CN106968110B - Fluorine-containing two-sided filled composite film of conducting polymer containing chlorine of one kind and preparation method thereof - Google Patents
Fluorine-containing two-sided filled composite film of conducting polymer containing chlorine of one kind and preparation method thereof Download PDFInfo
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- CN106968110B CN106968110B CN201710251603.2A CN201710251603A CN106968110B CN 106968110 B CN106968110 B CN 106968110B CN 201710251603 A CN201710251603 A CN 201710251603A CN 106968110 B CN106968110 B CN 106968110B
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- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
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Abstract
The invention discloses a kind of fluorine-containing two-sided filled composite films of conducting polymer containing chlorine and preparation method thereof, the two-sided filled composite thin-film material of fluorine-containing conducting polymer containing chlorine includes microporous membrane skeleton and fluorine-containing conducting polymer containing chlorine, the two-sided hole of the microporous membrane skeleton is more than 60% to be filled by fluorine-containing conductive polymer resin containing chlorine, its physical mechanical strength is high, waterproof, oil resistant, pollution resistance are higher, this film is able to satisfy to resisting water and prevent that poisonous and harmful chemicals intrusion performance is higher, penetrability is higher；When being applied to biochemical protective clothes, there is light and the permanent protective property energy to water and poisonous and harmful chemicals, fighting capacity that is comfortable, warming, can greatly promoting soldier；For the application of fuel cell, because of its electrical conductivity height, the electrical property of acquisition is preferable, and fuel such as hydrogen or alcohol compared with completely burned compared with can utilize.
Description
Technical field
The present invention relates to the fluorine-containing filled composite of conductive polymer resin containing chlorine thin-film materials, and in particular to fluorine-containing conductive containing chlorine
Macromolecule resin filled composite thin-film material and preparation method thereof.
Background technique
Homopolymerization, modification or the copolymerized macromolecule resin of fluoro containing polymers, especially tetrafluoroethene all have excellent physics
Mechanical performance and chemical stability, in chemical materials, mechano-electronic, aerospace, military project protection, new material and new energy etc.
Each field, which suffers from, to be widely applied；Macromolecule containing chlorine, as the homopolymerization of chlorotrifluoroethylene, modification or copolymerized macromolecule resin are equal
With excellent physical mechanical property and anti-chemical penetrability, there is significant contribution in chemical protection.Fluorine-containing conducting polymer is such as
The Nafion resin of Du Pont has excellent electric conductivity and chemical stability, is widely used in fuel cell and chlor-alkali cell, but
There are still many disadvantages, if electric conductivity is high not enough, the electrical conductivity at room temperature (Conductivity) < 0.1 (S/cm) of monofilm；
Chemical penetrability is high, can not effectively obstruct poisonous and harmful chemicals and penetrate.
Expanded PTFE preparation is the polytetrafluoroethyldispersion dispersion resin using high-crystallinity, is obtained through biaxial tension extruding
, with the microcellular structure that height micron or nanofiber are combined closely, there is excellent physical and chemical performance, mechanical performance is prevented
Water gas permeability and chemical stability just be used to manufacture wire cable insulating material, artificial blood vessel, sealing since the seventies
Band, environmental protection filtering and garment material etc.；But the disadvantage is that the paracentesis resistance of these microns or nanofiber is bad, and by
These microns or nanofiber will continue to be elongated and pull loose after power, and membrane tissue is caused to deform, and leads to functional decline, seriously affects
Film integral protection sexual function.
Summary of the invention
In view of the deficiencies of the prior art, the present invention is directed to propose a kind of fluorine-containing two-sided filled composite of conducting polymer containing chlorine is thin
Membrane material, mechanical strength and waterproof with higher, moisture-inhibiting, resistance to greasy dirt, water-fastness, fire-retardant, antibiotic weapon penetrates and height is led
The outstanding physical and chemical performance such as electrical.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of fluorine-containing two-sided filled composite film of conducting polymer containing chlorine, including microporous membrane skeleton contain chlorine conduction with fluorine-containing
Macromolecule resin, the two-sided pore volume of the microporous membrane skeleton are more than 60% by the fluorine-containing institute of conductive polymer resin containing chlorine
Filling；
The fluorine-containing conductive polymer resin containing chlorine is prepared via a method which to obtain: first by weight percentage can be free
Base polymerization fluorine-containing band sulfuryl fluoride liquid monomer 1%~20%, pure water 79%~98%, fluorine-containing surfactant 0.01%~
High-speed stirred is carried out in 1% addition reaction kettle, obtains pre-polymerization precursor emulsion；Then tetrafluoroethene, inclined fluorine second are passed through in reaction kettle
The gas phase mix monomer of one or both of alkene and chlorotrifluoroethylene, reaction pressure are 5 kilograms or more；Then pass to freedom
Base initiator, at 20-120 DEG C, reaction pressure obtains reaction and produces reaction temperature at 5-25 kilograms, reaction time 15-180min
The fluorine-containing macromolecule emulsion containing chlorine with sulfuryl fluoride of object；The fluorine-containing band sulfuryl fluoride liquid monomer and the gas phase mix monomer are practical
Participating in the ratio between total weight of Raolical polymerizable is 1:3~3:1；Radical initiator is passed through total weight and fluorine-containing band sulphonyl
The weight ratio of fluorine liquid monomer is 0.01%~3.0%；Finally it is hydrolyzed containing chlorine with the macromolecule emulsion of sulfuryl fluoride to fluorine-containing,
Fluorine-containing conductive polymer resin containing chlorine is obtained after cohesion, washing, drying again.
The production method of the above-mentioned two-sided filled composite film of fluorine-containing conducting polymer containing chlorine, includes the following steps:
By microporous membrane skeleton in a manner of being coated with or impregnate, in a subtle way the fluorine-containing filling of conductive polymer resin containing chlorine
Composite material is obtained in the two-sided hole of hole film skeleton；Composite material is dried, it is two-sided that fluorine-containing conducting polymer containing chlorine is made
Filled composite film.
It should be noted that the weight ratio of microporous membrane skeleton and the fluorine-containing conductive polymer resin containing chlorine is (5:95)-
(40:60)。
It should be noted that microporous membrane skeleton is prepared via a method which:
First by heat-fusible property fluorine resin or chlorinated and fluorinated resin, the fluorine-containing conductive polymer resin containing chlorine, carbon fiber
Precursor and its copolymer one of can be derivatized to the resin of carbon fiber, polyimides, polyamide, polyester, aramid fiber, polyether-ketone
Spinning is carried out, through hot melt spinneret or wet process spinneret, equably collects into random reticulated macroporous structure, form is received after heat setting
Rice microporous membrane skeleton.
