CN101693751B - Functional fluororesins and application thereof - Google Patents
Functional fluororesins and application thereof Download PDFInfo
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- CN101693751B CN101693751B CN2009102294418A CN200910229441A CN101693751B CN 101693751 B CN101693751 B CN 101693751B CN 2009102294418 A CN2009102294418 A CN 2009102294418A CN 200910229441 A CN200910229441 A CN 200910229441A CN 101693751 B CN101693751 B CN 101693751B
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Abstract
The invention discloses fluororesins with an ion exchanging function, which comprise tetrafluoroethylene, ethylene and one or pluralities of monomers with structures illustrated by following general formulas (I): in the formulas, a=0-5, b=0-5, a+b=/0, n=0-2; Rf and Rf' are chosen from -F, -C1, -Br or -CzF2z+1, wherein z=1-5; A is chosen from -SO2F, -SO2C1, -SO2Br or -SO2NR1R2; and R1 and R2 are chosen from -H or -CmH2m+1, wherein m=1-10. Fluorine-contained polymers with the 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 fuel battery 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 and improving the exchange capability of the ions.
Description
Technical field
The invention belongs to the fluoro-containing macromolecule material field, relate to that a class has functional fluororesins and as the application of ion-exchange membrane reinforcing fiber materials.
Background technology
After perfluorinated sulfonic acid type ion-exchange membrane was exhibited one's skill to the full in chlorine industry and Proton Exchange Membrane Fuel Cells, 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: Electrochimica Acta, 2005, vol.50, no.16-17, report is handled the ETFE mould material by gamma-ray irradiation, thereafter sulfonating surface, make it to have sulfonic acid group, this mould material has good thermostability and chemical stability, is applied in the direct methanol fuel cell; Journal of Membrane Science, 2006, vol.280, no.1-2 has characterized ethylene-tetrafluoroethylene copolymer membrane surface by radiation treatment sulfonation thereafter, and the functional membrane that obtains directly applies in the direct methanol fuel cell.Present a lot of research all is that the mode by 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, the chemical bond of fracture can not guarantee all to form sulfonic acid again, 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.
Technical scheme of the present invention is as follows:
Fluoro-resin with ion exchanging function of the present invention is the fluoro-resin that has ion-exchange group, is to be formed by following several 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: a=0～5, b=0～5 and a+b ≠ 0; N=0～2; R
f, R
f' can identical or differently be selected from-F ,-Cl ,-Br or-C
zF
2z+1, z=1～5 wherein;
A is selected from-SO
2F ,-SO
2Cl ,-SO
2Br or-SO
2NR
1R
2
R
1, R
2Can identical or differently be selected from-H or-C
mH
2m+1, m=1～10;
The molecular weight of described ion exchanging function fluoro-resin is: 20-60 ten thousand; Melt flow index under 300 ℃, 5Kg load is 1～100g/10min.
Preferably, general formula 3. described in monomer, n=0,1; A+b=1～4; R
f, R
f' be selected from-F or-CF
3A is selected from-SO
2F.
Contain in the above-mentioned fluoro-resin-SO
2F ,-SO
2Cl ,-SO
2Br ,-SO
2NR
1R
2Group 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.
The fluoro-resin that has ion-exchange group of the present invention is the monomeric random copolymerss of above-mentioned three classes.Preferably, above-mentioned have that monomer tetrafluoroethylene shared molar content in resin is 30～69.9% in the ion exchanging function fluoro-resin; Ethene shared molar content in resin is 60～30%; General formula 3. shown in monomer shared molar content total amount in resin be 0.1-10%.Melt flow index under 300 ℃ of 5Kg loads 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 40～59.5% 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.
A kind of fiber 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 fiber, fiber number is controlled at the 20-500 dawn.
The present invention also provides a kind of fluorine-contained polymerisate fibre with ion exchanging function, 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, the enhancing framework material of the battery proton exchange membrane that acts as a fuel or 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, perfluor sulfonyl 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 1MPa,
4) the lasting mixed gas that feeds tetrafluoroethylene and ethene makes reaction pressure remain on 0.8～1.0MPa, 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 sulphonyl monomer and dry polymer material, obtain the white powder product.
7) further with product in 100 ℃ of vacuum-dryings 6～10 hours.
