CN101693215B - Preparation and application of fluororesins with low ion exchange capacity - Google Patents
Preparation and application of fluororesins with low ion exchange capacity Download PDFInfo
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- CN101693215B CN101693215B CN2009102294422A CN200910229442A CN101693215B CN 101693215 B CN101693215 B CN 101693215B CN 2009102294422 A CN2009102294422 A CN 2009102294422A CN 200910229442 A CN200910229442 A CN 200910229442A CN 101693215 B CN101693215 B CN 101693215B
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Abstract
The invention discloses fluororesins with low ion exchange capacity and high mechanical strength, which comprise tetrafluoroethylene, ethylene and one or pluralities of monomers with structures illustrated by following general formulas (I): in the formulas, a=2-5, n=0-2; A is chosen from -COR0, -COOR1, -CONR2R3 or -CN; and R0-R3 are chosen from -CmH2m+1, wherein m=1-10. Molecular weight ranges from 150,000-650,000. Fluorine-contained polymers with ion exchanging function adopt an anticorrosive hastelloy melt spinning device to prepare polymer fibers with melt spinning serving as materials, the fibers are woven into fiber nets with the ion exchanging function via spinning technology, and the fiber nets serve as strengthening net materials of proton exchange membranes and chlor-alkali ion membranes, thereby achieving the purposes of simultaneously improving the capabilities of membrane materials in strengthening and increasing adhesion between the fibers and the membranes, increasing content of carboxylic acid ions and efficiently stopping back migration of hydroxyls.
Description
Technical field
The invention belongs to the fluoro-containing macromolecule material field, relate to that a class has the ion exchanging function fluoro-resin and as the application of ion-exchange membrane strongthener.
Background technology
After the perfluor ion-exchange composite membranes was exhibited one's skill to the full in chlorine industry, the countries in the world that are applied in of perfluorinated ion-exchange membrane had obtained extensive studies.No matter perfluorinated ion-exchange membrane is to use in chlorine industry or in fuel cell, technique known all needs to adopt the enhancing framework material to strengthen at present, no matter be to adopt poromerics to strengthen or fiber reinforcement, these strongtheners are a spot of sacrificial fiber material of tetrafluoroethylene, meltable poly and auxiliary usefulness nothing more than.These perfluor type strongtheners belong to the insulating material of no ion exchanging function, its volume specific resistance will exceed more than 14 orders of magnitude with the resistivity of perfluor type ion-exchange membrane than general chlorine industry, thereby at the directed back side that sees through film of positively charged ion " blind area " will appear, the corresponding useful area that reduces the cation permeation film, increased membrane resistance and bath voltage, this is a technical barrier of present this area; The another one technical barrier is no matter tetrafluoroethylene or meltable poly, all have very low surface energy, stick poor performance, a little less than the interlayer adhesion of itself and exchange membrane material, easily bubble between rete in the use, peel off, shorten the work-ing life of mould material.
Ethylene-tetrafluoroethylene copolymer (ETFE or F40) is since 20th century, be found the forties, because it has good electrical property, chemical resistant properties and ageing resistance, again because the introducing of ethene has improved the radioresistance of material greatly, the improvement of its mechanical property is more outstanding, main is that its processing characteristics is improved greatly, these premium propertiess, make this multipolymer a member as high performance engineering plastics, develop very rapidly, be widely used in automobile, the aspects such as lining of pipe line coating of the wire cable insulating material of aviation and robot and transmission special liquid medium.In the last few years, the ethylene-tetrafluoroethylene copolymer surface is handled, and the research that makes it to have functionalization constantly is in the news out, as: Journal of MembraneScience, 2007, vol.297, no.1-2, report is handled the ETFE mould material by gamma-ray irradiation, thereafter surface grafting copolymerization dimethylaminoethyl methacrylate, make it to have hydroxy-acid group, this mould material has good thermostability and chemical stability, is applied in the direct methanol fuel cell; Journal of Adhesion Science and Technology, 2006, vol.20, no.13 has characterized ethylene-tetrafluoroethylene copolymer membrane surface and has passed through CO
2Ion sputtering makes the surface generate hydroxy-acid group, has the ion transport function.Present many research methods all are that the mode by high-energy ray irradiation makes the ETFE functionalization, the shortcoming that the way of this irradiation exists is exactly the surface C-C bond rupture that makes film in the irradiation process, what can not accurately be controlled for the position of break chemical bonds and fracture, and the mechanical property of material itself, resistance toheat, resistance to chemical corrosion, weather resistance all can reduce.
Summary of the invention
At the deficiencies in the prior art, the invention provides the fluoro-resin that a class has ion exchanging function, the application of such fluoro-resin with ion exchanging function as the ion-exchange membrane strongthener also is provided simultaneously, such material has closely similar structure with the material itself that is enhanced, and layer has excellent adhesion performance with interlayer.Such strongthener with ion exchanging function can effectively increase the useful area of cation permeation film, reduces membrane resistance and bath voltage, for suitability for industrialized production cuts down the consumption of energy.
It is known using exchange membrane containing fluorine in electrolyzer.Especially use anolyte compartment's one side to contain the perfluor ion that sulfonic group, cathode compartment one side contain the carboxylic acid group and strengthen composite membrane, its chemically-resistant degradation property and the carboxyl interception that backmigration enters the anolyte compartment to the hydroxyl negatively charged ion, make that this use of composite membrane in electrolyzer with ion exchanging function is particularly important, in case the backmigration of hydroxyl negatively charged ion enters the anolyte compartment, the current efficiency of chlorine and caustic soda will descend greatly.But present technology, its loading capacity of resin with perfluor carboxyl is also little, for improving its spendable ion-exchange quantity, the present invention goes into spendable carboxylic acid ionic polymerization in the fortifying fibre, both played the effect that strengthens the ion composite membrane, play the effect that increases the carboxylic acid ion content again, improve the current efficiency in the electrolytic process.
Technical scheme of the present invention is as follows:
Fluoro-resin of the present invention is the fluoro-resin that has ion-exchange group, is to be formed by following three class monomer copolymerizations:
1., tetrafluoroethylene CF
2=CF
2
2., ethene CH
2=CH
2
3., one or more have the monomer of structure shown in the following general formula:
In the formula: the integer of the integer of a=2～5, n=0～2; A is selected from-COR
0,-COOR
1,-CONR
2R
3,-CN;
R
0, R
1, R
2, R
3Be selected from-C
mH
2m+1, m=1～10 wherein.
