane and a method for producing the same [ application No.: 201380052607.8], which patent application includes a polyvinyl alcohol-based copolymer P containing an anionic polymer segment having an anionic group and a vinyl alcohol polymer segment and having a microphase-separated structure with a domain size X in the range of 0nm < X.ltoreq.150 nm; and a method for producing the cation exchange membrane, the method comprising: the polyvinyl alcohol copolymer P contains a salt C, and a film is formed from the polyvinyl alcohol copolymer after adjustment by adjusting the weight ratio C/P of the salt C to the polyvinyl alcohol copolymer P to 4.5/95.5 or less.
The patent application of the invention claims that an anionic polymer segment having an anionic group and a vinyl alcohol polymer segment can suppress microphase separation, and that the ion channel structure does not change and has excellent durability, but it does not solve the above problems.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of a cation exchange membrane with an IPN structure, which has low membrane resistance and high exchange capacity.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a cation exchange membrane with an IPN structure comprises the following steps:
the method comprises the following steps: taking two different aromatic polymers as main materials, and mixing the two polymers according to the mass ratio of 1:0.5-1.5 to obtain a premix;
step two: adding the premix prepared in the step one into an extruder, adding a crosslinking initiator, heating to 150-260 ℃ for crosslinking, extruding by the extruder, and forming a film through a die head to obtain a base film;
step three: and sulfonating the base membrane prepared in the second step by using a sulfonating device to obtain the cation exchange membrane.
In the above method for preparing a cation exchange membrane with an IPN structure, the main material in the first step includes any two of polyetheretherketone, phthalazinone polyetherketone, and a styrene thermoplastic elastomer.
In the preparation method of the cation exchange membrane with the IPN structure, the crosslinking initiator in the second step is obtained by mixing the crosslinking agent and the initiator, and the mass ratio of the crosslinking agent to the initiator is 1: 0.05-0.5.
In the above method for preparing the cation exchange membrane with the IPN structure, the crosslinking agent is divinylbenzene or dicumyl peroxide, and the initiator is dibenzoyl peroxide or azobisisobutyronitrile.
In the preparation method of the cation exchange membrane with the IPN structure, the mass ratio of the crosslinking initiator to the main material in the second step is 0.01-0.1: 1.
In the preparation method of the cation exchange membrane with the IPN structure, the extruder in the second step is a three-screw extruder, the speed-rotation ratio of the three-screw extruder is 1:20-100, and the length-diameter ratio is 1: 20-60.
In the preparation method of the cation exchange membrane with the IPN structure, the sulfonation device comprises an unreeling mechanism, a traction mechanism, a sulfonation groove, a drying box and a reeling mechanism which are sequentially communicated, wherein an ion exchange membrane is reeled in the unreeling mechanism, a sulfonation solution for sulfonating the ion exchange membrane is arranged in the sulfonation groove, and a cation exchange membrane is reeled in the reeling mechanism.
In the preparation method of the cation exchange membrane with the IPN structure, the unreeling speed of the unreeling mechanism is 0.05-0.85 m/min, the sulfonation solution in the sulfonation tank is a sulfuric acid solution with the mass fraction of more than 56%, and the temperature of the sulfonation solution is 50-86 ℃.
In the above method for preparing the cation exchange membrane with the IPN structure, the drying temperature in the drying oven is 60-80 ℃.
In the preparation method of the cation exchange membrane with the IPN structure, the main materials in the step one are mixed by a high-speed mixer for more than 30min to obtain a premix.
Compared with the prior art, the invention has the advantages that:
1. the invention takes two different aromatic polymers as main materials, and the cation exchange membrane with the IPN structure is obtained after cross-linking polymerization, thereby eliminating the structural defect that the cation exchange resin powder and the macromolecular binder in the traditional heterogeneous cation exchange membrane are incompatible, and having lower membrane resistance and higher exchange capacity.
2. The preparation method of the cation exchange membrane provided by the invention has the advantages of simple manufacturing method, easily controlled conditions and easily operated process, and is suitable for large-scale popularization and application.
