CN102716678A - Polytetrafluoroethylene microporous film and production method thereof - Google Patents
Polytetrafluoroethylene microporous film and production method thereof Download PDFInfo
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- CN102716678A CN102716678A CN2012102289591A CN201210228959A CN102716678A CN 102716678 A CN102716678 A CN 102716678A CN 2012102289591 A CN2012102289591 A CN 2012102289591A CN 201210228959 A CN201210228959 A CN 201210228959A CN 102716678 A CN102716678 A CN 102716678A
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- microporous teflon
- teflon membran
- water
- garment material
- moisture permeability
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 229920001343 polytetrafluoroethylene Polymers 0.000 title abstract description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 title abstract description 16
- -1 Polytetrafluoroethylene Polymers 0.000 title abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000011347 resin Substances 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 230000035699 permeability Effects 0.000 claims abstract description 42
- 239000006185 dispersion Substances 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000004744 fabric Substances 0.000 claims abstract description 10
- 239000010687 lubricating oil Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000004809 Teflon Substances 0.000 claims description 60
- 229920006362 Teflon® Polymers 0.000 claims description 60
- 210000004379 membrane Anatomy 0.000 claims description 58
- 239000000463 material Substances 0.000 claims description 46
- 239000000839 emulsion Substances 0.000 claims description 20
- 239000011164 primary particle Substances 0.000 claims description 19
- 238000013459 approach Methods 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- 230000005484 gravity Effects 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000004677 Nylon Substances 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical group OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 230000002459 sustained effect Effects 0.000 claims description 4
- WUMVZXWBOFOYAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluoro-1-(1,2,3,3,4,4,4-heptafluorobut-1-enoxy)but-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)F WUMVZXWBOFOYAW-UHFFFAOYSA-N 0.000 claims description 3
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims description 2
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 claims description 2
- UPVJEODAZWTJKZ-UHFFFAOYSA-N 1,2-dichloro-1,2-difluoroethene Chemical group FC(Cl)=C(F)Cl UPVJEODAZWTJKZ-UHFFFAOYSA-N 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 206010043268 Tension Diseases 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 2
- CSJWOWRPMBXQLD-UHFFFAOYSA-N perfluoromethylvinylether group Chemical group FC(=C(C(F)(F)F)F)OC(=C(F)C(F)(F)F)F CSJWOWRPMBXQLD-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims 1
- 239000002121 nanofiber Substances 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000011258 core-shell material Substances 0.000 abstract 1
- 238000009998 heat setting Methods 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 238000005096 rolling process Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920006361 Polyflon Polymers 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 239000002473 artificial blood Substances 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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Abstract
The invention discloses a production method of a polytetrafluoroethylene microporous film. The production method comprises the following steps of 1) mixing polytetrafluoroethylene dispersion resin with a core-shell structure with lubricating oil, evenly stirring and then pressing the mixture into cylindrical paste mixture; 2) squeezing and extruding the paste mixture at 20-120DEG C through an extruder, rolling the paste into bands and then removing the lubricating oil in the bands at 100-300DEG C or by using volatile organic solvent; and 3) unidirectionally or bidirectionally drawing the de-oiled bands at 100-390DEG C and finally conducting heat setting. The invention additionally discloses the polytetrafluoroethylene microporous film which is produced by adopting the production method of the polytetrafluoroethylene microporous film, wherein the content of nano-fibers in the polytetrafluoroethylene microporous film is high and the physical and mechanical strength is high. When the polytetrafluoroethylene microporous film is used in the clothing industry, after the polytetrafluoroethylene microporous film is compounded with clothing fabrics, the obtained compound fabrics have advantages that the water pressure resistance, the moisture permeability and the air permeability are improved, the water washing resistance is excellent and the compound fabrics can be accepted by the market.
Description
Technical field
The present invention relates to fluorine resin, be specifically related to a kind of microporous teflon membran and manufacturing approach thereof.
Background technology
Fluorine resin, particularly polyflon have excellent physical and mechanical performance and chemical stability, all have a wide range of applications in each fields such as chemical materials, mechano-electronic, space flight military project, new material and new forms of energy.Polytetrafluoroethyldispersion dispersion resin is adopted the paste extruding and extrudes also de-oiling; Pass through unidirectional or biaxial tension again; Can obtain to have the polytetrafluoroethylene (PTFE) poromerics of micropore; Because its property, this material becomes a kind of functional fluoropolymer property material of high-end applications, for example as environmental protection filter material, garment material, man-made organ material, electronic material and sealed insulating material etc.