The molecular weight of described ion exchanging function fluoro-resin is 1～100g/10min at 15-65 ten thousand in the melt flow index under 300 ℃ of 5Kg loads.
Preferably, general formula 3. described in monomer, n=0 or 1; The integer of a=2～4; A is selected from-CO
2CH
3
Contain in the above-mentioned fluoro-resin-COR
0,-COOR
1,-CONR
2R
3,-CN group is stable group in melt extruding processing, extrudes fiber through after stretching fast, draw, finalizing the design, and promptly becomes stable fibre product.Can be to pass through the alkali lye treatment trough again behind the netted enhancing skeleton with the fiber establishment, be the fiber with ion exchanging function transition, thereafter compound with the exchange membrane material again, it is compound with the ion exchange membrane material that is enhanced behind the netted enhancing skeleton also fiber can being worked out, and in use is treated to by alkali lye thereafter to have the ion exchanging function strongthener.
Fluoro-resin with ion-exchange group of the present invention is the monomeric random copolymerizations of above-mentioned three classes,
Preferably, above-mentioned have that monomer tetrafluoroethylene shared molar content in resin is 40～69.9% in the ion exchanging function fluoro-resin; Ethene shared molar content in resin is 50～30%; General formula 3. shown in monomer shared molar content total amount in resin be 0.1-10%.
Melt flow index under 300 ℃, 5Kg load is 1～100g/10min, and this resinoid can melt extrude spinning by melt extruding equipment in 200～400 ℃ of scopes, prepare the fluorine-contained polymerisate fibre material with ion exchanging function.
Preferably, tetrafluoroethylene shared molar content preferred 45～59.5% in resin; Ethene shared molar content preferred 50～40% in resin; General formula 3. shown in monomer shared preferred 0.5-5% of molar content total amount in resin.
The present invention also provides described application with fluoro-resin of ion exchanging function, and this resinoid melt extrudes spinning by melt extruding equipment in 200～400 ℃ of scopes, is fiber through drawing-off, cooling and shaping.
Fluorine-contained polymerisate fibre with ion exchanging function of the present invention is characterized in that, described fluoro-resin with ion exchanging function melt extrudes spinning by melt extruding equipment in 200～400 ℃ of scopes, forms through drawing-off, cooling and shaping.
Preferably, described fluorine-contained polymerisate fibre with ion exchanging function, fiber number is controlled at the 20-500 dawn.
Fluorine-contained polymerisate fibre with ion exchanging function provided by the invention, it is characterized in that, described fiber prepares after handling by alkali lye, and described alkali lye is the sodium hydroxide solution of massfraction 5-30% or the potassium hydroxide solution of massfraction 5-30%.
The present invention also provides described application with fluorine-contained polymerisate fibre material of ion exchanging function, it is characterized in that described fluorine-contained polymerisate fibre material with ion exchanging function, be woven into fibrous reticulum by textile technology, as the enhancing framework material of chlor-alkali ion composite membrane.
Preparation method with ion exchanging function fluoro-resin, be one or more to be contained the vinyl ether monomers of ion-exchange group and ethene and tetrafluoroethylene monomer shown in 3. carry out free-radical polymerized under the living radical initiator causes and prepare, polymerization process can adopt suspension polymerization, dispersion polymerization, solution polymerization, letex polymerization and micro-emulsion polymerization.The fluoropolymer of preparing with ion exchanging function can carry out the fiber that the spinning preparation has ion exchanging function by the mode that melt extrudes.
Polymerization process can adopt any known method, and the present invention recommends to use following method:
A kind of solution polymerization method with ion exchanging function fluoro-resin comprises the following steps:
1) reactor is cleaned and thorough drying after vacuumize, the inflated with nitrogen displacement, is evacuated to-0.1MPa below 10ppm until Control for Oxygen Content,
2) perfluorocarbon solvent, perfluorocarboxylic acid monomer are added in the reactor, stir and be warming up to 35～45 ℃,
3) treat that system temperature is constant after, add the perfluor peroxide initiator with volume pump, feed the mixed gas of tetrafluoroethylene and ethene, to pressure arrival 1.1MPa,
4) the lasting mixed gas that feeds tetrafluoroethylene and ethene makes reaction pressure at 0.8～1.1MPa, and reaction is constantly carried out,
5) adopt discontinuous manner in system, to add the perfluor peroxide initiator, when the mixed gas add-on of tetrafluoroethylene and ethene reaches 1000～1200g, stop to add, allow reaction proceed by volume pump;
6) when the still internal pressure is reduced to 0.8MPa, stopped reaction is recovered into unreacted mix monomer in the accumulator tank, put into rake type dryer by discharging valve of reaction kettle goalkeeper material, reclaim reaction solvent and unreacted carboxylic acid monomer, and the dry polymer material, the white powder product obtained;
7) further with product in 100 ℃ of vacuum-dryings 6～10 hours.
In the reaction, the mixed gas add-on of tetrafluoroethylene and ethene calculates by pressure change.
Preferably, described perfluorocarboxylic acid monomer is selected from
In the formula: the integer of the integer of a=2～5, n=0～2; A is selected from-COR
0,-COOR
1,-CONR
2R
3,-CN; R
0, R
1, R
2, R
3Be selected from-C
mH
2m+1, m=1～10 wherein.
Preferred, described perfluorocarboxylic acid monomer is selected from 3-methoxycarbonyl-propoxy-vinyl ether (molecular formula: CH
3OOCCF
2CF
2OCF=CF
2).
Described perfluorocarbon solvent is selected from: HFC225, perfluoro-2-methyl cyclobutane, perfluor furans, perfluor pyrans, its add-on is for being the 60-65% of reactor volume.
Described perfluor peroxide initiator is a peroxidation perfluor butyryl radicals compound, and its structural formula is CF
3CF
2CF
2CO-OO-OCCF
2CF
2CF
3
In the mixed gas of tetrafluoroethylene and ethene, gas ratio is a tetrafluoroethylene: ethene equals (90～10): (10～90), volume ratio.