It should be noted that microporous membrane skeleton to be to be coated with or immersion process, by active powdered carbon, graphite powder, graphene, dilute
There is one or more of metal powder, is mixed with the fluorine-containing conductive polymer resin containing chlorine and be packed into its microporous membrane pair together
In the hole in face.
Need further exist for explanation, one of the activity powdered carbon, graphite powder, graphene, rare metal powder or several
The total weight of kind is no more than the 25% of the weight of the fluorine-containing conductive polymer resin containing chlorine.
Further it should be noted that the rare metal powder is silver, platinum or palladium.
It should be noted that heat-fusible property fluorine resin or chlorinated and fluorinated resin include heat-fusible property polytetrafluorethylene copolymer
One or more of object, polytrifluorochloroethylene or its copolymer, Kynoar or its copolymer.
It should be noted that the equivalent number (meq/g) of the fluorine-containing conductive polymer resin containing chlorine is in 400-1500.
It should be noted that in the production method, using wet type phase change method, temperature difference phase change method, dry type solvent method,
Method of electrostatic spinning or ultracentrifugation spin processes carry out spinning.
The beneficial effects of the present invention are: the two-sided filled composite thin-film material of fluorine-containing conducting polymer containing chlorine, object
High mechanical strength is managed, waterproof, oil resistant, pollution resistance are higher, this film is able to satisfy to resistance water and poisonous and harmful chemicals is prevented to invade
Enter that performance is higher, penetrability is higher；When being applied to biochemical protective clothes, have light and to water and poisonous and harmful chemicals
Permanent protective property energy, fighting capacity comfortable, warming, that soldier can be greatly promoted；For the application of fuel cell, because of its electrical conductivity
The electrical property of height, acquisition is preferable, and fuel such as hydrogen or alcohol compared with completely burned compared with can utilize.
Specific embodiment
The invention will be further described below, it should be noted that the present embodiment premised on the technical program,
The detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to the present embodiment.
A kind of fluorine-containing two-sided filled composite film of conducting polymer containing chlorine, including microporous membrane skeleton contain chlorine conduction with fluorine-containing
Macromolecule resin, the two-sided pore volume of the microporous membrane skeleton are more than 60% (preferably > 75%, optimal > 90%) is contained
Fluorine conductive polymer resin containing chlorine is filled；
The fluorine-containing conductive polymer resin containing chlorine is prepared via a method which to obtain: first by weight percentage can be free
Base polymerization fluorine-containing band sulfuryl fluoride liquid monomer 1%~20%, pure water 79%~98%, fluorine-containing surfactant 0.01%~
High-speed stirred is carried out in 1% addition reaction kettle, obtains pre-polymerization precursor emulsion；Then tetrafluoroethene, inclined fluorine second are passed through in reaction kettle
The gas phase mix monomer of one or both of alkene and chlorotrifluoroethylene, reaction pressure are 5 kilograms or more；Then pass to freedom
Base initiator, at 20-120 DEG C, reaction pressure obtains reaction and produces reaction temperature at 5-25 kilograms, reaction time 15-180min
The fluorine-containing macromolecule emulsion containing chlorine with sulfuryl fluoride of object；The fluorine-containing band sulfuryl fluoride liquid monomer and the gas phase mix monomer are practical
Participating in the ratio between total weight of Raolical polymerizable is 1:3~3:1；Radical initiator is passed through total weight and fluorine-containing band sulphonyl
The weight ratio of fluorine liquid monomer is 0.01%~3.0%；Finally it is hydrolyzed containing chlorine with the macromolecule emulsion of sulfuryl fluoride to fluorine-containing,
Fluorine-containing conductive polymer resin containing chlorine is obtained after cohesion, washing, drying again.
Further, the fluorine-containing band sulfuryl fluoride liquid monomer includes CF2=CF-O-Rf-SO2F、CF2=CF-O-Rf1-O-
Rf2-SO2F、CF2=CF-CF2-O-Rf3-SO2It is one or more of in F, wherein Rf、Rf1、Rf2It is 1-6 carbon containing fluoroalkyl, Rf3
It is 0-5 carbon containing fluoroalkyl.
Further, the fluorine-containing band sulfuryl fluoride liquid monomer includes CF2=CF-O-CF2CF2-SO2F, CF2=CF-O-
CF2CFCF3-O-CF2CF2-SO2F、CF2=CF-CF2-O-SO2F、CF2=CF-CF2-O-CF2CF2-SO2One of F or several
Kind.
Further, when the fluorine-containing conductive polymer resin containing chlorine is applied to field of batteries, fluorine-containing band sulfuryl fluoride
Liquid monomer is formed with following weight percent: CF2=CF-O-CF2CF2-SO2F 0-80%, CF2=CF-O-CF2CFCF3-O-
CF2CF2-SO2F 20%-99%, CF2=CF-CF2-O-SO2F 0%-20%, CF2=CF-CF2-O-CF2 CF2-SO2F 0%-
80%.
Further, when the fluorine-containing conductive polymer resin containing chlorine is applied to NBC protection membrane material, fluorine-containing band
Sulfuryl fluoride liquid monomer is formed with following weight percent: CF2=CF-O-CF2CF2-SO2F 0-80%, CF2=CF-O-
CF2CFCF3-O-CF2CF2-SO2F 0%-20%, CF2=CF-CF2-O-SO2F 20%-100%, CF2=CF-CF2-O-CF2
CF2-SO2F 0%-80%.
It further, can be described fluorine-containing containing fluorine-containing without sulphonyl fluorine reagent in the fluorine-containing band sulfuryl fluoride liquid monomer
It is less than or equal to 30% without sulphonyl fluorine reagent and the fluorine-containing weight ratio with sulfuryl fluoride liquid monomer.
Further, it is described it is fluorine-containing without sulphonyl fluorine reagent include contain fluoroalkyl, fluorine-containing alkyl ether, perfluoromethylvinyl
Base ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, 3, one of 3,3- trifluoro propylenes or perfluoro alkyl ethylene or
It is a variety of.