Microporous teflon membran is because of having good physical and chemical performance, mechanical performance, and water-proof breathable properties and chemical stability just have been used to make wire cable insulating material, artificial blood vessel, band, environmental protection filtration and garment material etc. since the seventies.Usually adopt the high-purity tetrafluoroethylene monomer in the industry, carry out polymerization or copolymerization prepares dispersion resin through dispersion polymerization processes.Gather the tetrafluoro dispersion resin and can not carry out molten thermoplastic processing, normally, extrude through the paste extruding, de-oiling, microporous membrane material is processed in unidirectional again or biaxial tension.
The aperture of the microporous teflon membran of making at present is bigger, and its water pressure resistance property or filter effect can not satisfy application requirements; When being applied to apparel industry, water resistance and moisture permeability also do not reach requirement.
Summary of the invention
In view of this, the objective of the invention is to propose a kind of microporous teflon membran and manufacturing approach thereof, to improve mechanical strength or the water pressure resistance property or the air penetrability of microporous barrier.
Based on above-mentioned purpose, the present invention provides a kind of manufacturing approach of microporous teflon membran, and said manufacturing approach comprises following operation:
The polytetrafluoroethyldispersion dispersion resin that 1) will have a nucleocapsid structure mixes with lubricating oil and stirs, and is pressed into columned paste mixture then;
2) under 20 ~ 120 ℃, said paste mixture is pushed and extrudes, then said paste is rolled into band, under 100 ~ 300 ℃ temperature or with volatile organic solvent, slough the lubricating oil in the said band then through the pushing machine;
3) with the unidirectional or biaxial tensiones under 100 ~ 390 ℃ of the said band after the de-oiling, carry out thermal finalization at last, be made for said microporous teflon membran.
Alternatively, said polytetrafluoroethyldispersion dispersion resin with nucleocapsid structure mixes according to weight ratio 4 ~ 5:1 with said lubricating oil.
Alternatively, said polytetrafluoroethyldispersion dispersion resin with nucleocapsid structure makes according to following operation:
1) in autoclave, adds deionized water and perfluorinated surfactant, vacuumize in the still, heat up; Stirring is to form emulsion, and in still, feeding with the tetrafluoroethylene monomer then is main mix monomer gas, adds radical initiator; The started copolymer reaction, temperature in the kettle maintains 70 ~ 110 ℃; Pressure is along with reaction reduces, when the still internal pressure is reduced to less than 5kg/cm
2The time, the core copolymerization of said polytetrafluoroethyldispersion dispersion resin primary particle is accomplished, emulsion solid content 0.5 ~ 9%, and the average grain diameter of primary particle is 60 ~ 130nm;
2) after copolymerization is accomplished, vacuumize in the still, feed the polytetrafluoroethyl-ne alkene monomer of molar concentration＞99.999% again, temperature in the kettle maintains 70 ~ 110 ℃, and homopolymerization begins; The still internal pressure maintains 20kg/cm at least
2, sustained response is 20 ~ 39% to emulsion solid content, is cooled to room temperature, stop to stir, and reaction terminating, this moment, the housing parts homopolymerization of said polytetrafluoroethyldispersion dispersion resin primary particle was accomplished, and the average grain diameter of primary particle is 160 ~ 250nm;
3) emulsion is through breakdown of emulsion, and cohesion obtains polytetrafluoroethyldispersion dispersion resin after the drying, and its standard specific gravity is 2.14 ~ 2.20g/cm
3, housing parts accounts for 70 ~ 99% weight ratios, and the core accounts for 1 ~ 30% weight ratio.
Alternatively, said perfluorinated surfactant is meant the perfluor organic matter that contains 6 ~ 14 carbon, and contains the functional group of a carboxylic acid or sulfonic acid at least.
Preferably, said perfluorinated surfactant can be perfluorooctanoic acid.
Alternatively, said radical initiator is selected from any one or its combination in hydrogen peroxide solution, persulfate or the organic peroxy compound.Said radical initiator can produce free radical 50 ~ 250 ℃ of decomposition.
Preferably, said persulfate can be selected from any one or its combination in ammonium persulfate, sodium peroxydisulfate or the potassium peroxydisulfate.