A kind of suspension polymerization preparation method with ion exchanging function fluoro-resin comprises the following steps:
1) autoclave is cleaned and is vacuumized, fill the high pure nitrogen displacement, until oxygen level below 10ppm,
2) be evacuated to-0.1MPa, add pure water, the perfluorocarboxylic acid monomer contain perfluor propoxy-carboxylic acid ammonium in reactor, be warming up to 70 ℃, the mixed gas that feeds tetrafluoroethylene and ethene is to 4.0MPa,
3) adopt volume pump to continue to add initiator in reactor, reaction begins to carry out;
4) by in system, constantly adding the mixed gas and the initiator of tetrafluoroethylene and ethene, keep reaction pressure at 4.0MPa;
5) the mix monomer amount that enters reaction system by calculation of pressure stops to feed mix monomer when 1310g,
6) when the still internal pressure is reduced to 3.8MPa, stopped reaction reclaims unreacted mixing gas phase monomer, emits mixture by dispensing valve, and press filtration obtains the white polymer wet mash, wet mash after deionized water repeatedly washs, 100 ℃ of vacuum-dryings.Filtrate goes to the unreacted alkene ether monomer of recovery tower Separation and Recovery.
In the reaction, the mixed gas add-on of tetrafluoroethylene and ethene calculates by pressure change.
Preferably, the add-on of described pure water is the 60-65% of reactor volume, and described perfluor propoxy-carboxylic acid ammonium's add-on is for adding the 0.2-0.5% of pure water volume.
Described perfluor propoxy-carboxylic acid ammonium's molecular formula is CF
3CF
3CF
2OCFCF
3CF
2-OCFCF
3COONH
4
Preferably, described perfluorocarboxylic acid monomer is selected from
In the formula: the integer of the integer of a=2～5, n=0～2; A is selected from-COR
0,-COOR
1,-CONR
2R
3,-CN; R
0, R
1, R
2, R
3Be selected from-C
mH
2m+1, m=1～10 wherein.
Preferred, described perfluorocarboxylic acid monomer is selected from perfluor 4-oxa--5-methyl-8-alkene-methyl pelargonate, and molecular formula is CH
3OOCCF
2CF
2OCF (CF
3) CF
2OCF=CF
2
Preferably, the monomeric add-on of perfluorocarboxylic acid is the 5-10% of reactor volume.
Preferably, the blending ratio of tetrafluoroethylene, ethene mixed gas is: tetrafluoroethylene: ethene=(90～10): (10～90), volume ratio.
Preferably, initiator is a potassium persulfate solution, and concentration is 0.0005～0.0007mol/L.
A kind of emulsion-polymerizing preparation method with ion exchanging function fluoro-resin comprises the following steps:
1) reactor is cleaned and is vacuumized, fill the high pure nitrogen displacement, until Control for Oxygen Content below 10ppm,
2) be evacuated to-0.1MPa, in reactor, add pure water, the perfluorocarboxylic acid monomer that contains perfluor propoxy-carboxylic acid ammonium,
3) be warming up to 75 ℃, the mixed gas that feeds tetrafluoroethylene and ethene is to 4.2MPa,
4) continue to add initiator with volume pump in reactor, reaction begins to carry out.
5) mixed gas by constantly adding tetrafluoroethylene and ethene in system is to keep reaction pressure at 4.2MPa, and the tetrafluoroethylene monomer amount of reaction system stops to feed mix monomer when 1300g,
6) when the still internal pressure is reduced to 4.0MPa, stopped reaction, reclaim unreacted tetrafluoroethylene monomer, emit mixture as smashing to pieces in the bucket by dispensing valve, by high speed shear breakdown of emulsion in smashing bucket to pieces, obtain the white polymer wet mash, wet mash after deionized water repeatedly washs, 100 ℃ of vacuum-dryings; Filtrate goes to unreacted alkene ether monomer of recovery tower Separation and Recovery and solvent.
In the reaction, the mixed gas add-on of tetrafluoroethylene and ethene obtains by calculation of pressure.
Described perfluor propoxy-carboxylic acid ammonium's molecular formula is CF
3CF
3CF
2OCFCF
3CF
2-OCFCF
3COONH
4
Preferably, the add-on of described pure water is the 60-65% of reactor volume, and described perfluor propoxy-carboxylic acid ammonium's add-on is for adding the 0.2-0.5% of pure water volume.
Preferably, described perfluorocarboxylic acid monomer is selected from
In the formula: the integer of the integer of a=2～5, n=0～2; A is selected from-COR
0,-COOR
1,-CONR
2R
3,-CN; R
0, R
1, R
2, R
3Be selected from-C
mH
2m+1, m=1～10 wherein.
Preferred, described perfluorocarboxylic acid monomer is selected from 3-methoxycarbonyl-perfluoro propyl vinyl ether, molecular formula: CH
3OOCCF
2CF
2OCF=CF
2
Preferably, the monomeric add-on of perfluorocarboxylic acid is the 5-10% of reactor volume.
Preferably, the blending ratio of tetrafluoroethylene, ethene mixed gas is: tetrafluoroethylene: ethene=(90～10): (10～90), volume ratio.
Preferably, described initiator is a Potassium Persulphate, and concentration is 0.0004～0.0005mol/L, and preferred, concentration is 0.00047mol/L.
The present invention has the application of the fluoro-resin of ion exchanging function, and this resin can prepare fiber by the mode that melt extrudes spinning in 200～400 ℃ of scopes, and what prepare is the fluorine-contained polymerisate fibre material with ion exchanging function.Wherein spinning equipment adopts the Hastelloy material at high temperature and the part that contacts with resin during spinning, prevents to introduce foreign ion and pollute fiber in resin.
The invention has the beneficial effects as follows:
Of the present invention to have the ion exchanging function fluoro-resin be the fluoropolymer with low ion exchange capacity, and the fiber by this resins is to have low ion exchange capacity, high-intensity fiber.This fluorine-contained polymerisate fibre material with ion exchanging function, be woven into fibrous reticulum by textile technology, enhancing net materials as the chlor-alkali ionic membrane, can reach enhancing simultaneously, increase the ability of sticking and increase the purpose of carboxylic acid ion exchanging function, further stop the backmigration effect of hydroxyl, improve the purity of industry system alkali from cathode compartment anode chamber.As the enhancing net materials of chlor-alkali ionic membrane, can increase the useful area of cation permeation film, corresponding reduction membrane resistance and bath voltage have well solved the technical barrier of present this area; Further promote the bonding ability that strengthens between net and rete simultaneously again, promote the work-ing life of mould material.