Further, the gas phase mix monomer is contained with molar ratio computing: the tetrafluoroethene of 25%-90%, 0%-70%
The chlorotrifluoroethylene of vinylidene, 5%-50%.
Further, the fluorine-containing surfactant includes the organic matter containing 6-16 carbon, and at least containing a carboxylic acid or
The functional group of person's sulfonic acid.
Further, the radical initiator include one of persulfate, hydrogen peroxide, organic per-compounds or
It is a variety of.
The production method of the above-mentioned two-sided filled composite film of fluorine-containing conducting polymer containing chlorine, includes the following steps:
Step 1: production microporous membrane skeleton: first by raw material with wet type phase change method, temperature difference phase change method, dry type solvent
Method, method of electrostatic spinning or ultracentrifugation spin processes spinning are gushed out through hot melt spinneret or wet process (containing solvent or water) spinneret
About 50-1000 nanometers of its diameter of silk, can uniformly collect into random reticulated macroporous structure, this reticulated macroporous structure is through heat setting
Feasible at nanometer micropore film afterwards, this microporous membrane skeleton weighs about 1-50 grams per square meters, and preferred 3-25 grams per square meters, aperture gap
Rate about 50%-95%, preferred 70%-90%.
The raw material of the microporous membrane skeleton is selected from: fluorine-containing (the containing chlorine) resin of (I) heat-fusible property is selected from heat-fusible property poly- four
Fluoride copolymers, polytrifluorochloroethylene or its copolymer, Kynoar or its copolymer；(II) fluorine-containing conductive polymer containing chlorine
Subtree rouge (equivalents (meq/g) of its sulfonic acid or carboxylic acid in 1000-2000, preferably in 1200-1600)；(III) carbon fiber
Precursor such as polyacrylonitrile and its copolymer or other resins for being derivatized to carbon fiber, it is preferred that carbon fiber precursor was produced
Microporous membrane can become carbon nano-fiber microporous membrane through processing procedures such as high temperature pre-oxidation, graphitization, carbonizations；(IV) other advanced
Engineering material is selected from: polyimides, polyamide (nylon), polyester (PET), aramid fiber, polyether-ketone (PEEK) etc.；
Step 2: fluorine-containing conductive polymer resin containing chlorine is packed into the two-sided hole of microporous membrane skeleton: by step 1
Fluorine-containing conductive polymer resin containing chlorine is packed into microporous membrane bone with coating or immersion process by resulting microporous membrane skeleton
In the two-sided hole of frame, the equivalent number (meq/g) of fluorine-containing conductive polymer resin containing chlorine herein, sulfonic acid or carboxylic acid exists
400-1500, preferably in 500-1100, more preferably in 600-950；Composite material is dried, is made that conducting polymer is two-sided fills out
Fill laminated film；
The two-sided filled composite film of fluorine-containing conducting polymer containing chlorine, microporous membrane skeleton and the fluorine-containing conduction containing chlorine are high
The weight ratio of molecule resin is (5:95)-(40:60), preferably in (10:90)-(30:70), this fluorine-containing conducting polymer containing chlorine
Two-sided filled composite film gross weight is at 5-200 grams per square meters, preferred 10-100 grams per square meters, optimal at 20-90 grams per square meters,
Its thickness is at 3 microns -100 microns, optimal at 10 microns -45 microns preferably at 5 microns -50 microns, fluorine-containing conductive containing chlorine
The electrical conductivity at room temperature (Conductivity) > 0.10 (S/cm) of the two-sided filled composite film of macromolecule, preferred > 0.15 (S/
Cm), more preferably > 0.20 (S/cm)；The two-sided hole major part of microporous membrane skeleton (> 60%, preferred > 75%, optimal >
90%) it is filled by fluorine-containing conductive polymer resin containing chlorine, the two-sided filled composite film air permeable of fluorine-containing conducting polymer containing chlorine
Rate is low, allows time > 3 minute needed for 100 milliliters of air permeable this laminated films with Gurley Permeability gauge measurement, preferred > 10
Minute.
Optionally, in the step 2, by the microporous membrane skeleton of step 1, with coating or immersion process, containing
Fluorine conductive polymer resin containing chlorine, and a small amount of active powdered carbon, graphite powder, graphene or rare metal powder, are packed into its micropore
In the hole of film double-sided, composite material is dried, the two-sided filled composite film of fluorine-containing conducting polymer containing chlorine is made；It is described few
The active powdered carbon of amount, graphite powder, graphene or rare metal powder total weight be no more than fluorine-containing conductive polymer resin containing chlorine
25% weight is preferably no more than the weight of fluorine-containing conductive polymer resin containing chlorine 11%；Preferably, the rare metal powder
Selected from silver (Ag), platinum (Pt), palladium (Pd).
The resulting two-sided filled composite film of fluorine-containing conducting polymer containing chlorine, gross weight is at 5-250 grams per square meters, preferably
At 10-150 grams per square meters, optimal at 20-100 grams per square meters, thickness is at 3 microns -100 microns, preferably at 5 micron -50
Micron, optimal at 10 microns -30 microns, electrical conductivity at room temperature (Conductivity) > 0.1 (S/cm), preferred > 0.15
(S/cm), more preferably > 0.20 (S/cm)；The hole of microporous membrane skeleton it is most of (> 60%, it is preferred > 75%, it is optimal >
90%) by fluorine-containing (containing chlorine) high conductivity macromolecule, and a small amount of active powdered carbon, graphite powder, graphene or rare metal powder institute
Filling, the two-sided filled composite film air permeable rate of fluorine-containing conducting polymer containing chlorine is low, allows 100 milliliters with Gurley Permeability gauge measurement
Time > 3 minute needed for air permeable laminated film, it is preferred > 10 minutes.
Embodiment 1:
In the closed pre-emulsification reaction kettle A of about 100 liters of internal volumes, 39000g pure water, 100g are added under room temperature
Perfluorooctanoic acid, high shear agitation is opened, then toward the weight ratio 70%CF for being slowly added into 5000g in kettle2=CF-O-
CF2CFCF3-O-CF2CF2-SO2F and 30%CF2=CF-O-CF2CF2-SO2The fluorine-containing band sulfuryl fluoride liquid monomer of F mixing composition,
After about 30 points of continuous high speed shear agitation, pre-polymerization precursor emulsion is made；
In the reaction kettle B of another about 100 liters of internal volumes, first deoxygenation in kettle, until oxygen content is less than 20ppm in kettle,
Then the whole pre-polymerization precursor emulsions come from reaction kettle A are added, gas phase mix monomer is passed through in kettle, molar ratio is 90% tetrafluoro second
Alkene and 10% chlorotrifluoroethylene, are warming up to 70 degree, and pressure maintains 11 kilograms in kettle, and 2.5 grams of ammonium persulfates are added and are pre-dissolved in 1 liter
Deionized water, start free radical polymerization.