Alternatively; Contain percent by volume in the said mix monomer gas and be 0.5 ~ 30% and can with the fluorochemical monomer of tetrafluoroethene copolymerization; Said fluorochemical monomer is selected from perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, vinylidene, PVF, trifluoro-ethylene, CTFE, difluoro dichloroethylene, 3; 3, the 3-trifluoropropyl rare with hexafluoropropene in any one or its combination.
The present invention also provides a kind of microporous teflon membran, and said microporous teflon membran is that the manufacturing approach according to above-mentioned microporous teflon membran makes.
Alternatively, point pastes 30 ~ 150g/m on said microporous teflon membran
2Polyester fabric after, the compound garment material water pressure resistance of gained is greater than 3kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day; After said compound garment material was washed through 10 times, its water pressure resistance was greater than 3kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day.
Alternatively, point pastes 30 ~ 150g/m on said microporous teflon membran
2Nylon 6 linings after, the compound garment material water pressure resistance of gained is greater than 5kg/cm
2, moisture permeability is greater than 10kg water/m
2/ day; After said compound garment material was washed through 10 times, its water pressure resistance was greater than 5kg/cm
2, moisture permeability is greater than 10kg water/m
2/ day.
Alternatively, point pastes 50 ~ 180g/m on said microporous teflon membran
2Cotton fabric after, the compound garment material water pressure resistance of gained is greater than 3kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day; After said compound garment material was washed through 10 times, its water pressure resistance was greater than 3kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day.
Alternatively, point pastes 60 ~ 250g/m on said microporous teflon membran
2The aramid fiber lining after, the compound garment material water pressure resistance of gained is greater than 3kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day; After said compound garment material was washed through 10 times, its water pressure resistance was greater than 3kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day.
Saidly can find out from top; According to the microporous teflon membran that manufacturing approach provided by the invention obtained; Its nanofiber content is high; Physical mechanical strength such as tension stress, water pressure resistance, hot strength are higher, and its extra small nanometer micropore can satisfy the higher or filter effect better application requirement of water pressure resistance.When being applied to apparel industry, after compound with garment material, the water pressure resistance of the composite material of gained, moisture permeability, gas permeability improve; Water-wash resistance is preferable, can be accepted by market.
Description of drawings
Fig. 1 is the scanning electron microscope diagram of the embodiment of the invention 2 polytetrafluoroethyldispersion dispersion resins;
Fig. 2 is the scanning electron microscope diagram of the embodiment of the invention 4 microporous teflon membrans;
Fig. 3 is the scanning electron microscope diagram of the embodiment of the invention 5 microporous teflon membrans.
The specific embodiment
For making the object of the invention, technical scheme and advantage clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, to further explain of the present invention.
Embodiment 1 (manufacturing) with polytetrafluoroethyldispersion dispersion resin of nucleocapsid structure
In one about 100 liters horizontal high-pressure agitated reactor, at first add the deionized water of 50L and the perfluorooctanoic acid of 15g, vacuumizing deoxygenation in the still, up to oxygen content<20ppm opens stirring to form emulsion; Temperature in the kettle rises to about 70 ℃, and feeding with the tetrafluoroethylene monomer in the still then is main mix monomer gas, contains 1% perfluoro methyl vinyl ether in the said mix monomer gas, and the still internal pressure reaches about 20kg/>cm
2Add 1g ammonium persulfate (being dissolved in advance in the 500mL water) in the still as initator, the started copolymer reaction, temperature in the kettle maintains 70 ~ 110 ℃, and pressure is reduced to less than 5kg/cm after about 1 hour along with reaction reduces
2This moment, core (TFE copolymer) polymerization of polytetrafluoroethyldispersion dispersion resin primary particle was accomplished, and emulsion solid content is about 6%, the about 80nm of the average grain diameter of primary particle.