Embodiment
The present invention is described by the following examples, but does not limit the present invention.
The living radical initiator that is adopted that reacts in solvent phase of the present invention is selected from the perfluoroalkyl acyl superoxide initiator.The perfluoroalkyl initiator that the present invention is adopted in building-up process can prepare according to techniques well known, and the preparation method that the present invention recommends is referring to J.Org.Chem., and 1982,47 (11): 2009-2013.
The Potassium Persulphate that the present invention is adopted in building-up process, ammonium persulphate, benzoyl peroxide, Diisopropyl azodicarboxylate all can be bought and obtain.
The comonomer tetrafluoroethylene that the present invention is adopted in building-up process, ethene, general formula 3. shown in various alkene ether monomers can buy and obtain, also can prepare by approach well known, the preparation method the present invention that can Gong select for use will describe by embodiment.
Embodiment 1 (perfluorocarbon solvent system, fluorine-containing organo-peroxide is made initiator)
Polymerization single polymerization monomer is selected tetrafluoroethylene, ethene; The alkene ether monomer: methoxycarbonyl-(molecular formula is CF to perfluor propoxy-second isopropyl-ethylene base ether
2=CFO-CF
2(CF
3) CFOCF
2CF
2COOCH
3(be n=1, a=2, A=-COOCH
3), molecular weight is 422g/mol, preparation reference USP.4578512 preparation)
10L stainless steel autoclave is cleaned and vacuumized, fill high pure nitrogen displacement three times, until Control for Oxygen Content below 10ppm, be evacuated to-0.1MPa, in reactor, add perfluorocarbon solvent 6L (described perfluorocarbon solvent is HFC225), the 400g methoxycarbonyl-(molecular formula is CF to perfluor propoxy-second isopropyl-ethylene base ether
2=CFO-CF
2(CF
3) CFOCF
2CF
2COOCH
3), stir and be warming up to 40 ℃, treat that system temperature is constant after, add 40ml with volume pump and contain 4.54g peroxidation perfluor butyryl radicals compound (CF
3CF
2CF
2CO-OO-OCCF
2CF
2CF
3), feed the mixed gas (ratio of gas mixture is a tetrafluoroethylene: ethene equals 72: 18) of tetrafluoroethylene and ethene, to pressure arrival 1.1MPa, continuing to feed mixed gas makes reaction pressure at 0.8～1.1MPa, reaction is constantly carried out, adopted discontinuous manner in system, to add the perfluor peroxide initiator, calculate when the mixed gas add-on reaches 1120g by pressure change by volume pump, stop to add, allow reaction proceed.When the still internal pressure is reduced to 0.8MPa, stopped reaction is recovered into unreacted mix monomer in the accumulator tank, puts as in the rake type dryer by discharging valve of reaction kettle goalkeeper material, reclaim reaction solvent and unreacted alkene ether monomer and dry polymer material, obtain the white powder product.Further with product in 100 ℃ of vacuum-dryings 8 hours, obtain the 1010g resin.
Through F
19NMR, H NMR, IR analyze and turn out to be the design synthetic product.
Through F
19NMR, IR analyze and confirm that alkene ether monomer methoxycarbonyl-perfluor propoxy-second isopropyl-ethylene base ether molar content is 1.9% in the polymers, the tetrafluoroethylene monomer molar content is 52.5% in the polymkeric substance, the vinyl monomer molar content is 45.6% in the polymkeric substance, and its loading capacity is 0.205mol/Kg.Polymer data: by fusion index instrument measure resin melting index 20.5g/10mim (300 ℃, 5kg); 1% weight decomposition temperature (T of TGA test resin
d) be 394 ℃; IR spectrogram: 1778cm
-1Be C=O vibration absorption peak in the carbonyl; 1200 and 1148cm
-1Two absorptions the strongest are caused by the CF vibration; 984cm
-1Be CF
3Vibration causes; 720cm
-1, 641cm
-1Cause 2975cm by the TFE vibration
-1, 2885cm
-1, 1454cm
-1Cause by the ethene vibration.
Take by weighing powdery resin 500g, use the vulcanizing press compressing tablet, temperature is 300 ℃, then the resin behind the compressing tablet is cut into the particle of diameter 2mm, long 4mm, the resinous polymer pellet is carried out melt-spinning, adopt the single screw extrusion machine monofilament to extrude, 295 ℃ of melt zone temperature, 305 ℃ of screw extrusion press head temperatures, 310 ℃ of nozzle plate temperature, 400 meters/minute of drawing speeds adopt traditional batching with winding apparatus to collect the fiber of extruding, the filament strength of fiber surpasses 45MPa, and the control drawing speed makes filament denier between 50～500 dawn.
Described fiber prepares the fluorine-contained polymerisate fibre with ion exchanging function after handling by alkali lye, and described alkali lye comprises the sodium hydroxide solution of massfraction 5-30% or the potassium hydroxide solution of massfraction 5-30%.
Braiding has the fiber type enhancing screen cloth that interweaves of ion exchanging function on 1.4m wide cut fibrage machine, the warp fiber number is at 50～250 dawn, the parallel fiber number is at 100～550 dawn, the direction of warp and weft upper density is respectively at 10～30 pieces/centimetre and 10～15 pieces/centimetre, regulate the fiber number and the density of warp and woof according to needs of production, because this fibrid has high mechanical strength and the perfluorinated ion-exchange membrane material is had good adhesion, therefore, the porosity that strengthens net can be than high a lot of in the prior art.
Embodiment 2:(solution polymerization, fluorocarbon solvent, perfluoroalkyl acyl superoxide initiator)
Polymerization single polymerization monomer is selected tetrafluoroethylene, ethene; (its 1 molecular formula is CF to two kinds of alkene ether monomers
2=CFO-CF
2CF (CF
3) O-CF
2CF
2COOCH
3(be n=1, a=2, A=-COOCH
3), molecular weight 422g/mol, its 2 molecular formula is CF
2=CFO-CF
2CF (CF
3) O-CF
2CF
2CF
2COOCH
3(be n=1, a=3, A=-COOCH
3), molecular weight 472g/mol, it is free-radical polymerized to carry out solution.