It is described fluorine-containing total with sulfuryl fluoride liquid monomer and the gas phase mix monomer actual participation Raolical polymerizable
Weight ratio is about 4:5；The total weight that is passed through of radical initiator is with the fluorine-containing weight ratio with sulfuryl fluoride liquid monomer
0.05%；
Reaction temperature is controlled at 70~75 degree, the reaction time one hour, temperature in the kettle is cooled to room temperature, and stirring is stopped,
Reactant blowing obtains the fluorine-containing lotion of conducting polymer containing chlorine, and about 100 nanometers of the average grain diameter of primary particle, lotion contains admittedly
Amount about 19%, the fluorine-containing lotion of conducting polymer containing chlorine of gained is through sulfuryl fluoride (- SO2F) hydrolyze after obtain it is fluorine-containing containing chlorine band sulfonic acid (-
SO3H conducting polymer), after dry, than weighing about 1.99, equivalent number (meq/g) about 900, the electrical conductivity at room temperature of monofilm
(Conductivity)>0.15(S/cm)。
Embodiment 2
In the closed pre-emulsification reaction kettle A of about 100 liters of internal volumes, 39000g deionized water is added under room temperature,
The perfluorooctanoic acid of 100g opens high shear agitation, then toward the weight ratio 80%CF for being slowly added into 5000g in kettle2=CF-O-
CF2CFCF3-O-CF2CF2-SO2F and 20%CF2=CF-O-CF2CF2-SO2The mixture of F, about 30 points of continuous high speed shear agitation
Afterwards, pre-polymerization precursor emulsion is made；In the reaction kettle B of another about 100 liters of internal volumes, first deoxygenation in kettle, until oxygen content in kettle
Less than 20ppm, the whole pre-polymerization precursor emulsions come from reaction kettle A are then added, is passed through gaseous mixture in kettle and mixes monomer, mole
Than being warming up to 70 degree for 75% tetrafluoroethene, 20% vinylidene and 5% chlorotrifluoroethylene, pressure maintains 9 kilograms in kettle,
The deionized water that 2.5 grams of ammonium persulfates are pre-dissolved in 1 liter is added, starts free radical polymerization.
It is described fluorine-containing total with sulfuryl fluoride liquid monomer and the gas phase mix monomer actual participation Raolical polymerizable
Weight ratio is about 5:4；The total weight that is passed through of radical initiator is with the fluorine-containing weight ratio with sulfuryl fluoride liquid monomer
0.05%；
Reaction temperature is controlled at 70~75 degree, the reaction time about one hour, temperature in the kettle is cooled to room temperature, stops stirring
It mixes, reactant blowing, obtains the fluorine-containing lotion of conducting polymer containing chlorine, about 120 nanometers of the average grain diameter of primary particle, lotion is solid
Content about 21%, the fluorine-containing lotion of conducting polymer containing chlorine of gained is through sulfuryl fluoride (- SO2F it is obtained after) hydrolyzing fluorine-containing containing chlorine band sulfonic acid
(-SO3H conducting polymer), after dry, than weighing about 1.91, equivalent number (meq/g) about 800, the room temperature conductance of monofilm
Rate (Conductivity) > 0.20 (S/cm).
Embodiment 3:
In the closed pre-emulsification kettle A of about 100 liters of internal volumes, 39000g pure water is added under room temperature, 100g's is complete
Fluorine ammonium caprylate opens high shear agitation, then toward the weight ratio 50%[CF for being slowly added into 3000g in kettle2=CF-O-
CF2CFCF3-O-CF2CF2-SO2F] and 50%[CF2=CF-CF2-O-CF2CF2-SO2F] mixture, continuous high speed shearing stir
After mixing about 30 points, pre-polymerization precursor emulsion is made；In the reaction kettle B of another about 100 liters of internal volumes, first deoxygenation in kettle, until kettle
In oxygen content be less than 20ppm, the whole pre-polymerization precursor emulsions come from reaction kettle A are then added, are passed through gas phase mix monomer in kettle,
Molar ratio is 50% tetrafluoroethene and 50% chlorotrifluoroethylene, is warming up to 70 degree, and pressure maintains 14 kilograms in kettle, is added 1.5
Gram ammonium persulfate is pre-dissolved in 1 liter of deionized water, starts free radical polymerization.
It is described fluorine-containing total with sulfuryl fluoride liquid monomer and the gas phase mix monomer actual participation Raolical polymerizable
Weight ratio is about 1:3；The total weight that is passed through of radical initiator is with the fluorine-containing weight ratio with sulfuryl fluoride liquid monomer
0.05%；
Reaction temperature is controlled at 70~75 degree, the reaction time about one hour, temperature in the kettle is cooled to room temperature, stops stirring
It mixes, reactant blowing, obtains the fluorine-containing lotion of conducting polymer containing chlorine, about 150 nanometers of the average grain diameter of primary particle, lotion is solid
Content about 22%, the fluorine-containing lotion of conducting polymer containing chlorine of gained is through sulfuryl fluoride (- SO2F it is obtained after) hydrolyzing fluorine-containing containing chlorine band sulfonic acid
(-SO3H conducting polymer), after dry, than weighing about 2.02, the room temperature of equivalent number (meq/g) about 1500, monofilm is electric
Conductance (Conductivity) > 0.02 (S/cm).
Embodiment 4:
In the closed pre-emulsification reaction kettle A of about 100 liters of internal volumes, 39000g deionized water is added under room temperature,
The perfluorooctanoic acid of 300g opens high shear agitation, then toward the weight ratio 20%[CF for being slowly added into 6000g in kettle2=CF-
O-CF2CFCF3-O-CF2CF2-SO2F] and 80%[CF2=CF-CF2-O-CF2CF2-SO2F] mixture, continuous high speed shearing
After stir about 30 divides, pre-polymerization precursor emulsion is made；In the reaction kettle B of another about 100 liters of internal volumes, first deoxygenation in kettle, until
Oxygen content is less than 20ppm in kettle, and the whole pre-polymerization precursor emulsions come from reaction kettle A are then added, are passed through gas phase mix monomer in kettle,
Its molar ratio is 70% tetrafluoroethene and 30% chlorotrifluoroethylene, is warming up to 70 degree, and pressure maintains 10 kilograms in kettle, is added 3
Gram ammonium persulfate is pre-dissolved in 1 liter of deionized water, starts free radical polymerization.