With vacuumizing in the still, feed the tetrafluoroethylene monomer of molar concentration＞99.999% more then, pressure heavily is raised to about 20kg/cm again
2, temperature maintenance is at 70 ~ 110 ℃, and the tetrafluoroethene homopolymerization begins, and pressure maintains about 20kg/cm
2, sustained response reaches about 30% to emulsion solid content, is cooled to room temperature, stop to stir, reaction terminating, this moment the polytetrafluoroethyldispersion dispersion resin primary particle housing parts (proplast) polymerization accomplish the about 160nm of the average grain diameter of primary particle.Emulsion is through breakdown of emulsion, and cohesion after the drying, detects the standard specific gravity of polytetrafluoroethyldispersion dispersion resin, is about 2.17g/cm
3
Embodiment 2 (manufacturing) with polytetrafluoroethyldispersion dispersion resin of nucleocapsid structure
In one about 100 liters horizontal high-pressure agitated reactor, at first add the deionized water of 50L and the perfluorooctanoic acid of 18g, vacuumizing deoxygenation in the still, up to oxygen content<20ppm opens stirring to form emulsion; Temperature in the kettle is raised to about 70 ℃, and feeding with the tetrafluoroethylene monomer in the still then is main mix monomer gas, contains 1% perfluoroethylvinyl ether in the said mix monomer gas, and the still internal pressure reaches about 10kg/>cm
2Add 0.2g ammonium persulfate (being dissolved in advance in the 500mL water) in the still as initator, the started copolymer reaction, temperature in the kettle maintains 70 ~ 110 ℃, and pressure is reduced to less than 5kg/cm after about 1 hour along with reaction reduces
2, this moment, core (TFE copolymer) polymerization of polytetrafluoroethyldispersion dispersion resin primary particle was accomplished, and emulsion solid content is about 3%, the about 100nm of the average grain diameter of primary particle.
With vacuumizing in the still, feed the tetrafluoroethylene monomer of molar concentration＞99.999% more then, pressure heavily is raised to about 20kg/cm again
2, temperature maintenance is at 70 ~ 110 ℃, and the tetrafluoroethene homopolymerization begins, and pressure maintains about 20kg/cm
2, sustained response reaches about 30% to emulsion solid content, is cooled to room temperature, stop to stir, reaction terminating, this moment the polytetrafluoroethyldispersion dispersion resin primary particle housing parts (proplast) polymerization accomplish the about 220nm of the average grain diameter of primary particle.Emulsion is through breakdown of emulsion, and cohesion after the drying, detects the standard specific gravity of polytetrafluoroethyldispersion dispersion resin, is about 2.155g/cm
3With reference to figure 1, it is the scanning electron microscope diagram of the polytetrafluoroethyldispersion dispersion resin of present embodiment.
Embodiment 3 (manufacturing of microporous teflon membran)
Mix with the weight ratio of about 5:1 with U.S. Exxon Mobil senior lubricant (trade mark Isopar M) making the polytetrafluoroethyldispersion dispersion resin that obtains among the embodiment 1 with nucleocapsid structure; The first precompressed in back that stirs becomes cylinder; Extrude paste at about 50 ℃ of following high pressure again, and roll into the band of the about 0.1mm of thickness.With behind about 3 times of this band cross directional stretch in about 260 ℃ baking oven de-oiling obtain dry film.With about 10 times of this dry film longitudinal stretching under about 340 ℃ hot conditions, and then under about 360 ℃ hot conditions about 10 times of cross directional stretch, typing under about 390 ℃ of high temperature at last promptly obtains microporous teflon membran.
Through detecting, the average pore size of gained microporous teflon membran is about 60 ~ 80nm, and porosity is about 85 ~ 90%, and hot strength (laterally and vertically) is all greater than 300kg/cm
2, water pressure resistance is greater than 3kg/cm
2, moisture permeability is greater than 10kg water/m
2/ day, air penetrability is about 9 ~ 11 seconds.
With polyurethane adhesive with 70g/m
2The polyester fabric point be affixed on this microporous teflon membran that makes, the compound garment material water pressure resistance of gained is greater than 3kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day.This garment material still can keep water pressure resistance greater than 3kg/cm after washing through 10 times
2, moisture permeability is greater than 8kg water/m
2The excellent properties in/sky.
Embodiment 4 (manufacturing of microporous teflon membran)
Mix with the weight ratio of about 4:1 with U.S. Exxon Mobil senior lubricant (trade mark Isopar M) making the polytetrafluoroethyldispersion dispersion resin that obtains among the embodiment 2 with nucleocapsid structure; The first precompressed in back that stirs becomes cylinder; Extrude paste at about 50 ℃ of following high pressure again, and roll into the band of the about 0.6mm of thickness.With behind about 3.8 times of this band cross directional stretch in about 260 ℃ baking oven de-oiling obtain dry film.With about 30 times of this dry film longitudinal stretching under about 340 ℃ hot conditions, and then under about 360 ℃ hot conditions about 15 times of cross directional stretch, typing under about 390 ℃ of high temperature at last promptly obtains microporous teflon membran.With reference to figure 2, it is the scanning electron microscope diagram of the microporous teflon membran of present embodiment.