10L stainless steel autoclave cleaned and thorough drying after vacuumize; inflated with nitrogen displacement three times; until Control for Oxygen Content below 10ppm; be evacuated to-0.1MPa; 6.0L perfluorocarbon solvent (described perfluorocarbon solvent is a perfluoro-2-methyl cyclobutane), 230g perfluor alkene ether monomer 1 and 250g perfluor alkene ether monomer 2 are added in the reactor; stir also and be warming up to 40 ℃, treat that system temperature is constant after, add 70ml with volume pump and contain the different propionyl superoxide of 8.52g perfluor propoxy-(CF
3CF
2CF
2OCF (CF
3) CO-OO-OC (CF
3) CFOCF
2CF
2CF
3), feed tetrafluoroethylene, ethene mixed gas (gas ratio is a tetrafluoroethylene: ethene equals 60: 40) to pressure arrival 1MPa, and at 0.8～1.0MPa reaction is constantly carried out to keep pressure by continue adding the gas phase mix monomer, adopt discontinuous manner in system, to add the perfluor peroxide initiator by volume pump, calculate when the tetrafluoroethylene add-on reaches 1000g by pressure change, stop to add, allow reaction proceed.When the still internal pressure is reduced to 0.8MPa, stopped reaction is recovered into unreacted mix monomer in the accumulator tank, puts as in the rake type dryer by discharging valve of reaction kettle goalkeeper material, reclaim reaction solvent and unreacted alkene ether monomer and dry polymer material, obtain the white powder product.Further with product in 100 ℃ of vacuum-dryings 8 hours, obtain the 830g resin.
Through F
19NMR, H NMR, IR analyze and turn out to be the design synthetic product.
Through F
19NMR, IR analyze and confirm that alkene ether monomer 1 molar content is 1.5% in the polymers, alkene ether monomer 2 molar contents are 0.9%, the tetrafluoroethylene monomer molar content is 56% in the polymkeric substance, the vinyl monomer molar content is 41.6% in the polymkeric substance, and the loading capacity of resin is 0.267mol/Kg.Polymer data: the melting index of measuring resin by fusion index instrument be 12.5g/10mim (300 ℃, 5kg); 1% weight decomposition temperature (T of TGA test resin
d) be 392 ℃; IR spectrogram: 1778cm
-1Be C=O vibration absorption peak in the carbonyl; 1200 and 1148cm
-1Two absorptions the strongest are caused by the CF vibration; 984cm
-1Be CF
3Vibration causes; 720cm
-1, 641cm
-1Cause 2975cm by the TFE vibration
-1, 2885cm
-1, 1454cm
-1Cause by the ethene vibration.
Take by weighing powdery resin 500g, use the vulcanizing press compressing tablet, temperature is 300 ℃, then the resin behind the compressing tablet is cut into the particle of diameter 2mm, long 4mm, the resinous polymer pellet is carried out melt-spinning, adopt the single screw extrusion machine monofilament to extrude 300 ℃ of melt zone temperature, 315 ℃ of screw extrusion press temperature, 320 ℃ of nozzle plate temperature, 550 meters/minute of drawing speeds adopt traditional batching with winding apparatus to collect the fiber of extruding, and the filament strength of fiber surpasses 45MPa.
Embodiment 3 (suspension polymerization, persulphate is an initiator, water is as dispersion medium)
Polymerization single polymerization monomer is selected tetrafluoroethylene, ethene; Alkene ether monomer: CF
2=CFO-CF
2CF (CF
3) O-CF
2CF
2COOCH
3, molecular weight 422g/mol.
10L stainless steel autoclave is cleaned and vacuumized, fill high pure nitrogen displacement three times, below 10ppm, be evacuated to-0.1MPa, in reactor, add and contain 3.2g perfluor propoxy-carboxylic acid ammonium (molecular formula CF until oxygen level
3CF
3CF
2OCFCF
3CF
2-OCFCF
3COONH
4) pure water 6L, 150g alkene ether monomer (CF
2=CFO-CF
2CF (CF
3) O-CF
2CF
2COOCH
3Molecular weight 422g/mol), is warming up to 70 ℃, feeds tetrafluoroethylene, (blending ratio is the ethene mixed gas: tetrafluoroethylene: ethene=50: 50) to 4.0MPa, adopting volume pump to continue to add concentration in reactor is the potassium persulfate solution of 0.0007mol/L, and reaction begins to carry out.By in system, constantly adding mix monomer and initiator, keep reaction pressure at 4.0MPa.The mix monomer amount that enters reaction system by calculation of pressure is when 1310g, stop to feed mix monomer, when the still internal pressure is reduced to 3.8MPa, stopped reaction, reclaim unreacted mixing gas phase monomer, emit mixture by dispensing valve, press filtration obtains the white polymer wet mash, after deionized water repeatedly washs, 100 ℃ of vacuum-dryings.Filtrate goes to the unreacted alkene ether monomer of recovery tower Separation and Recovery.
Through F
19NMR, H NMR, IR analyze and turn out to be the design synthetic product.
Alkene ether monomer molar content is 1.6% in the polymers, and the tetrafluoroethylene monomer molar content is 58% in the polymkeric substance, and the vinyl monomer molar content is 40.4% in the polymkeric substance, and its loading capacity is 0.173mol/Kg.The melting index of measuring resin by fusion index instrument be 9.8g/10mim (300 ℃, 5kg); 1% weight decomposition temperature (T of TGA test resin
d) be 399 ℃; In the IR spectrogram: 1778cm
-1Be C=O vibration absorption peak in the carbonyl; 1200cm
-1And 1148cm
-1Two absorptions the strongest are caused by the CF vibration; 984cm
-1Be CF
3Vibration causes; 720cm
-1, 641cm
-1Cause by the TFE vibration; 2986cm
-1And 2876cm
-1Two peaks are the methyl vibration absorption peak; 1036cm
-1For-C-O-C-strong vibration absorption peak, 2975cm
-1, 2885cm
-1, 1454cm
-1Cause by the ethene vibration.