Drawings
FIG. 1 is a schematic diagram of the structure of an IPN;
FIG. 2 is a transmission electron micrograph of the cation exchange membrane prepared in example 1;
FIG. 3 is a schematic diagram of the configuration of the sulfonation unit;
in the figure: the device comprises an unwinding mechanism 1, a traction mechanism 2, a sulfonation groove 3, a drying box 4, a winding mechanism 5 and a sulfonation device 100.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Example 1
The embodiment provides a preparation method of a cation exchange membrane with an IPN structure, which is shown in fig. 1 to 3 and comprises the following steps:
the method comprises the following steps: taking 100g of polyether-ether-ketone and 50g of SEBS resin as main materials, adding the main materials into a high-speed mixer, and mixing for 30min to obtain a premix;
step two: adding the premix prepared in the step one into a three-screw extruder with the length-diameter ratio of 1:20-60, adding a crosslinking initiator, wherein the crosslinking initiator is formed by mixing 1g of divinylbenzene and 0.5g of dibenzoyl peroxide, heating to 150 ℃ for crosslinking, the rotation speed ratio of the three-screw extruder is 1:20 in the crosslinking process, and extruding by the three-screw extruder to form a film through a die head to obtain a base film;
step three: winding the base film prepared in the step two onto an unwinding mechanism 1, drawing the base film into a sulfonation tank 3 by using a drawing mechanism 2, wherein the unwinding speed of the unwinding mechanism 1 is 0.05m/min, sulfonating the base film by passing through a 56% sulfuric acid solution at 50 ℃ in the sulfonation tank 3, and grafting a sulfonic functional group (R-HSO) onto a main material at the time3) And then the obtained product enters a drying box 4 to be dried at 60 ℃ to obtain a cation exchange membrane, and finally the cation exchange membrane is wound on a winding mechanism 5.
The high-speed mixing machine, the three-screw extruder, the die head, the unreeling mechanism 1, the traction mechanism 2, the sulfonation tank 3, the drying box 4 and the reeling mechanism 5 can all adopt devices or structures which can realize corresponding functions in the prior art, when the three-screw extruder extrudes and forms a film through the die head, the width and the thickness of the extruded ion exchange film can be controlled by adjusting the die head, for example, the width of the ion exchange film can be adjusted to be between 400 and 1000mm, and the thickness can be adjusted to be between 0.15 and 0.4 mm.
The polyether-ether-ketone is a high polymer consisting of a repeating unit containing one ketone bond and two ether bonds in a main chain structure, and belongs to a special high polymer material. Has the physical and chemical properties of high temperature resistance, chemical corrosion resistance and the like, is a semi-crystalline polymer material, has the melting point of 334 ℃, the softening point of 168 ℃, the tensile strength of 132-. Generally, a polyaryl ether high polymer obtained by condensation with aromatic dihydric phenol is adopted. Such materials have a large number of applications in the aerospace, medical device and industrial fields.
The SEBS resin is a saturated SBS resin or hydrogenated SBS resin, and is prepared by hydrogenating a special linear SBS resin to saturate double bonds, and the SBS resin is moderately and directionally hydrogenated in the presence of a catalyst to hydrogenate a polybutadiene chain segment into a polyethylene (E) and a polybutylene (B) chain segment, so that the SEBS resin is called SEBS resin, and the SBS resin is a styrene-butadiene-styrene block copolymer.
Example 2
The embodiment provides a preparation method of a cation exchange membrane with an IPN structure, which is shown in fig. 1 to 3 and comprises the following steps:
the method comprises the following steps: taking 100g of polyether-ether-ketone and 150g of SIS resin as main materials, adding the main materials into a high-speed mixer, and mixing for 60min to obtain a premix;
step two: adding the premix prepared in the step one into a three-screw extruder with the length-diameter ratio of 1:60, and adding a crosslinking initiator, wherein the crosslinking initiator is prepared by mixing 19g of divinylbenzene and 1g of dibenzoyl peroxide, heating to 260 ℃ for crosslinking, the speed-rotation ratio of the three-screw extruder is 1:100 in the crosslinking process, and the three-screw extruder extrudes and forms a film through a die head to obtain a base film;
step three: and (2) winding the base membrane prepared in the step (II) onto an unwinding mechanism 1, drawing the base membrane into a sulfonation tank 3 by using a drawing mechanism 2, controlling the unwinding speed of the unwinding mechanism 1 to be 0.85m/min, sulfonating 90% sulfuric acid solution passing through the sulfonation tank 3 at the temperature of 86 ℃, drying the sulfonated solution in a drying box 4 at the temperature of 80 ℃ to obtain a cation exchange membrane, and finally winding the cation exchange membrane onto a winding mechanism 5.