It is described fluorine-containing total with sulfuryl fluoride liquid monomer and the gas phase mix monomer actual participation Raolical polymerizable
Weight ratio is about 3:1；The total weight that is passed through of radical initiator is with the fluorine-containing weight ratio with sulfuryl fluoride liquid monomer
0.05%；
Reaction temperature is controlled at 70~75 degree, the reaction time about one hour, temperature in the kettle is cooled to room temperature, stops stirring
It mixes, reactant blowing, obtains the fluorine-containing lotion of conducting polymer containing chlorine, about 70 nanometers of the average grain diameter of primary particle, lotion is solid
Content about 19.5%, the fluorine-containing lotion of conducting polymer containing chlorine of gained obtain fluorine-containing containing chlorine band sulphur after sulfuryl fluoride (- SO2F) hydrolysis
The conducting polymer of sour (- SO3H), after dry, than weighing about 1.97, the room temperature of equivalent number (meq/g) about 500, monofilm is electric
Conductance (Conductivity) > 0.35 (S/cm).
Embodiment 5
In the closed pre-emulsification kettle A of about 100 liters of internal volumes, 39000g deionized water is added under room temperature, 300g's
Perfluorooctanoic acid opens high shear agitation, then toward the weight ratio 60%CF for being slowly added into 3 kilograms in kettle2=CF-CF2-O-
SO2F and 40%CF2=CF-CF2-O-CF2CF2-SO2After about 30 points of continuous high speed shear agitation, performed polymer is made in the mixture of F
Lotion；In the reaction kettle B of another about 100 liters of internal volumes, first deoxygenation in kettle, until oxygen content is less than 20ppm in kettle, then
The whole pre-polymerization precursor emulsions come from reaction kettle A are added, are passed through gas phase mix monomer in kettle, molar ratio be 25% tetrafluoroethene,
70% vinylidene, 5% chlorotrifluoroethylene, are warming up to 80 degree, and pressure maintains 17 kilograms in kettle, and 1.5 grams of ammonium persulfates are added
It is pre-dissolved in 1 liter of deionized water, starts free radical polymerization.
It is described fluorine-containing total with sulfuryl fluoride liquid monomer and the gas phase mix monomer actual participation Raolical polymerizable
Weight ratio is about 1:2.5；The total weight that is passed through of radical initiator is with the fluorine-containing weight ratio with sulfuryl fluoride liquid monomer
0.05%；
Reaction temperature is controlled at 80~85 degree, the reaction time about 45 minutes, temperature in the kettle is cooled to room temperature, stops stirring
It mixes, reactant blowing, obtains fluorine-containing conducting polymer lotion, about 50 nanometers of the average grain diameter of primary particle, emulsion solid content
About 20%, the fluorine-containing conducting polymer lotion of gained is through sulfuryl fluoride (- SO2F) it is hydrolyzed into sulfonic acid (- SO3H), (- CF2-O-SO2F) water
Solution contains sulfonic acid/carboxylic acid conducting polymer at the fluorine-containing of carboxylic acid (- COOH), after dry, than weighing about 1.72, and equivalent number (meq/
G) about 950, the electrical conductivity at room temperature (Conductivity) > 0.10 (S/cm) of monofilm.
Embodiment 6
By the fluorine-containing conductive polymer resin containing chlorine being made in embodiment 3 and dimethyl acetamide with the weight of about 1:4
Than mixing, heating stirring after resin dissolution, sprays nanofibers with method of electrostatic spinning, about 5 grams of production capacity per minute, produced to receive
Rice fiber filament is collected with release shape paper, and obtained nanofibers are deposited on strippable paper, and strippable paper is with 0.1 meter per minute
Speed is advanced, and collected is about 1 meter of a breadth of nanofiber cortina, this cortina is gradually dried in the case where about 90 DEG C of hot winds are handled
Dry nanofibers film, final line is at about 20 microns of thickness, the nanofibers film that about 100 centimetres of width, and fiber is put down
Equal about 170 nanometers of diameter, through detecting, film weighs about 10 grams per square meters, porosity about 78-82%, specific gravity 0.39, gas permeability
Gurley is surveyed 100 milliliters of air permeable speed of method about 7~12 seconds.
Embodiment 7
Polyacrylonitrile (PAN) resin (is generated into copolymerization poly- third by acrylonitrile and a small amount of acrylic acid first vinegar, the copolymerization of two rouge of methene fourth
Alkene nitrile resin, molecular weight are higher than 6 to 8 and ten thousand) are mixed with dimethyl alum with the weight ratio of about 1:4, heating stirring, resin dissolution
Afterwards, with ultracentrifugation spin processes spray nanofibers, about 20 grams of production capacity per minute, the release shape paper of produced nanofibers
It collects, obtained nanofibers are deposited on strippable paper, and strippable paper obtains speed with 0.1 meter per minute and advances, collected
Be about 1 meter of a breadth of nanofiber cortina, it is thin that this cortina is gradually dried nanofibers in the case where about 160 DEG C of hot winds are handled
Film, final line at about 70 microns of thickness, receive by the nanofibers film that about 100 centimetres of width, the average diameter of fiber about 350
Rice；Through detecting, film weighs about 39 grams per square meters, porosity about 82-86%, and specific gravity 0.28, gas permeability Gurley surveys 100 milliliters of method
Air permeable speed about 13~17 seconds.