Described perfluor sulfonyl monomer is selected from:
In the formula: a=0～5, b=0～5, a+b ≠ 0, n=0～2; R
f, R
f' can identical or differently be selected from-F ,-Cl ,-Br or-C
zF
2z+1, z=1～5 wherein;
A is selected from-SO
2F ,-SO
2Cl ,-SO
2Br or-SO
2NR
1R
2
R
1, R
2Can identical or differently be selected from-H or-C
mH
2m+1, m=1～10.
Preferably, described perfluor sulfonyl monomer is selected from perfluor 3-oxa--4-alkene-penta sulfonic acid fluoride, molecular formula: FO
2SCF
2CF
2OCF=CF
2
Described perfluorocarbon solvent is selected from: HFC225, perfluoro-2-methyl cyclobutane, perfluor furans, perfluor pyrans, its add-on are the 50-65% of reactor volume.
Described perfluor peroxide initiator is selected from peroxidation perfluor butyryl radicals compound, and 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.
In the reaction, the mixed gas add-on of tetrafluoroethylene and ethene calculates by pressure change.
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 perfluor sulfonyl 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) adopting volume pump to continue to add initiator for reaction in reactor begins to carry out;
4) by in system, constantly adding the mix monomer and the initiator of tetrafluoroethylene and ethene, keep reaction pressure at 4.0MPa;
5) the mix monomer amount that enters the tetrafluoroethylene of reaction system and ethene 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.
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 perfluor sulfonyl monomer is selected from:
In the formula: a=0～5, b=0～5, a+b ≠ 0, n=0～2; R
f, R
f' can identical or differently be selected from-F ,-Cl ,-Br or-C
zF
2z+1, z=1～5 wherein;
A is selected from-SO
2F ,-SO
2Cl ,-SO
2Br or-SO
2NR
1R
2
R
1, R
2Can identical or differently be selected from-H or-C
mH
2m+1, m=1～10.
Preferred, described perfluor sulfonyl monomer is selected from perfluor 3-oxa--4-alkene-penta sulfonic acid fluoride, molecular formula: FO
2SCF
2CF
2OCF=CF
2
Described perfluor propoxy-carboxylic acid ammonium's molecular formula is CF
3CF
3CF
2OCFCF
3CF
2-OCFCF
3COONH
4
Preferably, the monomeric add-on of perfluor sulfonyl is the 5-10% of reactor volume.
Preferably, the blending ratio of tetrafluoroethylene, ethene mixed gas is: tetrafluoroethylene: ethene=(90～10): (10～90)
Described initiator is a potassium persulfate solution, and concentration is 0.0005～0.0007mol/L.
In the reaction, the mixed gas add-on of tetrafluoroethylene and ethene calculates by pressure change.
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 perfluor sulfonyl monomer that contains perfluor propoxy-carboxylic acid ammonium,
3) be warming up to 75 ℃, the mixed gas that feeds tetrafluoroethylene and ethene is to 3.8MPa,
4) contain initiator lasting the adding with volume pump in reactor, reaction begins to carry out.
5) mix monomer by constantly adding tetrafluoroethylene and ethene in system is to keep reaction pressure at 3.8MPa, and the tetrafluoroethylene monomer amount that enters reaction system stops to feed mix monomer when 1300g,
6) when the still internal pressure is reduced to 3.7MPa, 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.
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 perfluor sulfonyl monomer is selected from:
In the formula: a=0～5, b=0～5, a+b ≠ 0, n=0～2; R
f, R
f' can identical or differently be selected from-F ,-Cl ,-Br or-C
zF
2z+1, z=1～5 wherein;
A is selected from-SO
2F ,-SO
2Cl ,-SO
2Br or-SO
2NR
1R
2
R
1, R
2Can identical or differently be selected from-H or-C
mH
2m+1, m=1～10.
Preferred, described perfluor sulfonyl monomer is selected from perfluor 3-oxa--4-alkene-penta sulfonic acid fluoride, molecular formula: FO
2SCF
2CF
2OCF=CF
2
Described perfluor propoxy-carboxylic acid ammonium's molecular formula is CF
3CF
3CF
2OCFCF
3CF
2-OCFCF
3COONH
4
Described initiator is the 0.00047mol/L Potassium Persulphate.