The SIS resin is a styrene-isoprene-styrene segmented copolymer, has excellent corrugated sealing property and high-temperature retention, has unique superiority when being used as an adhesive due to a unique micro phase-separated structure, is widely applied to the fields of medical treatment, electrical insulation, packaging, protection and masking, marking, bonding and fixing and the like, and particularly has the characteristics of no solvent, no pollution, low energy consumption, simple equipment and wide bonding range in the production of hot-melt pressure-sensitive adhesive (HMPSA).
Example 3
The embodiment provides a preparation method of a cation exchange membrane with an IPN structure, which is shown in fig. 1 to 3 and comprises the following steps:
the method comprises the following steps: taking 100g of polyether-ether-ketone and 100g of heteronaphthalene biphenyl polyether-ketone as main materials, wherein the heteronaphthalene biphenyl polyether-ketone is PPEK resin, and adding the PPEK resin into a high-speed mixer to mix for 45min to obtain a premix;
step two: adding the premix prepared in the step one into a three-screw extruder with the length-diameter ratio of 1:40, and adding a crosslinking initiator, wherein the crosslinking initiator is prepared by mixing 8g of divinylbenzene and 2g of dibenzoyl peroxide, heating to 210 ℃ for crosslinking, the speed-rotation ratio of the three-screw extruder in the crosslinking process is 1:60, and extruding by the three-screw extruder to form a film through a die head to obtain a base film;
step three: and (2) winding the base membrane prepared in the step (II) onto an unwinding mechanism 1, drawing the base membrane into a sulfonation tank 3 by using a drawing mechanism 2, controlling the unwinding speed of the unwinding mechanism 1 to be 0.45m/min, sulfonating 80% sulfuric acid solution passing through the sulfonation tank 3 at 68 ℃, drying the sulfonated solution in a drying oven 4 at 70 ℃ to obtain a cation exchange membrane, and finally winding the cation exchange membrane onto a winding mechanism 5.
Example 4
The embodiment provides a preparation method of a cation exchange membrane with an IPN structure, which is shown in fig. 1 to 3 and comprises the following steps:
the method comprises the following steps: taking 100g of polyether-ether-ketone and 100g of SBS resin as main materials, adding the main materials into a high-speed mixer, and mixing for 45min to obtain a premix;
step two: adding the premix prepared in the step one into a three-screw extruder with the length-diameter ratio of 1:40, and adding a crosslinking initiator, wherein the crosslinking initiator is formed by mixing 8g of dicumyl peroxide and 2g of azobisisobutyronitrile, heating to 210 ℃ for crosslinking, the rotation speed ratio of the three-screw extruder is 1:60 in the crosslinking process, and extruding by the three-screw extruder to form a film through a die head to obtain a base film;
step three: and (2) winding the base membrane prepared in the step (II) onto an unwinding mechanism 1, drawing the base membrane into a sulfonation tank 3 by using a drawing mechanism 2, controlling the unwinding speed of the unwinding mechanism 1 to be 0.45m/min, sulfonating 80% sulfuric acid solution passing through the sulfonation tank 3 at 68 ℃, drying the sulfonated solution in a drying oven 4 at 70 ℃ to obtain a cation exchange membrane, and finally winding the cation exchange membrane onto a winding mechanism 5.
Example 5
The embodiment provides a preparation method of a cation exchange membrane with an IPN structure, which is shown in fig. 1 to 3 and comprises the following steps:
the method comprises the following steps: taking 100g of polyether-ether-ketone and 100g of SEPS resin as main materials, adding the main materials into a high-speed mixer, and mixing for 45min to obtain a premix;
step two: adding the premix prepared in the step one into a three-screw extruder with the length-diameter ratio of 1:40, and adding a crosslinking initiator, wherein the crosslinking initiator is prepared by mixing 8g of divinylbenzene and 2g of azobisisobutyronitrile, heating to 210 ℃ for crosslinking, the speed-rotation ratio of the three-screw extruder is 1:60 in the crosslinking process, and the three-screw extruder extrudes and forms a film through a die head to obtain a base film;
step three: and (2) winding the base membrane prepared in the step (II) onto an unwinding mechanism 1, drawing the base membrane into a sulfonation tank 3 by using a drawing mechanism 2, controlling the unwinding speed of the unwinding mechanism 1 to be 0.45m/min, sulfonating 80% sulfuric acid solution passing through the sulfonation tank 3 at 68 ℃, drying the sulfonated solution in a drying oven 4 at 70 ℃ to obtain a cation exchange membrane, and finally winding the cation exchange membrane onto a winding mechanism 5.
The SEPS resin is hydrogenated styrene isoprene copolymer, and also belongs to one of styrene thermoplastic elastomers.