Embodiment 8
The polyacrylonitrile nano microporous membrane that will be manufactured in embodiment 7 is heated to about 270 DEG C, heat preservation under air
The color of 2h, polyacrylonitrile (PAN) resin nano microporous membrane gradually become yellow, brown by white, eventually form the pre- of black
Microporous membrane is aoxidized, is polyacrylonitrile linear polymeric after by thermal oxide, a series ofization such as oxidation, pyrolysis, crosslinking, cyclisation occur
It is high molecular as a result, pre-oxidation microporous membrane is then carried out 1600 DEG C of high-temperature process in nitrogen that reaction forms heat-resisting ladder type
Carbonization treatment, then nanofiber further generates the reactions such as crosslinking cyclisation, aromatisation and polycondensation, and it is former to remove hydrogen, nitrogen, oxygen
Son eventually forms the PAN base nano carbon fibre of Two-dimensional Carbon plane of a loop reticular structure with the coarse parallel random graphits structure of synusia
Film, final line at about 15 microns of thickness, receive by the nanofibers film that about 100 centimetres of width, the average diameter of fiber about 160
Rice, through detecting, film weighs about 7 grams per square meters, porosity about 89-93%, and specific gravity 0.27, gas permeability Gurley surveys 100 milliliters of skies of method
Gas penetration speed about 7~9 seconds.
Embodiment 9
ECTFE resin (ethylene and chlorotrifluoroethylene come from Su Wei company) is fine with melt spinning method spray ECTFE
Nano wire is tieed up, about 20 grams of spinneret per minute, produced nanofibers are collected with release shape paper, obtained nanofibers heap
Product is on strippable paper, and strippable paper is advanced with 1 meter of speed per minute, and collected is about 1 meter of a breadth of ECTFE Nanowire
Cortina is tieed up, final line is at about 45 microns of thickness, the nanofibers film that about 100 centimetres of width, the average diameter of fiber about 450
Nanometer, through detecting, film weighs about 20 grams per square meters, porosity about 75-80%, and specific gravity 0.42, gas permeability Gurley surveys 100 milli of method
Lift-off gas penetration speed about 12~15 seconds.
Embodiment 10
PET polyester resin is mixed with ethylene carbonate with the weight ratio of about 1:4, heating stirring, after resin dissolution, slightly
Be coated on strippable paper comprehensively under solution temperature more than 200 DEG C, PET film generated through rapid cooling to room temperature, tear off from
This PET film is gradually dried PET film in the case where about 170 DEG C of hot winds are handled by shape paper, and final line is at about 50 microns of thickness, width about 160
Centimetre nanometer micropore film, through detecting, the film of the fluorine-containing microporous membrane containing chlorine of gained weighs about 15 grams per square meters, porosity about 68-
72%, specific gravity 0.29, gas permeability Gurley is surveyed 100 milliliters of air permeable speed of method about 17~23 seconds.
Embodiment 11
The fluorine-containing conductive polymer resin containing chlorine manufactured in embodiment 1 is first dissolved in dimethyl acetamide/ethyl alcohol
In (1:1) solution, concentration of the fluorine-containing conductive polymer resin containing chlorine in solution about 20% contains what is be made in embodiment 6
Fluorine conducting polymer containing chlorine (equivalent number 1500) microporous membrane skeleton, room temperature two-sided immersion are led containing chlorine made 20% is fluorine-containing
Electric macromolecule (equivalent number 900) solution Rio one minute, takes out the film of immersion, gently scrapes off film surface surplus liquid,
It is slowly dried under 90 degree, i.e. acquisition laminated film；Through detecting, about 25 microns of laminated film final thickness, about 100 centimetres of width
Transparent membrane, film weigh about 45 grams per square meters, and specific gravity 1.81, gas permeability Gurley surveys 100 milliliters of air permeable speed of method and is greater than 3
Minute, composite membrane electrical conductivity (Conductivity) about 0.11 (S/cm).(tensile strength is greater than the mechanical strength of this composite membrane
30MPa) being much better than the individually film obtained by fluorine-containing conducting polymer containing chlorine (equivalent number 900), (tensile strength is less than
20MPa), it is suitble to do fuel cells applications.
Embodiment 12
The fluorine-containing conductive polymer resin containing chlorine manufactured in embodiment 4 is first dissolved in dimethyl acetamide/ethyl alcohol
In (1:1) solution, concentration of the conducting polymer in solution about 20% adds the graphite powder and 1ppm of solution weight about 5%
The nano particle of metal platinum, fluorine-containing conducting polymer containing chlorine (equivalent number 1500) microporous membrane that will be made in embodiment 6
Skeleton, room temperature two-sided immersion took out the film of immersion, gently scrape off the extra liquid of film surface made solution Rio one minute
Body is slowly dried under 90 degree, i.e. acquisition laminated film；Through detecting, about 25 microns of gained laminated film final thickness, width is about
100 centimetres of transparent membrane, film weigh about 47 grams per square meters, and specific gravity 1.83, gas permeability Gurley surveys 100 milliliters of air permeables of method
Speed is greater than 3 minutes；Composite membrane electrical conductivity (Conductivity) about 0.23 (S/cm).The mechanical strength of this composite membrane (stretches
Intensity is greater than 30MPa) it is much better than the individually film (tensile strength obtained by fluorine-containing conducting polymer containing chlorine (equivalent number 500)
Less than 10MPa, entirely without intensity), it is suitble to do fuel cells applications.
Embodiment 13
The fluorine-containing conductive polymer resin containing chlorine (equivalent number 900) manufactured in embodiment 1 is first dissolved in diformazan
In yl acetamide/ethyl alcohol (1:1) solution, concentration of the conducting polymer in solution about 20% adds 10ppm graphene, will
The carbon fiber microporous membrane skeleton being made in embodiment 8, room temperature two-sided immersion take out leaching made solution Rio one minute
The film of bubble gently scrapes off film surface surplus liquid, slowly dries under 90 degree, that is, obtains extraordinary laminated film；Through detecting, institute
About 19 microns of laminated film final thickness are obtained, the transparent membrane that about 100 centimetres of width, film weighs about 37 grams per square meters, and specific gravity is about
1.93, gas permeability Gurley survey 100 milliliters of air permeable speed of method and are greater than 3 minutes, composite membrane electrical conductivity (Conductivity)
About 0.19 (S/cm).The mechanical strength (tensile strength is greater than 60MPa) of this composite membrane is much better than individually conductive high containing chlorine with fluorine-containing
Film obtained by molecule (equivalent number 900) (tensile strength is less than 20MPa), is suitble to do fuel cells applications.