Through detecting, the average pore size of gained microporous teflon membran is about 45 ~ 60nm, and porosity is about 88 ~ 92%, and hot strength (laterally and vertically) is all greater than 500kg/cm
2, water pressure resistance is greater than 5kg/cm
2, moisture permeability is greater than 12kg water/m
2/ day, air penetrability is 6 ~ 8 seconds.
With polyurethane adhesive with 90g/m
2Nylon 6 linings point be affixed on this microporous teflon membran that makes, the compound garment material water pressure resistance of gained is greater than 5kg/cm
2, moisture permeability is greater than 10kg water/m
2/ day.This garment material still can keep water pressure resistance greater than 5kg/cm after washing through 10 times
2, moisture permeability is greater than 10kg water/m
2The excellent properties in/sky.
Embodiment 5 (manufacturing of microporous teflon membran)
Mix with the weight ratio of about 5:1 with U.S. Exxon Mobil senior lubricant (trade mark Isopar M) making the polytetrafluoroethyldispersion dispersion resin that obtains among the embodiment 2 with nucleocapsid structure; The first precompressed in back that stirs becomes cylinder; Extrude paste at about 50 ℃ of following high pressure again, and roll into the band of the about 0.05mm of thickness.This band is immersed in the volatile organic solvent, lubricating oil is extracted from band, volatile organisms such as organic solvent commonly used such as alcohol, acetone, ethyl acetate all can use, and use acetone in the present embodiment.Band after the de-oiling is finalized the design under about 345 ℃ hot conditions, and then under about 360 ℃ hot conditions about 15 times of cross directional stretch, typing under about 390 ℃ of high temperature at last promptly obtains microporous teflon membran.With reference to figure 3, it is the scanning electron microscope diagram of the microporous teflon membran of present embodiment.
Through detecting, the average pore size of gained microporous teflon membran is about 100 ~ 110nm, and porosity is about 83 ~ 88%, and hot strength (laterally and vertically) is all greater than 300kg/cm
2, water pressure resistance is greater than 3kg/cm
2, moisture permeability is greater than 15kg water/m
2/ day, air penetrability is about 11 ~ 12 seconds.
With polyurethane adhesive with 100g/m
2The cotton fabric point be affixed on this microporous teflon membran that makes, the compound garment material water pressure resistance of gained is greater than 3kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day.This garment material still can keep water pressure resistance greater than 3kg/cm after washing through 10 times
2, moisture permeability is greater than 8kg water/m
2The excellent properties in/sky.
Embodiment 6 (manufacturing of microporous teflon membran)
Mix mutually with the weight ratio of about 5:1 with U.S. Exxon Mobil senior lubricant (trade mark Isopar M) making the polytetrafluoroethyldispersion dispersion resin that obtains among the embodiment 2 with nucleocapsid structure; The first precompressed in back that stirs becomes cylinder; Extrude paste at about 50 ℃ of following high pressure again, and roll into the band of the about 0.6mm of thickness.Then the de-oiling in about 260 ℃ baking oven of this band is obtained dry film, with about 10 times of this dry film longitudinal stretching under about 360 ℃ hot conditions, typing under about 390 ℃ of high temperature at last promptly obtains microporous teflon membran.
Through detecting, the average pore size of gained microporous teflon membran is about 150 ~ 160nm, and porosity is about 60 ~ 65%, and hot strength (vertically) is greater than 300kg/cm
2, water pressure resistance is greater than 3kg/cm
2, moisture permeability is greater than 10kg water/m
2/ day, air penetrability is about 15 ~ 16 seconds.
With polyurethane adhesive with 120g/m
2Aramid fiber (Dupont
) the lining point is affixed on this microporous teflon membran that makes, the compound garment material water pressure resistance of gained is greater than 3kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day.This garment material still can keep water pressure resistance greater than 3kg/cm after washing through 10 times
2, moisture permeability is greater than 8kg water/m
2The excellent properties in/sky.
Comparative example 1 (comparative example of embodiment 3)
Reference implementation example 3 is about 2.16g/cm with standard specific gravity
3Polytetrafluoroethyldispersion dispersion resin (derive from the big capital company of Japan; The resin trade mark 106) mixes with the weight ratio of about 5:1 with U.S. Exxon Mobil senior lubricant (trade mark Isopar M); The first precompressed in back that stirs becomes cylinder; Extrude paste at about 50 ℃ of following high pressure again, and roll into the band of the about 0.1mm of thickness.With behind about 3 times of this band cross directional stretch in about 260 ℃ baking oven de-oiling obtain dry film.With about 10 times of this dry film longitudinal stretching under about 340 ℃ hot conditions, and then under about 360 ℃ hot conditions about 10 times of cross directional stretch, typing under about 390 ℃ of high temperature at last.