Preferably, the monomeric add-on of perfluor sulfonyl is the 5-10% of reactor volume.
Preferably, the blending ratio of tetrafluoroethylene, ethene mixed gas is: tetrafluoroethylene: ethene=(90～10): (10～90).
In the reaction, the mixed gas add-on of tetrafluoroethylene and ethene calculates by pressure change.
The present invention has the application of the perfluorinated 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 perfluorinated resin be the (per) 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, the enhancing net materials of the battery proton exchange membrane that acts as a fuel and chlor-alkali ionic membrane can reach enhancing simultaneously, increases the ability of sticking and increase the purpose of ion exchanging function.As the enhancing net materials of proton exchange membrane and 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 acyl superoxide 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:(solution polymerization, fluorocarbon solvent, perfluoroalkyl acyl superoxide initiator)
Polymerization single polymerization monomer is selected tetrafluoroethylene, ethene, perfluor sulfonyl monomer, and its molecular formula is CF
2=CFO-CF
2CF (CF
3) O-CF
2CF
2SO
2F (be n=1, Rf '=F, a=1, b=0, A=SO
2F), it is free-radical polymerized molecular weight 446g/mol, reference USP.3282875 preparation) 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; 5.8L perfluorocarbon solvent, 420g perfluor sulfonyl monomer are added in the reactor; stir also and be warming up to 40 ℃, treat that system temperature is constant after, add 40ml with volume pump and contain 4.94g 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 73: 17) of tetrafluoroethylene and ethene, to pressure arrival 1MPa, continuing to feed mixed gas makes reaction pressure at 0.8～1.0MPa, reaction is constantly carried out, adopted discontinuous manner in system, to add the perfluor peroxide initiator, calculate when the mixed gas add-on reaches 1100g 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 sulphonyl monomer and dry polymer material, obtain the white powder product.Further with product in 100 ℃ of vacuum-dryings 8 hours, obtain the 1020g resin.Molecular weight is 20-60 ten thousand.Through F
19NMR, IR analyze and confirm that perfluor sulfonyl monomer molar percentage composition is 2.0% in the polymers, the tetrafluoroethylene monomer molar content is 66.22% in the polymkeric substance, the vinyl monomer molar content is 31.78% in the polymkeric substance, and its loading capacity is 0.245mol/Kg.Polymer data: the melting index of measuring resin by fusion index instrument be 30.5g/10mim (300 ℃, 5kg); 1% weight decomposition temperature (Td) of TGA test resin is 396 ℃; IR spectrogram: 1468cm
-1Be S=O vibration in the sulfonic acid fluoride; 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, 310 ℃ of screw extrusion press head temperatures, 315 ℃ of nozzle plate temperature, 450 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 50～200 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.Described perfluorocarbon solvent is selected from HFC225, and its add-on is 5.8L.
Embodiment 2:(solution polymerization, fluorocarbon solvent, perfluoroalkyl acyl superoxide initiator)
Polymerization single polymerization monomer is selected tetrafluoroethylene, ethene; Two kinds of its 1 molecular formula of perfluor sulfonyl monomer are CF
2=CFO-CF
2CF (CF
3) O-CF
2CF
2SO
2F (be n=1, Rf '=F, a=1, b=0, A=SO
2F), molecular weight 446g/mol, preparation reference USP.3282875; Its 2 molecular formula is CF
2=CFO-CF
2CF
2SO
2F (be n=0, Rf '=F, a=1, b=0, A=SO
2F), molecular weight 280g/mol, preparation reference USP.3560568, 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, 260g perfluor sulfonyl monomer 1 and 160g perfluor sulfonyl monomer 2 are added in the reactor; stir also and be warming up to 40 ℃, treat that system temperature is constant after, add 60ml with volume pump and contain the different propionyl superoxide of 8.04g 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 1100g 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 sulphonyl monomer and dry polymer material, obtain the white powder product.Further with product in 100 ℃ of vacuum-dryings 8 hours, obtain the 830g resin.Molecular weight is 20-60 ten thousand.Through F
19It is 1.5% that NMR, IR analyze the molar content that confirms perfluor sulfonyl monomer 1 in the polymers, the molar content of perfluor sulfonyl monomer 2 is 0.7%, the tetrafluoroethylene monomer molar content is 66.8%, the vinyl monomer molar content is 31%, and the loading capacity of resin is 0.297mol/Kg.Polymer data: the melting index of measuring resin by fusion index instrument be 18.5g/10mim (300 ℃, 5kg); 1% weight decomposition temperature (T of TGA test resin
d) be 412 ℃; IR spectrogram: 1468cm
-1Be S=O vibration in the sulfonic acid fluoride; 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.Described perfluorocarbon solvent is selected from perfluoro-2-methyl cyclobutane, and its add-on is 6.0L.