Embodiment 14
The fluorine-containing conductive polymer resin containing chlorine (equivalent number 500) manufactured in embodiment 4 is first dissolved in diformazan
In yl acetamide/ethyl alcohol (1:1) solution, concentration of the conducting polymer in solution about 20%, by what is be made in embodiment 9
ECTFE microporous membrane skeleton, room temperature two-sided immersion is in 20% made fluorine-containing conducting polymer containing chlorine (equivalent number 500) solution
Rio one minute, takes out the film of immersion, gently scrapes off film surface surplus liquid, slowly dries under 90 degree, that is, obtains compound
Film；Through detecting, about 50 microns of gained laminated film final thickness, the transparent membrane that about 100 centimetres of width, film weigh about 98 grams/
Square meter, specific gravity 1.96, gas permeability Gurley survey 100 milliliters of air permeable speed of method and are greater than 3 minutes, composite membrane electrical conductivity
(Conductivity) about 0.17 (S/cm).The mechanical strength (tensile strength is greater than 50MPa) of this composite membrane is much better than independent use
Film obtained by fluorine-containing conducting polymer containing chlorine (equivalent number 500) (tensile strength is less than 10MPa) is entirely without intensity), it is suitble to
Do fuel cells applications.
Embodiment 15
The fluorine-containing conductive polymer resin containing chlorine (equivalent number 950) manufactured in embodiment 5 is first dissolved in diformazan
In base formamide/ethyl alcohol (1:1) solution, concentration of the conducting polymer in solution about 20%, the carbon that will be made in embodiment 8
Fiber microporous membrane skeleton, room temperature two-sided immersion is in 20% made fluorine-containing conducting polymer containing chlorine (equivalent number 950) solution
Rio one minute, takes out the film of immersion, gently scrapes off film surface surplus liquid, slowly dries under 90 degree, that is, obtains compound
Film；Through detecting, about 21 microns of gained laminated film final thickness, the transparent membrane that about 100 centimetres of width, film weigh about 39 grams/
Square meter, specific gravity are about 1.86, and gas permeability Gurley surveys 100 milliliters of air permeable speed of method and is greater than 3 minutes, this laminated film is conductive
It spends (Conductivity) about 0.13 (S/cm), the mechanical strength of this laminated film is much better than individually with fluorine-containing conductive polymer containing chlorine
Film obtained by sub (equivalent number 950).
This laminated film and 6 flat fabric of nylon (90 grams per square meters) answer film and cloth through dotted polyurethane fitting glue point
It closes, this composite material, water pressure resistance (JIS L1092 method) is initially greater than 200kPa, and after washing 10 times, water pressure resistance is still greater than
100kPa；Moisture vapor permeable rate > 4000g/m2/day surveys imitative rotten to the corn poison according to 3 April 2002 of U.S. military discipline MIL-DTL-32102
Gas: dichloroethyl ether (ClCH2CH2OCH2CH2Cl) penetrance qualification < 4 μ g/cm2/day, it was demonstrated that this laminated film is antibiotic to penetrate energy
Power is strong.
Comparative example 1 (the two-sided filled composite film of perfluor conducting polymer, conductivity are low)
After the D520 perfluor sulfoacid resin solution of Du Pont Nafion is vacuumized concentration, until perfluor conducting polymer
Concentration of the Nafion in solution about 20% does microporous membrane skeleton with the puffed polytetrafluoroethylsealing film that online shopping comes, and room temperature is double
Face is immersed in 20% made perfluor conductive polymer solution Rio one minute, takes out the film of immersion, gently scrapes off film surface
Surplus liquid is slowly dried under 90 degree, that is, obtains extraordinary laminated film；Through detecting, the extraordinary fluorine-containing two-sided filling containing chlorine of gained
About 25 microns of laminated film final thickness, the transparent membrane that about 100 centimetres of width, film weighs about 50 grams per square meters, specific gravity 1.98,
Gas permeability Gurley surveys 100 milliliters of air permeable speed of method and is greater than 3 minutes, and composite membrane electrical conductivity at room temperature (Conductivity) is about
0.08 (S/cm), the electrical conductivity at room temperature of this composite membrane cannot be connect less than 0.1 (S/cm) by the application of fuel cell membranes market
By.
Comparative example 2 (the two-sided filled composite film of perfluoro-polymer, biochemistry protection are poor)
520 perfluor sulfoacid resin solutions of Du Pont Nafion are vacuumized into dense institute, until conducting polymer is in solution
Concentration about 20%, the carbon fiber microporous membrane skeleton that will be made in embodiment 8, room temperature two-sided immersion is in 20% made perfluor
Conductive polymer solution Rio one minute, takes out the film of immersion, gently scrapes off film surface surplus liquid, slowly dries under 90 degree
It is dry, that is, obtain extraordinary laminated film；Through detecting, the extraordinary fluorine-containing two-sided filled composite film of conducting polymer containing chlorine of gained is finally thick
About 21 microns of degree, the transparent membrane that about 100 centimetres of width, film weighs about 40 grams per square meters, and specific gravity is about 1.89, gas permeability Gurley
100 milliliters of air permeable speed of survey method are greater than 3 minutes, this extraordinary fluorine-containing two-sided filled composite film room temperature of conducting polymer containing chlorine
Conductivity (Conductivity) about 0.09 (S/cm).
This extraordinary laminated film and 6 flat fabric of nylon (90 grams per square meters) are bonded glue point for film and cloth through dotted polyurethane
Compound, this composite material, water pressure resistance (JIS L1092 method) is initially greater than 200kPa, and after washing 10 times, film is separated with cloth, nothing
Method is market receiving；Moisture vapor permeable rate > 4000g/m2/day is surveyed imitative according to 3 April 2002 of U.S. military discipline MIL-DTL-32102
Vesicating gas: dichloroethyl ether (ClCH2 CH2O CH2 CH2Cl) penetrance qualification > 40 μ g/cm2/day illustrate that this laminated film is anti-
Biochemical penetration capacity is poor.
The performance that above embodiments and comparative example will become apparent from the two-sided filled composite film of fluorine-containing conducting polymer containing chlorine is excellent
In the two-sided filled composite film of perfluor conducting polymer.
For those skilled in the art, it can be made various corresponding according to above technical solution and design
Change and modification, and all these change and modification should be construed as being included within the scope of protection of the claims of the present invention.