Embodiment 4 (perfluorocarbon solvent and water mixed system, fluorine-containing organo-peroxide is made initiator)
Polymerization single polymerization monomer is selected tetrafluoroethylene, ethene; Alkene ether monomer: CF
2=CFO-CF
2CF (CF
3) O-CF
2CF
2COOCH
3, molecular weight 422g/mol
10L stainless steel autoclave is cleaned and vacuumized, fill high pure nitrogen displacement three times, below 10ppm, be evacuated to-0.1MPa, in reactor, add pure water 3.5L, perfluorocarbon solvent 2.5L, 400g alkene ether monomer (CF until Control for Oxygen Content
2=CFO-CF
2CF (CF
3) O-CF
2CF
2COOCH
3, molecular weight 422g/mol), be warming up to 43 ℃, feed tetrafluoroethylene, ethene mixed gas to pressure is 1.0MPa, in reactor, add 55ml with volume pump and contain 4.8g perfluor butyryl radicals superoxide (CF
3CF
2CF
2CO-OO-OCCF
2CF
2CF
3), reaction begins to carry out.By in system, constantly adding mix monomer keeping reaction pressure, and take interrupter method to add initiator at 1.0MPa.The tetrafluoroethylene monomer amount that enters reaction system by calculation of pressure is when 1200g, stop to feed tetrafluoroethylene monomer, when the still internal pressure is reduced to 0.8MPa, stopped reaction, reclaim unreacted mix monomer, emit mixture by dispensing valve, press filtration obtains the white polymer wet mash, after deionized water repeatedly washs, 100 ℃ of vacuum-dryings.Filtrate goes to unreacted alkene ether monomer of recovery tower Separation and Recovery and solvent.
Through F
19NMR, H NMR, IR analyze and turn out to be the design product.
Alkene ether monomer molar content is 2.1% in the polymers, the tetrafluoroethylene monomer molar content is 56% in the polymkeric substance, the vinyl monomer molar content is 41.9% in the polymkeric substance, its loading capacity is 0.193mol/Kg, the melting index of measuring resin by fusion index instrument be 12.8g/10mim (300 ℃, 5kg); 1% weight decomposition temperature (T of TGA test resin
d) be 389 ℃; In the IR spectrogram: 1778cm
-1Be C=O vibration absorption peak in the carbonyl; 1200cm
-1And 1148cm
-1Two absorptions the strongest are caused by the CF vibration; 984cm
-1Be CF
3Vibration causes; 720cm
-1, 641cm
-1Cause by the TFE vibration; 2986cm
-1And 2876cm
-1Two peaks are the methyl vibration absorption peak; 1036cm
-1For-C-O-C-strong vibration absorption peak, 2975cm
-1, 2885cm
-1, 1454cm
-1Cause by the ethene vibration.
Embodiment 5 (emulsion system, persulphate is made initiator)
Polymerization single polymerization monomer is selected tetrafluoroethylene, ethene; Alkene ether monomer: CF
2=CFO-CF
2CF (CF
3) O-CF
2CF
2COOCH
3, molecular weight 422g/mol
10L stainless steel autoclave is cleaned and vacuumized, fill high pure nitrogen displacement three times, below 10ppm, be evacuated to-0.1MPa, in reactor, add and contain 13.8g perfluor propoxy-carboxylic acid ammonium (molecular formula CF until Control for Oxygen Content
3CF
3CF
2OCFCF
3CF
2-OCFCF
3COONH
4) pure water 6L, 100g alkene ether monomer (CF
2=CFO-CF
2CF (CF
3) O-CF
2CF
2COOCH
3, molecular weight 422g/mol), be warming up to 75 ℃, feed tetrafluoroethylene, ethene mixed gas (gas mole ratio is 70: 30) to 4.2MPa, contain 0.0004mol/L Potassium Persulphate initiator lasting in reactor, the adding with volume pump, reaction begins to carry out.By in system, constantly adding mix monomer to keep reaction pressure at 4.2MPa, the tetrafluoroethylene monomer amount that enters reaction system by calculation of pressure is when 1300g, stop to feed mix monomer, when the still internal pressure is reduced to 4.0MPa, stopped reaction, reclaim unreacted tetrafluoroethylene monomer, emit mixture as smashing to pieces in the bucket by dispensing valve,, obtain the white polymer wet mash by high speed shear breakdown of emulsion in smashing bucket to pieces, after deionized water repeatedly washs, 100 ℃ of vacuum-dryings.Filtrate goes to unreacted alkene ether monomer of recovery tower Separation and Recovery and solvent.
Through F
19NMR, H NMR, IR analyze and turn out to be terpolymer.
Alkene ether monomer molar content is 1.3% in the polymers, the tetrafluoroethylene monomer molar content is 50% in the polymkeric substance, the vinyl monomer molar content is 48.7% in the polymkeric substance, its loading capacity melting index that to be 0.13mol/Kg measure resin by fusion index instrument be 6.5g/10mim (300 ℃, 5kg); 1% weight decomposition temperature (T of TGA test resin
d) be 402 ℃; In the IR spectrogram: 1778cm
-1Be C=O vibration absorption peak in the carbonyl; 1200cm
-1And 1148cm
-1Two absorptions the strongest are caused by the CF vibration; 984cm
-1Be CF
3Vibration causes; 720cm
-1, 641cm
-1Cause 2975cm by the TFE vibration
-1, 2885cm
-1, 1454cm
-1By ethene.
Embodiment 6, other is with embodiment 1, and difference is that the carboxylic acid monomer is selected from:
In the formula: a=4, n=0; A is selected from-COR
0R
0Be selected from-C
mH
2m+1, m=1～10 wherein.
Described perfluorocarbon solvent is the perfluor furans.Add-on is 6.5L.
Through F
19NMR, H NMR, IR analyze and turn out to be the design synthetic product.
Through F
19NMR, IR analyze and confirm that perfluor sulfonyl monomer molar percentage composition is 0.5-5% in the polymers, the tetrafluoroethylene monomer molar content is 45-59.5% in the polymkeric substance, the vinyl monomer molar content is 50-40% in the polymkeric substance, and its loading capacity is 0.01-0.5mol/Kg.Polymer data: the melting index of being measured resin by fusion index instrument is 1-100g/10mim.
Embodiment 7, other is with embodiment 1, and difference is that the carboxylic acid monomer is selected from:
In the formula: a=2, n=2; A is selected from-CONR
2R
3R
2～R
3Be selected from-C
mH
2m+1, m=1～10 wherein.
Described perfluorocarbon solvent is the perfluor pyrans.Add-on is 6.2L.
Through F
19NMR, H NMR, IR analyze and turn out to be the design synthetic product.