Embodiment 3 (suspension polymerization, persulphate is an initiator, water is as dispersion medium)
Polymerization single polymerization monomer is selected tetrafluoroethylene, ethene; Perfluor sulfonyl monomer (CF
2=CFO-CF
2CF
2SO
2F, molecular weight 280g/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 2.3g perfluor propoxy-carboxylic acid ammonium (molecular formula CF until oxygen level
3CF
3CF
2OCFCF
3CF
2-OCFCF
3COONH
4) pure water 6L, 100g perfluor sulfonyl monomer (CF
2=CFO-CF
2CF
2SO
2F, molecular weight 280g/mol), is warming up to 70 ℃, feeds tetrafluoroethylene, (blending ratio is the ethene mixed gas: tetrafluoroethylene: ethene=55: 45) to 4.0MPa, adopting volume pump to continue to add concentration in reactor is the potassium persulfate solution of 0.0006mol/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.Molecular weight is 20-60 ten thousand.Through F
19NMR, H NMR, IR analyze and turn out to be the design synthetic product.
Perfluor sulfonyl monomer molar percentage composition is 1.6% in the polymers, and the tetrafluoroethylene monomer molar content is 55%, and the vinyl monomer molar content is 43.4%, the melting index of measuring resin by fusion index instrument be 14.8g/10mim (300 ℃, 5kg); 1% weight decomposition temperature (T of TGA test resin
d) be 405 ℃; In the IR spectrogram: 1468cm
-1For in the sulfonic acid fluoride-S=O vibration; 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; Perfluor sulfonyl monomer (CF
2=CFO-CF
2CF
2SO
2F, molecular weight 280g/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 perfluor sulfonyl monomer (CF until Control for Oxygen Content
2=CFO-CF
2CF
2SO
2F, molecular weight 280g/mol), be warming up to 43 ℃, feed tetrafluoroethylene, ethene mixed gas to pressure is 1.0MPa, in reactor, add 50ml with volume pump and contain 4.2g 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.Molecular weight is 20-60 ten thousand.Through F
19NMR, H NMR, IR analyze and turn out to be the design product.
Perfluor sulfonyl monomer molar percentage composition is 2.5% in the polymers, and the tetrafluoroethylene monomer molar content is 49%, and the vinyl monomer molar content is 48.5%, the melting index of measuring resin by fusion index instrument be 10.8g/10mim (300 ℃, 5kg); 1% weight decomposition temperature (T of TGA test resin
d) be 416 ℃; In the IR spectrogram: 1468cm
-1For in the sulfonic acid fluoride-S=O vibration; 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; Perfluor sulfonyl monomer (CF
2=CFO-CF
2CF
2SO
2F, molecular weight 280g/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 13.3g perfluor propoxy-carboxylic acid ammonium (molecular formula CF until Control for Oxygen Content
3CF
3CF
2OCFCF
3CF
2-OCFCF
3COONH
4) pure water 6L, 200g perfluor sulfonyl monomer (CF
2=CFO-CF
2CF
2SO
2F, molecular weight 280g/mol), be warming up to 75 ℃, feed tetrafluoroethylene, ethene mixed gas (gas mole ratio is 70: 30) to 3.8MPa, contain 0.00047mol/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 3.8MPa, 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 3.7MPa, 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.Molecular weight is 20-60 ten thousand.Through F
19NMR, H NMR, IR analyze and turn out to be terpolymer.
Perfluor sulfonyl monomer molar percentage composition is 1.3% in the polymers, and the tetrafluoroethylene monomer molar content is 59%, and the vinyl monomer molar content is 39.7%, the melting index of measuring resin by fusion index instrument be 8.5g/10mim (300 ℃, 5kg); 1% weight decomposition temperature (T of TGA test resin
d) be 422 ℃; In the IR spectrogram: 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
-1Cause by the ethene vibration.