Claims (9)
1. a kind of fluorine-containing two-sided filled composite film of conducting polymer containing chlorine, which is characterized in that including microporous membrane skeleton with contain
Fluorine conductive polymer resin containing chlorine, the two-sided pore volume of the microporous membrane skeleton are more than 60% by fluorine-containing conductive high containing chlorine
Molecule resin is filled；
The fluorine-containing conductive polymer resin containing chlorine is prepared via a method which to obtain: first by weight percentage gathering free redical
The fluorine-containing band sulfuryl fluoride liquid monomer 1%~20% of conjunction, pure water 79%~98%, fluorine-containing surfactant 0.01%~1%
It is added in reaction kettle and carries out high-speed stirred, obtain pre-polymerization precursor emulsion；Then tetrafluoroethene is passed through in reaction kettle, in vinylidene
One or two and the gas phase mix monomers of chlorotrifluoroethylene, reaction pressure be 5 kilograms or more；Free radical is then passed to draw
Agent is sent out, at 20-120 DEG C, reaction pressure obtains reaction product and contain reaction temperature in 5-25 kilograms, reaction time 15-180min
Macromolecule emulsion of the fluorine containing chlorine with sulfuryl fluoride；The fluorine-containing band sulfuryl fluoride liquid monomer and the gas phase mix monomer actual participation
The ratio between total weight of Raolical polymerizable is 1:3~3:1；Radical initiator is passed through total weight and fluorine-containing band sulfuryl fluoride liquid
The weight ratio of phase monomer is 0.01%~3.0%；It is finally hydrolyzed, then passes through with the macromolecule emulsion of sulfuryl fluoride containing chlorine to fluorine-containing
Fluorine-containing conductive polymer resin containing chlorine is obtained after cohesion, washing, drying；The fluorine-containing band sulfuryl fluoride liquid monomer includes CF2=
CF-O-CF2CF2-SO2F, CF2=CF-O-CF2CFCF3-O-CF2CF2-SO2F、CF2=CF-CF2-O-SO2F、CF2=CF-CF2-
O-CF2CF2-SO2One or more of F.
2. a kind of production method of fluorine-containing two-sided filled composite film of conducting polymer containing chlorine as described in claim 1, special
Sign is, includes the following steps:
By microporous membrane skeleton in a manner of being coated with or impregnate, it is thin that the fluorine-containing conductive polymer resin containing chlorine is packed into micropore
Composite material is obtained in the two-sided hole of membrane bone frame；Composite material is dried, the two-sided filling of fluorine-containing conducting polymer containing chlorine is made
Laminated film.
3. production method according to claim 2, which is characterized in that microporous membrane skeleton and fluorine-containing conducting polymer containing chlorine
The weight ratio of resin is (5:95)-(40:60).
4. production method according to claim 2, which is characterized in that microporous membrane skeleton is prepared via a method which:
First by heat-fusible property fluorine resin or chlorinated and fluorinated resin, the fluorine-containing conductive polymer resin containing chlorine, polyacrylonitrile and
One of its copolymer, polyimides, polyamide, polyester, polyether-ketone carry out spinning, through hot melt spinneret or wet process spinneret,
Random reticulated macroporous structure is collected into evenly, and microporous membrane skeleton is obtained after heat setting.
5. production method according to claim 2, which is characterized in that microporous membrane skeleton, will to be coated with or immersion process
One or more of active powdered carbon, graphite powder, graphene, silver metal powder, platinum powder or palladium metal powder fluorine-containing contain with described
The mixing of chlorine conductive polymer resin is packed into together in the two-sided hole of its microporous membrane.
6. production method according to claim 5, which is characterized in that the activity powdered carbon, graphite powder, graphene, silver gold
The total weight for belonging to one or more of powder, platinum powder or palladium metal powder is no more than the weight of the fluorine-containing conductive polymer resin containing chlorine
The 25% of amount.
7. production method according to claim 4, which is characterized in that heat-fusible property fluorine resin or chlorinated and fluorinated resin packet
Include heat-fusible property teflon-copolymers, one in polytrifluorochloroethylene or its copolymer, Kynoar or its copolymer
Kind is several.
8. production method according to claim 2, which is characterized in that the acid of the fluorine-containing conductive polymer resin containing chlorine is worked as
Number meq/g is measured in 400-1500.
9. production method according to claim 2, which is characterized in that using wet type phase change method, temperature difference phase change method, do
Formula solvent method, method of electrostatic spinning or ultracentrifugation spin processes carry out spinning.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710251603.2A CN106968110B (en) | 2017-04-18 | 2017-04-18 | Fluorine-containing two-sided filled composite film of conducting polymer containing chlorine of one kind and preparation method thereof |
| US16/605,668 US11136424B2 (en) | 2017-04-18 | 2018-04-04 | Preparation method for fluorine- and chlorine-containing conductive polymer resin and single- or double-sided filled composite thin film prepared using same and the preparation method therefor |
| GB1916736.0A GB2575951B (en) | 2017-04-18 | 2018-04-04 | Preparation method for fluorine- and chlorine-containing conductive polymer resin and single- or double-sided filled composite thin film prepared using same |
| PCT/CN2018/081864 WO2018192368A1 (en) | 2017-04-18 | 2018-04-04 | Preparation method for fluorine- and chlorine-containing conductive polymer resin and single- or double-sided filled composite thin film prepared using same and the preparation method therefor |
| DE112018002056.8T DE112018002056B4 (en) | 2017-04-18 | 2018-04-04 | Process for the production of a fluorine-containing, chlorine-containing electrically conductive polymer resin and a composite film produced therewith which is filled on one or both sides, as well as a process for producing the same |
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| WO2022206039A1 (en) | 2021-03-29 | 2022-10-06 | 浙江汉丞新能源有限公司 | Composite membrane of special highly-enhanced fluorine-containing proton or ion exchange membrane, composite membrane electrode, special highly-enhanced fluorine-containing chlor-alkali battery membrane, special release membrane, and preparation method therefor |
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| WO2018192368A1 (en) * | 2017-04-18 | 2018-10-25 | 浙江汉丞科技有限公司 | Preparation method for fluorine- and chlorine-containing conductive polymer resin and single- or double-sided filled composite thin film prepared using same and the preparation method therefor |
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| CN113067020B (en) * | 2021-03-29 | 2022-07-15 | 浙江汉丞新能源有限公司 | Composite membrane electrode of high-enhancement type fluorine-containing proton or ion exchange membrane |
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| WO2022206039A1 (en) | 2021-03-29 | 2022-10-06 | 浙江汉丞新能源有限公司 | Composite membrane of special highly-enhanced fluorine-containing proton or ion exchange membrane, composite membrane electrode, special highly-enhanced fluorine-containing chlor-alkali battery membrane, special release membrane, and preparation method therefor |
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