Through detecting, be the microporous teflon membran that polytetrafluoroethyldispersion dispersion resin obtains with Japan's big capital resin (trade mark 106), its average pore size is 120 ~ 150nm, porosity 82 ~ 86%, hot strength (laterally reaching vertically) is all less than 300kg/cm
2, water pressure resistance is less than 2kg/cm
2, moisture permeability is greater than 10kg water/m
2/ day, air penetrability is 13 ~ 15 seconds.
With polyurethane adhesive with 70g/m
2The polyester fabric point be affixed on this microporous teflon membran that makes, the compound garment material water pressure resistance of gained is less than 2kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day.After this garment material was washed through 10 times, water pressure resistance was less than 0.5kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day, such garment material is considered to low grade products on market.
Comparative example 2 (comparative example of embodiment 4)
Reference implementation example 4 is about 2.16g/cm with standard specific gravity
3Polytetrafluoroethyldispersion dispersion resin (derive from the big capital company of Japan; The resin trade mark 106) mixes with the weight ratio of about 5:1 with U.S. Exxon Mobil senior lubricant (trade mark Isopar M); The first precompressed in back that stirs becomes cylinder; Extrude paste at about 50 ℃ of following high pressure again, and roll into the band of the about 0.6mm of thickness.With behind about 3.8 times of this band cross directional stretch in about 260 ℃ baking oven de-oiling obtain dry film.With about 30 times of this dry film longitudinal stretching under about 340 ℃ hot conditions, and then under about 360 ℃ hot conditions about 15 times of cross directional stretch, typing under about 390 ℃ of high temperature at last.
Through detecting, its average pore size is 80 ~ 100nm, and porosity is 85 ~ 90%, and hot strength (laterally reaching vertically) is all less than 300kg/cm
2, water pressure resistance is less than 2kg/cm
2, moisture permeability is greater than 10kg water/m
2/ day, air penetrability is 18 ~ 19 seconds.
With polyurethane adhesive with 90g/m
2Nylon 6 linings point be affixed on this microporous teflon membran that makes, the compound garment material water pressure resistance of gained is less than 2kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day.After this garment material was washed through 10 times, water pressure resistance was less than 0.5kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day, such garment material is thought low grade products by market.
Generally speaking; The average grain diameter of the primary particle of conventional polytetrafluoroethyldispersion dispersion resin is 260 ~ 400nm; And the average grain diameter of the primary particle of the used polytetrafluoroethyldispersion dispersion resin with nucleocapsid structure of the present invention is less, be 160 ~ 250nm, and specific area is bigger.The average grain diameter of primary particle is more little, and the probability that runs foul of each other is just big more, and contact area is also just big more, and the nanofiber of pulling out is just many more.
And because the part of resin core is the copolymer of polytetrafluoroethylene (PTFE), its mechanical strength is higher than conventional polytetrafluoroethylene (PTFE) homopolymers, and this also is one of factor of the higher hydraulic pressure of film ability that drawn of nucleocapsid structure resin; Housing parts is the polytetrafluoroethylene (PTFE) homopolymers, is the critical materials that forms nanofiber, and core, shell complement each other, and are used to improve the mechanical strength of microporous teflon membran.
So the polytetrafluoroethyldispersion dispersion resin that will have nucleocapsid structure is as the raw material of producing microporous teflon membran, the aperture of the microporous barrier that obtains is less relatively, and water pressure resistance increases naturally; Because nanofiber content increases, mechanical strength also strengthens thereupon.
Saidly can find out from top; According to the microporous teflon membran that manufacturing approach provided by the invention obtained; Its nanofiber content is high; Physical mechanical strength such as tension stress, water pressure resistance, hot strength are higher, and its extra small nanometer micropore can satisfy the higher or filter effect better application requirement of water pressure resistance.When being applied to apparel industry, after compound with garment material, the water pressure resistance of the composite material of gained, moisture permeability, gas permeability improve; Water-wash resistance is preferable, can be accepted by market.