Embodiment 6
Other are with embodiment 1, and difference is: the perfluor sulfonyl monomer is selected from:
In the formula: a=0, b=1, n=1; R
f=-F, R
fThe CF of '=-
3A=-SO
2Br.
Described perfluorocarbon solvent is selected from perfluoro-2-methyl cyclobutane, and its add-on is 6.5L.
Molecular weight is 20-60 ten thousand.Through F
19NMR, IR analyze and confirm that perfluor sulfonyl monomer molar percentage composition is 0.1-10% in the polymers, and the tetrafluoroethylene monomer molar content is 30-69.9% in the polymkeric substance, and the vinyl monomer molar content is 60-30% in the polymkeric substance.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 are with embodiment 1, and difference is: the perfluor sulfonyl monomer is selected from:
In the formula: a=1, b=1, n=1; R
f=-CF
3, R
fThe CF of '=-
3A=--SO
2Cl.
Described perfluorocarbon solvent is selected from the perfluor furans, and its add-on is 5.5L.
Molecular weight is 20-60 ten thousand.Through F
19NMR, IR analyze and confirm that perfluor sulfonyl monomer molar percentage composition can be 0.1-10% in the polymers, and the tetrafluoroethylene monomer molar content is 30-69.9% in the polymkeric substance, and the vinyl monomer molar content is 60-30% in the polymkeric substance.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 are with embodiment 1, and difference is: the perfluor sulfonyl monomer is selected from:
In the formula: a=2, b=0, n=1; R
f=CF
3, R
fThe F of '=-; A=-SO
2NR
1R
2, R
1=R
2=-CH
3
Described perfluorocarbon solvent is selected from the perfluor pyrans, and its add-on is 6.2L.
Molecular weight is 20-60 ten thousand.Through F
19NMR, IR analyze and confirm that perfluor sulfonyl monomer molar percentage composition can be 0.1-10% in the polymers, the tetrafluoroethylene monomer molar content is 30-69.9% in the polymkeric substance, the vinyl monomer molar content is 60-30% 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 (10)
1. the fluoro-resin that has ion exchanging function 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: a=0～5, b=0～5 and a+b=1～4; N=0; R
f, R
f' be selected from-F or-CF
3A is selected from-SO
2F;
The molecular weight of described ion exchanging function fluoro-resin is: 20-60 ten thousand; Melt flow index under 300 ℃, 5Kg load is 1～100g/10min;
Tetrafluoroethylene monomer structural unit shared molar content in resin is 30～69.9%; Vinyl monomer structural unit shared molar content in resin is 60～30%; General formula 3. shown in monomer structure unit shared molar content total amount in resin be 0.1-10%.
2. the fluoro-resin with ion exchanging function as claimed in claim 1 is characterized in that tetrafluoroethylene monomer structural unit shared molar content in resin is 40～59.5%; Vinyl monomer structural unit shared molar content in resin is 50～40%; General formula 3. shown in monomer structure unit shared molar content total amount in resin be 0.5-5%.
3. 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.
4. 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.
5. the fluorine-contained polymerisate fibre with ion exchanging function as claimed in claim 4 is characterized in that fiber number is controlled at the 20-500 dawn.
6. the fluorine-contained polymerisate fibre with ion exchanging function as claimed in claim 4, it is characterized in that, the described fiber of claim 4 prepares after handling by alkali lye, and sodium hydroxide solution or massfraction that described alkali lye is selected from massfraction 5-30% are the potassium hydroxide solution of 5-30%.
7. the application with fluorine-contained polymerisate fibre material of ion exchanging function as claimed in claim 4, it is characterized in that described fluorine-contained polymerisate fibre material with ion exchanging function, be woven into fibrous reticulum by textile technology, the enhancing framework material of the battery proton exchange membrane that acts as a fuel or chlor-alkali ion composite membrane.
8. 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, perfluor sulfonyl 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 1MPa,
4) the lasting mixed gas that feeds tetrafluoroethylene and ethene makes reaction pressure remain on 0.8～1.0MPa, 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 sulphonyl monomer and dry polymer material, obtain the white powder product;
7) further with product in 100 ℃ of vacuum-dryings 6～10 hours;
Described perfluor sulfonyl monomer is selected from
In the formula: a=0～5, b=0～5 and a+b=1～4; N=0; R
f, R
f' be selected from-F or-CF
3
A is selected from-SO
2F;
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;
Described perfluor peroxide initiator is selected from peroxidation perfluor butyryl radicals compound, and 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.