Through F
19NMR, IR analyze and confirm that perfluor sulfonyl monomer molar percentage composition is 0.5-5% in the polymers, the tetrafluoroethylene monomer molar content is 45-59.5% in the polymkeric substance, the vinyl monomer molar content is 50-40% in the polymkeric substance, and its loading capacity is 0.01-0.5mol/Kg.Polymer data: the melting index of being measured resin by fusion index instrument is 1-100g/10mim.
Embodiment 8, other is with embodiment 1, and difference is that the carboxylic acid monomer is selected from:
In the formula: a=5, n=0; A is selected from-CN.
Described perfluorocarbon solvent is the perfluor pyrans.Add-on is 6.3L.
Through F
19NMR, H NMR, IR analyze and turn out to be the design synthetic product.
Through F
19NMR, IR analyze and confirm that perfluor sulfonyl monomer molar percentage composition is 0.5-5% in the polymers, the tetrafluoroethylene monomer molar content is 45-59.5% in the polymkeric substance, the vinyl monomer molar content is 50-40% in the polymkeric substance, and its loading capacity is 0.01-0.5mol/Kg.Polymer data: the melting index of being measured resin by fusion index instrument is 1-100g/10mim.
Embodiment 9:
All synthetic of embodiment 3-8 have the ion exchanging function perfluorinated resin and all can adopt the throwing method among embodiment 1 and the embodiment 2 to prepare the perfluor fiber with ion exchanging function that design specification requires, these fibers can further be woven into the polymeric web of various models by the described Weaving method among the embodiment 1, various exchange membrane materials are strengthened.
Claims (11)
1. have the ion exchanging function fluoro-resin, form by following three class monomer copolymerizations:
1., tetrafluoroethylene CF
2=CF
2
2., ethene CH
2=CH
2
3., one or more have the monomer of structure shown in the following general formula:
In the formula: the integer of the integer of a=2～5, n=0～2; A is selected from-COR
0,-COOR
1,-CONR
2R
3,-CN;
R
0, R
1, R
2, R
3Be selected from-C
mH
2m+1, m=1～10 wherein; Molecular weight is 15-65 ten thousand, and the melt flow index under 300 ℃, 5Kg load is 1～100g/10min;
Tetrafluoroethylene monomer structural unit shared molar content in resin is 40～69.9%; Vinyl monomer structural unit shared molar content in resin is 50～30%; General formula 3. shown in monomer structure unit shared molar content total amount in resin be 0.1-10%.
2. as claimed in claim 1 have an ion exchanging function fluoro-resin, it is characterized in that monomer described in general formula 3., n=0 or 1; The integer of a=2-4; A is preferred-COOCH
3
3. as claimed in claim 1 have an ion exchanging function fluoro-resin, it is characterized in that tetrafluoroethylene monomer structural unit shared molar content preferred 45～59.5% in resin; Vinyl monomer structural unit shared molar content preferred 50～40% in resin; General formula 3. shown in monomer structure unit shared preferred 0.5-5% of molar content total amount in resin.
4. the application with fluoro-resin of ion exchanging function as claimed in claim 1, this resinoid melt extrudes spinning by melt extruding equipment in 200～400 ℃ of scopes, be fiber through drawing-off, cooling and shaping.
5. fluorine-contained polymerisate fibre with ion exchanging function, it is characterized in that, fluoro-resin with ion exchanging function as claimed in claim 1 melt extrudes spinning by melt extruding equipment in 200～400 ℃ of scopes, form through drawing-off, cooling and shaping.
6. the fluorine-contained polymerisate fibre with ion exchanging function as claimed in claim 5, fiber number is controlled at the 20-500 dawn.
7. the fluorine-contained polymerisate fibre with ion exchanging function as claimed in claim 5, it is characterized in that, the described fiber of claim 5 prepares after handling by alkali lye, and described alkali lye is selected from the sodium hydroxide solution of massfraction 5-30% or the potassium hydroxide solution of massfraction 5-30%.
8. the application with fluorine-contained polymerisate fibre material of ion exchanging function as claimed in claim 5, it is characterized in that described fluorine-contained polymerisate fibre material with ion exchanging function, be woven into fibrous reticulum by textile technology, as the enhancing framework material of chlor-alkali ion composite membrane.
9. the solution polymerization method with ion exchanging function fluoro-resin as claimed in claim 1 comprises the following steps:
1) reactor is cleaned and thorough drying after vacuumize, the inflated with nitrogen displacement, is evacuated to-0.1MPa below 10ppm until Control for Oxygen Content,
2) perfluorocarbon solvent, perfluorocarboxylic acid monomer are added in the reactor, stir and be warming up to 35～45 ℃,
3) treat that system temperature is constant after, add the perfluor peroxide initiator with volume pump, feed the mixed gas of tetrafluoroethylene and ethene, to pressure arrival 1.1MPa,
4) the lasting mixed gas that feeds tetrafluoroethylene and ethene makes reaction pressure at 0.8～1.1MPa, and reaction is constantly carried out,
5) adopt discontinuous manner in system, to add the perfluor peroxide initiator, when the mixed gas add-on of tetrafluoroethylene and ethene reaches 1000～1200g, stop to add, allow reaction proceed by volume pump;
6) when the still internal pressure is reduced to 0.8MPa, stopped reaction is recovered into unreacted mix monomer in the accumulator tank, puts into rake type dryer by discharging valve of reaction kettle goalkeeper material, reclaim reaction solvent and unreacted carboxylic acid monomer and dry polymer material, obtain the white powder product;
7) further with product in 100 ℃ of vacuum-dryings 6～10 hours;
Described perfluorocarboxylic acid monomer is selected from
In the formula: a=2～5, n=0～2; A is selected from-COR
0,-COOR
1,-CONR
2R
3,-CN; R
0, R
1, R
2, R
3Be selected from-C
mH
2m+1, m=1～10 wherein;
Described perfluorocarbon solvent is selected from: HFC225, perfluoro-2-methyl cyclobutane, perfluor furans, perfluor pyrans, its add-on are the 60-65% of reactor volume; In the mixed gas of tetrafluoroethylene and ethene, gas ratio is a tetrafluoroethylene: ethene equals (90～10): (10～90), volume ratio.