The method of testing and the instrument that are adopted among the above embodiment are respectively:
The method of testing of average pore size adopts Al Kut apertometer (Coulter Porometer) to detect according to ASTM standard E1298-89 method;
Hot strength utilizes tension intensity machine (Instron) to detect;
Watertight method of testing adopts Mu Leng hydraulic pressure appearance (Mullen Tester) to detect according to ASTM standard D751-2006 method;
The method of testing of moisture permeability is according to JIS standard L1099-B1 method;
The method of testing of air penetrability adopts air permeable appearance (Gurley Densometer) detection in the song according to ASTM standard 0726-58 method.
The those of ordinary skill in affiliated field is to be understood that: the above is merely specific embodiment of the present invention; Be not limited to the present invention; All within spirit of the present invention and principle, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (12)
1. the manufacturing approach of a microporous teflon membran is characterized in that, said manufacturing approach comprises following operation:
The polytetrafluoroethyldispersion dispersion resin that 1) will have a nucleocapsid structure mixes with lubricating oil and stirs, and is pressed into columned paste mixture then;
2) under 20 ~ 120 ℃, said paste mixture is pushed and extrudes, then said paste is rolled into band, under 100 ~ 300 ℃ temperature or with volatile organic solvent, slough the lubricating oil in the said band then through the pushing machine; With
3) with the unidirectional or biaxial tensiones under 100 ~ 390 ℃ of the said band after the de-oiling, carry out thermal finalization at last, be made for said microporous teflon membran.
2. the manufacturing approach of microporous teflon membran according to claim 1 is characterized in that, said polytetrafluoroethyldispersion dispersion resin with nucleocapsid structure mixes according to weight ratio 4 ~ 5:1 with said lubricating oil.
3. the manufacturing approach of microporous teflon membran according to claim 1 is characterized in that, said polytetrafluoroethyldispersion dispersion resin with nucleocapsid structure makes according to following operation:
1) in autoclave, adds deionized water and perfluorinated surfactant; Vacuumize in the still, heat up, stirring to form emulsion; In still, feeding with the tetrafluoroethylene monomer then is main mix monomer gas; Add radical initiator, the started copolymer reaction, temperature in the kettle maintains 70 ~ 110 ℃; Pressure is along with reaction reduces, when the still internal pressure is reduced to less than 5kg/cm
2The time, the core copolymerization of said polytetrafluoroethyldispersion dispersion resin primary particle is accomplished, emulsion solid content 0.5 ~ 9%, and the average grain diameter of primary particle is 60 ~ 130nm;
2) after copolymerization is accomplished, vacuumize in the still, feed the polytetrafluoroethyl-ne alkene monomer of molar concentration＞99.999% again, temperature in the kettle maintains 70 ~ 110 ℃, and homopolymerization begins; The still internal pressure maintains 20kg/cm at least
2, sustained response is 20 ~ 39% to emulsion solid content, is cooled to room temperature, stop to stir, and reaction terminating, this moment, the housing parts homopolymerization of said polytetrafluoroethyldispersion dispersion resin primary particle was accomplished, and the average grain diameter of primary particle is 160 ~ 250nm;
3) emulsion is through breakdown of emulsion, and cohesion obtains polytetrafluoroethyldispersion dispersion resin after the drying, and its standard specific gravity is 2.14 ~ 2.20g/cm
3, housing parts accounts for 70 ~ 99% weight ratios, and the core accounts for 1 ~ 30% weight ratio.
4. the manufacturing approach of microporous teflon membran according to claim 3 is characterized in that, said perfluorinated surfactant is a perfluorooctanoic acid.
5. the manufacturing approach of microporous teflon membran according to claim 3 is characterized in that, said radical initiator is selected from any one or its combination in persulfate, hydrogen peroxide solution or the organic peroxide.
6. the manufacturing approach of microporous teflon membran according to claim 5 is characterized in that, said persulfate is selected from any one or its combination in ammonium persulfate, sodium peroxydisulfate or the potassium peroxydisulfate.
7. the manufacturing approach of microporous teflon membran according to claim 3; It is characterized in that; Contain percent by volume in the said mix monomer gas and be 0.5 ~ 30% and can with the fluorochemical monomer of tetrafluoroethene copolymerization, said fluorochemical monomer is selected from perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, vinylidene, PVF, trifluoro-ethylene, CTFE, difluoro dichloroethylene, 3; 3, the 3-trifluoropropyl rare with hexafluoropropene in any one or its combination.
8. a microporous teflon membran is characterized in that, said microporous teflon membran is that the manufacturing approach according to any described microporous teflon membran in the claim 1 ~ 7 makes.