9. 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 perfluor sulfonyl 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) adopting volume pump to continue to add initiator for reaction in reactor begins to carry out;
4) by in system, constantly adding the mix monomer and the initiator of tetrafluoroethylene and ethene, keep reaction pressure at 4.0MPa;
5) the mix monomer amount that enters the tetrafluoroethylene of reaction system and ethene 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 perfluor sulfonyl monomer is selected from:
In the formula: a=0～5, b=0～5 and a+b=1～4; N=0; R
f, R
f' identical or differently be selected from-F or-CF
3
A is selected from-SO
2F;
Described perfluor propoxy-carboxylic acid ammonium's molecular formula is CF
3CF
3CF
2OCFCF
3CF
2-OCFCF
3COONH
4
The monomeric add-on of perfluor sulfonyl 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 persulfate solution, and concentration is 0.0005～0.0007mol/L.
10. 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 perfluor sulfonyl monomer that contains perfluor propoxy-carboxylic acid ammonium,
3) be warming up to 75 ℃, the mixed gas that feeds tetrafluoroethylene and ethene is to 3.8MPa,
4) continue to add initiator with volume pump in reactor, reaction begins to carry out;
5) mix monomer by constantly adding tetrafluoroethylene and ethene in system is to keep reaction pressure at 3.8MPa, and the tetrafluoroethylene monomer amount that enters reaction system stops to feed mix monomer when 1300g,
6) when the still internal pressure is reduced to 3.7MPa, 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.
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| WO2012082451A2 (en) * | 2010-12-17 | 2012-06-21 | 3M Innovative Properties Company | Fluorinated oligomers having pendant bromine-containing moieties |
| CN103347908B (en) | 2010-12-17 | 2017-02-08 | 3M创新有限公司 | Microemulsions and fluoropolymers made using microemulsions |
| US9266999B2 (en) | 2010-12-17 | 2016-02-23 | 3M Innovative Properties Company | Oligomers and co-oligomers of highly fluorinated sulfinic acid and salts thereof |
| CN105358592B (en) * | 2013-07-03 | 2017-09-19 | 旭硝子株式会社 | The manufacture method of fluoropolymer |
| CN106928395B (en) * | 2015-12-29 | 2020-04-21 | 山东东岳未来氢能材料有限公司 | Functional perfluorinated sulfonamide resin with good thermal stability as well as preparation method and application thereof |
| CN111040066B (en) * | 2019-12-31 | 2021-12-07 | 山东华夏神舟新材料有限公司 | High speed extruded fluoropolymer and method of making same |
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| JP2847850B2 (en) * | 1990-02-06 | 1999-01-20 | 旭硝子株式会社 | Ethylene-tetrafluoroethylene copolymer |
| JP3063907B2 (en) * | 1990-02-20 | 2000-07-12 | 旭硝子株式会社 | Method for producing ethylene-tetrafluoroethylene copolymer |
| CN101003588A (en) * | 2006-12-25 | 2007-07-25 | 山东东岳神舟新材料有限公司 | Polymer of containing fluorin, and application as material of ion exchange fiber |
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| JP3028964B2 (en) * | 1990-05-29 | 2000-04-04 | 旭硝子株式会社 | Method for producing high-strength and elongate ethylene tetrafluoride-ethylene copolymer |
| JPH07117188A (en) * | 1993-10-22 | 1995-05-09 | Asahi Glass Co Ltd | Laminated film for agriculture |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2847850B2 (en) * | 1990-02-06 | 1999-01-20 | 旭硝子株式会社 | Ethylene-tetrafluoroethylene copolymer |
| JP3063907B2 (en) * | 1990-02-20 | 2000-07-12 | 旭硝子株式会社 | Method for producing ethylene-tetrafluoroethylene copolymer |
| CN101003588A (en) * | 2006-12-25 | 2007-07-25 | 山东东岳神舟新材料有限公司 | Polymer of containing fluorin, and application as material of ion exchange fiber |
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