Example 6
The embodiment provides a preparation method of a cation exchange membrane with an IPN structure, which is shown in fig. 1 to 3 and comprises the following steps:
the method comprises the following steps: taking 100g of SBS resin and 100g of heteronaphthalene biphenyl polyether ketone, adding into a high-speed mixer, and mixing for 45min to obtain a premix;
step two: adding the premix prepared in the step one into a three-screw extruder with the length-diameter ratio of 1:40, and adding a crosslinking initiator, wherein the crosslinking initiator is prepared by mixing 8g of dicumyl peroxide and 2g of dibenzoyl peroxide, heating to 210 ℃ for crosslinking, the speed ratio of the three-screw extruder in the crosslinking process is 1:60, and extruding by the three-screw extruder to form a film through a die head to obtain a base film;
step three: and (2) winding the base membrane prepared in the step (II) onto an unwinding mechanism 1, drawing the base membrane into a sulfonation tank 3 by using a drawing mechanism 2, controlling the unwinding speed of the unwinding mechanism 1 to be 0.45m/min, sulfonating 80% sulfuric acid solution passing through the sulfonation tank 3 at 68 ℃, drying the sulfonated solution in a drying oven 4 at 70 ℃ to obtain a cation exchange membrane, and finally winding the cation exchange membrane onto a winding mechanism 5.
Comparative example 1
This embodiment provides a method for preparing a cation exchange membrane, which is shown in fig. 1 to 3 and includes the following steps:
the method comprises the following steps: taking 100g of polyether-ether-ketone as a main material;
step two: adding the main material in the step one into a three-screw extruder with the length-diameter ratio of 1:40, and adding a crosslinking initiator, wherein the crosslinking initiator is formed by mixing 4g of divinylbenzene and 1g of dibenzoyl peroxide, heating to 210 ℃ for crosslinking, the speed-rotation ratio of the three-screw extruder in the crosslinking process is 1:60, and extruding by the three-screw extruder to form a film through a die head to obtain a base film;
step three: and (2) winding the base membrane prepared in the step (II) onto an unwinding mechanism 1, drawing the base membrane into a sulfonation tank 3 by using a drawing mechanism 2, controlling the unwinding speed of the unwinding mechanism 1 to be 0.45m/min, sulfonating 80% sulfuric acid solution passing through the sulfonation tank 3 at 68 ℃, drying the sulfonated solution in a drying oven 4 at 70 ℃ to obtain a cation exchange membrane, and finally winding the cation exchange membrane onto a winding mechanism 5.
Comparative example 2
This embodiment provides a method for preparing a cation exchange membrane, which is shown in fig. 1 to 3 and includes the following steps:
the method comprises the following steps: taking 100g of polyether-ether-ketone and 100g of heteronaphthalene biphenyl polyether-ketone as main materials, wherein the heteronaphthalene biphenyl polyether-ketone is PPEK resin, and adding the PPEK resin into a high-speed mixer to mix for 45min to obtain a premix;
step two: adding the premix prepared in the step one into a three-screw extruder with the length-diameter ratio of 1:40, and adding a crosslinking initiator, wherein the crosslinking initiator is prepared by mixing 8g of divinylbenzene and 2g of dibenzoyl peroxide, heating to 140 ℃ for crosslinking, the speed-rotation ratio of the three-screw extruder in the crosslinking process is 1:120, and extruding by the three-screw extruder to form a film through a die head to obtain a base film;
step three: and (2) winding the base membrane prepared in the step (II) onto an unwinding mechanism 1, drawing the base membrane into a sulfonation tank 3 by using a drawing mechanism 2, controlling the unwinding speed of the unwinding mechanism 1 to be 0.45m/min, sulfonating 80% sulfuric acid solution passing through the sulfonation tank 3 at 68 ℃, drying the sulfonated solution in a drying oven 4 at 70 ℃ to obtain a cation exchange membrane, and finally winding the cation exchange membrane onto a winding mechanism 5.