10. the suspension polymerization preparation method with ion exchanging function fluoro-resin as claimed in claim 1 comprises the following steps:
1) autoclave is cleaned and is vacuumized, fill the high pure nitrogen displacement, until oxygen level below 10ppm,
2) be evacuated to-0.1MPa, add pure water solution, the perfluorocarboxylic acid monomer contain perfluor propoxy-carboxylic acid ammonium in reactor, be warming up to 70 ℃, the mixed gas that feeds tetrafluoroethylene and ethene is to 4.0MPa,
3) adopt volume pump to continue to add initiator in reactor, reaction begins to carry out;
4) by in system, constantly adding the mixed gas and the initiator of tetrafluoroethylene and ethene, keep reaction pressure at 4.0MPa;
5) the mix monomer amount that enters reaction system by calculation of pressure stops to feed mix monomer when 1310g,
6) when the still internal pressure is reduced to 3.8MPa, stopped reaction reclaims unreacted mixing gas phase monomer, emits mixture by dispensing valve, and press filtration obtains the white polymer wet mash, wet mash after deionized water repeatedly washs, 100 ℃ of vacuum-dryings; Filtrate goes to the unreacted alkene ether monomer of recovery tower Separation and Recovery;
The add-on of described pure water is the 60-65% of reactor volume, and described perfluor propoxy-carboxylic acid ammonium's add-on is for adding the 0.2-0.5% of pure water volume; Described perfluorocarboxylic acid monomer is selected from
In the formula: a=2～5, n=0～2; A is selected from-COR
0,-COOR
1,-CONR
2R
3,-CN; R
0, R
1, R
2, R
3Be selected from-C
mH
2m+1, m=1～10 wherein;
The monomeric add-on of perfluorocarboxylic acid is the 5-10% of reactor volume; The blending ratio of tetrafluoroethylene, ethene mixed gas is: tetrafluoroethylene: ethene=(90～10): (10～90); Initiator is a potassium persulfate solution, and concentration is 0.0005～0.0007mol/L.
11. the emulsion-polymerizing preparation method with ion exchanging function fluoro-resin as claimed in claim 1 comprises the following steps:
1) reactor is cleaned and is vacuumized, fill the high pure nitrogen displacement, until Control for Oxygen Content below 10ppm,
2) be evacuated to-0.1MPa, in reactor, add pure water solution, the perfluorocarboxylic acid monomer that contains perfluor propoxy-carboxylic acid ammonium,
3) be warming up to 75 ℃, the mixed gas that feeds tetrafluoroethylene and ethene is to 4.2MPa,
4) continue to add initiator with volume pump in reactor, reaction begins to carry out;
5) mixed gas by constantly adding tetrafluoroethylene and ethene in system is to keep reaction pressure at 4.2MPa, and the tetrafluoroethylene monomer amount of reaction system stops to feed mix monomer when 1300g,
6) when the still internal pressure is reduced to 4.0MPa, stopped reaction, reclaim unreacted tetrafluoroethylene monomer, emitting mixture by dispensing valve goes into to smash to pieces in the bucket, by high speed shear breakdown of emulsion in smashing bucket to pieces, obtain the white polymer wet mash, wet mash after deionized water repeatedly washs, 100 ℃ of vacuum-dryings; Filtrate goes to unreacted alkene ether monomer of recovery tower Separation and Recovery and solvent;
The add-on of described pure water is the 60-65% of reactor volume, and described perfluor propoxy-carboxylic acid ammonium's add-on is for adding the 0.2-0.5% of pure water volume; Described perfluorocarboxylic acid monomer is selected from
In the formula: a=2～5, n=0～2; A is selected from-COR
0,-COOR
1,-CONR
2R
3,-CN; R
0, R
1, R
2, R
3Be selected from-C
mH
2m+1, m=1～10 wherein;
The monomeric add-on of perfluorocarboxylic acid is the 5-10% of reactor volume; The blending ratio of tetrafluoroethylene, ethene mixed gas is: tetrafluoroethylene: ethene=(90～10): (10～90); Described initiator is a Potassium Persulphate, and concentration is 0.0004～0.0005mol/L.
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| CN114773517B (en) * | 2022-04-07 | 2023-04-07 | 国家电投集团氢能科技发展有限公司 | Fluorine-containing sulfonic acid resin and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4578512A (en) * | 1980-06-11 | 1986-03-25 | The Dow Chemical Company | Process to produce novel fluorocarbon vinyl ethers and resulting polymers |
| JP2847850B2 (en) * | 1990-02-06 | 1999-01-20 | 旭硝子株式会社 | Ethylene-tetrafluoroethylene copolymer |
| CN101003596A (en) * | 2006-12-25 | 2007-07-25 | 山东东岳神舟新材料有限公司 | Perfluoro - resin with ion exchange, and application |
| JP4104988B2 (en) * | 2003-01-08 | 2008-06-18 | 三菱レイヨン株式会社 | Optical fiber and optical fiber cable |
| CN101350418A (en) * | 2008-07-22 | 2009-01-21 | 山东东岳神舟新材料有限公司 | Microporous-film-and-fiber-reinforced multilayer fluorine-containing cross-linking doping ionic membrane and preparation method thereof |
| CN101350417A (en) * | 2008-07-22 | 2009-01-21 | 山东东岳神舟新材料有限公司 | Microporous-film-reinforced multilayer fluorine-containing cross-linking doping ionic membrane and preparation method thereof |
-
2009
- 2009-10-26 CN CN2009102294422A patent/CN101693215B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4578512A (en) * | 1980-06-11 | 1986-03-25 | The Dow Chemical Company | Process to produce novel fluorocarbon vinyl ethers and resulting polymers |
| JP2847850B2 (en) * | 1990-02-06 | 1999-01-20 | 旭硝子株式会社 | Ethylene-tetrafluoroethylene copolymer |
| JP4104988B2 (en) * | 2003-01-08 | 2008-06-18 | 三菱レイヨン株式会社 | Optical fiber and optical fiber cable |
| CN101003596A (en) * | 2006-12-25 | 2007-07-25 | 山东东岳神舟新材料有限公司 | Perfluoro - resin with ion exchange, and application |
| CN101350418A (en) * | 2008-07-22 | 2009-01-21 | 山东东岳神舟新材料有限公司 | Microporous-film-and-fiber-reinforced multilayer fluorine-containing cross-linking doping ionic membrane and preparation method thereof |
| CN101350417A (en) * | 2008-07-22 | 2009-01-21 | 山东东岳神舟新材料有限公司 | Microporous-film-reinforced multilayer fluorine-containing cross-linking doping ionic membrane and preparation method thereof |
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