9. microporous teflon membran according to claim 8 is characterized in that, point pastes 30 ~ 150g/m on said microporous teflon membran
2Polyester fabric form compound garment material after, the compound garment material water pressure resistance of gained is greater than 3kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day; After said compound garment material was washed through 10 times, its water pressure resistance was greater than 3kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day.
10. microporous teflon membran according to claim 8 is characterized in that, point pastes 30 ~ 150g/m on said microporous teflon membran
2Nylon 6 linings form compound garment material after, the compound garment material water pressure resistance of gained is greater than 5kg/cm
2, moisture permeability is greater than 10kg water/m
2/ day; After said compound garment material was washed through 10 times, its water pressure resistance was greater than 5kg/cm
2, moisture permeability is greater than 10kg water/m
2/ day.
11. microporous teflon membran according to claim 8 is characterized in that, point pastes 50 ~ 180g/m on said microporous teflon membran
2Cotton fabric form compound garment material after, the compound garment material water pressure resistance of gained is greater than 3kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day; After said compound garment material was washed through 10 times, its water pressure resistance was greater than 3kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day.
12. microporous teflon membran according to claim 8 is characterized in that, point pastes 60 ~ 250g/m on said microporous teflon membran
2The aramid fiber lining form compound garment material after, the compound garment material water pressure resistance of gained is greater than 3kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day; After said compound garment material was washed through 10 times, its water pressure resistance was greater than 3kg/cm
2, moisture permeability is greater than 8kg water/m
2/ day.
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| CN104001433A (en) * | 2014-05-14 | 2014-08-27 | 浙江舒普氟材科技有限公司 | Production process of hydrophilic polytetrafluoroethylene microporous film |
| CN104437126A (en) * | 2013-09-23 | 2015-03-25 | 上海碧科清洁能源技术有限公司 | Preparation method of super-hydrophobic polytetrafluoroethylene microporous membrane, membrane prepared by preparation method and application of super-hydrophobic polytetrafluoroethylene microporous membrane |
| CN105940026A (en) * | 2014-01-31 | 2016-09-14 | 3M创新有限公司 | Tetrafluoroethylene polymer dispersions stabilized with aliphatic non-ionic surfactants |
| CN106632796A (en) * | 2015-12-15 | 2017-05-10 | 浙江汉丞科技有限公司 | Bulk micro-porous material for high molecular weight tetrafluoroethylene copolymerizing dispersion resin |
| WO2017080475A1 (en) * | 2015-11-11 | 2017-05-18 | 重庆润泽医药有限公司 | Polytetrafluoroethylene fiber membrane |
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| CN104437126A (en) * | 2013-09-23 | 2015-03-25 | 上海碧科清洁能源技术有限公司 | Preparation method of super-hydrophobic polytetrafluoroethylene microporous membrane, membrane prepared by preparation method and application of super-hydrophobic polytetrafluoroethylene microporous membrane |
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| CN105940026A (en) * | 2014-01-31 | 2016-09-14 | 3M创新有限公司 | Tetrafluoroethylene polymer dispersions stabilized with aliphatic non-ionic surfactants |
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| CN104001433A (en) * | 2014-05-14 | 2014-08-27 | 浙江舒普氟材科技有限公司 | Production process of hydrophilic polytetrafluoroethylene microporous film |
| WO2017080475A1 (en) * | 2015-11-11 | 2017-05-18 | 重庆润泽医药有限公司 | Polytetrafluoroethylene fiber membrane |
| WO2017080460A1 (en) * | 2015-11-11 | 2017-05-18 | 重庆润泽医药有限公司 | A polytetrafluoroethylene hollow fiber membrane |
| CN106632796A (en) * | 2015-12-15 | 2017-05-10 | 浙江汉丞科技有限公司 | Bulk micro-porous material for high molecular weight tetrafluoroethylene copolymerizing dispersion resin |
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| CN113388134A (en) * | 2020-03-13 | 2021-09-14 | 中昊晨光化工研究院有限公司 | Polytetrafluoroethylene film for mask and preparation method thereof |
| CN112495192A (en) * | 2020-11-28 | 2021-03-16 | 北京上远科技有限公司 | Preparation method of modified polytetrafluoroethylene nanofiltration membrane and prepared nanofiltration membrane |
| CN115027081A (en) * | 2021-03-03 | 2022-09-09 | 哈尔滨纳新密封产品制造有限公司 | Polytetrafluoroethylene microporous membrane and preparation method and application thereof |
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