Application example 1
A cation exchange membrane 1 was produced by the method for producing a cation exchange membrane having an IPN structure described in example 1;
a cation exchange membrane 2 was prepared by the method for preparing a cation exchange membrane having an IPN structure described in example 2;
a cation exchange membrane 3 was produced by the method for producing a cation exchange membrane having an IPN structure described in example 3;
preparing a cation exchange membrane 4 by using the preparation method of the cation exchange membrane with the IPN structure described in the comparative example 1;
preparing a cation exchange membrane 5 by using the preparation method of the cation exchange membrane with the IPN structure described in the comparative example 2;
the exchange membranes with the same area are respectively cut from the cation exchange membrane 1, the cation exchange membrane 2, the cation exchange membrane 3, the cation exchange membrane 4 and the cation exchange membrane 5, parameters such as the average membrane thickness, the water content, the exchange capacity, the membrane surface resistance, the selective transmittance, the PH stability, the bursting strength and the like are respectively measured, and the results are shown in the following table:
Figure BDA0002528754140000091
Figure BDA0002528754140000101
and (4) analyzing results: from the above table, it can be seen that the overall performance of the cation exchange membrane 4 and the cation exchange membrane 5, especially the exchange capacity and the membrane area resistance are far different from those of the cation exchange membranes 1 to 3, which may be caused by the fact that the cation exchange membrane 4 is made of a single material as a main material and cannot form an IPN structure, the crosslinking temperature and the crosslinking speed of the cation exchange membrane 5 are not in an appropriate range, and the IPN structure cannot be well formed, so that the cation exchange membrane provided by the invention has lower membrane resistance and higher exchange capacity, and the expected purpose of the invention is achieved.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Although the terms unreeling mechanism 1, drawing mechanism 2, sulfonation tank 3, drying oven 4, reeling mechanism 5, sulfonation unit 100, etc. are used more herein, the possibility of using other terms is not excluded. These terms are used merely to more conveniently describe and explain the nature of the present invention; they are to be construed as being without limitation to any additional limitations that may be imposed by the spirit of the present invention.

Claims (10)

1. A preparation method of a cation exchange membrane with an IPN structure is characterized by comprising the following steps:
the method comprises the following steps: taking two different aromatic polymers as main materials, and mixing the two polymers according to the mass ratio of 1:0.5-1.5 to obtain a premix;
step two: adding the premix prepared in the step one into an extruder, adding a crosslinking initiator, heating to 150-260 ℃ for crosslinking, extruding by the extruder, and forming a film through a die head to obtain a base film;
step three: and sulfonating the base membrane prepared in the second step by using a sulfonating device (100) to obtain the cation exchange membrane.
2. The method for preparing a cation exchange membrane of IPN structure according to claim 1, wherein: the main materials in the first step comprise any two of polyether-ether-ketone, naphthalene biphenyl polyether-ketone and styrene thermoplastic elastomer.
3. The method for preparing a cation exchange membrane of IPN structure according to claim 1, wherein: and the crosslinking initiator in the second step is obtained by mixing a crosslinking agent and an initiator, wherein the mass ratio of the crosslinking agent to the initiator is 1: 0.05-0.5.
4. The method for preparing a cation exchange membrane with an IPN structure according to claim 3, wherein: the cross-linking agent is divinylbenzene or dicumyl peroxide, and the initiator is dibenzoyl peroxide or azobisisobutyronitrile.
5. The method for preparing a cation exchange membrane of IPN structure according to claim 1, wherein: the mass ratio of the crosslinking initiator to the main material in the second step is 0.01-0.1: 1.
6. The method for preparing a cation exchange membrane of IPN structure according to claim 1, wherein: the extruder in the second step is a three-screw extruder, the speed-rotation ratio of the three-screw extruder is 1:20-100, and the length-diameter ratio is 1: 20-60.
7. The method for preparing a cation exchange membrane of IPN structure according to claim 1, wherein: sulfonation device (100) are including unwinding mechanism (1), drive mechanism (2), sulfonation groove (3), drying cabinet (4) and winding mechanism (5) that communicate in proper order, it has ion exchange membrane to coil in unwinding mechanism (1), it has the sulfonated solution that is used for sulfonated ion exchange membrane to coil in sulfonation groove (3), it has cation exchange membrane to coil in winding mechanism (5).
8. The method for preparing a cation exchange membrane of IPN structure according to claim 7, wherein: the unreeling speed of the unreeling mechanism (1) is 0.05-0.85 m/min, the sulfonation solution in the sulfonation tank (3) is a sulfuric acid solution with the mass fraction of more than 56%, and the temperature of the sulfonation solution is 50-86 ℃.
9. The method for preparing a cation exchange membrane of IPN structure according to claim 7, wherein: the drying temperature in the drying box (4) is 60-80 ℃.
10. The method for preparing a cation exchange membrane of IPN structure according to claim 1, wherein: and (3) mixing the main materials in the step one for more than 30min by using a high-speed mixer to obtain a premix.
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