CN103483749A - Special fluorine-containing dispersion resin mixture and microporous film thereof - Google Patents
Special fluorine-containing dispersion resin mixture and microporous film thereof Download PDFInfo
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 87
- 239000011737 fluorine Substances 0.000 title claims abstract description 87
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000006185 dispersion Substances 0.000 title claims abstract description 82
- 229920005989 resin Polymers 0.000 title claims abstract description 54
- 239000011347 resin Substances 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 239000000839 emulsion Substances 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000007787 solid Substances 0.000 claims abstract description 22
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000010687 lubricating oil Substances 0.000 claims abstract description 8
- 238000009775 high-speed stirring Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 37
- 239000012982 microporous membrane Substances 0.000 claims description 36
- 230000005484 gravity Effects 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 19
- 239000012943 hotmelt Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 230000015556 catabolic process Effects 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000006392 deoxygenation reaction Methods 0.000 claims description 6
- 239000011164 primary particle Substances 0.000 claims description 6
- 230000002459 sustained effect Effects 0.000 claims description 6
- 239000004809 Teflon Substances 0.000 claims description 5
- 229920006362 Teflon® Polymers 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 210000004379 membrane Anatomy 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 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 claims description 2
- 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 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
- PKBXXIJDESMGDN-UHFFFAOYSA-N 1-fluorobuta-1,2,3-triene Chemical compound FC=C=C=C PKBXXIJDESMGDN-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- YAUDMZWROUAYDU-UHFFFAOYSA-N C(C(C(C(F)(F)Cl)F)(F)F)(C(C(Cl)Cl)(F)F)F Chemical compound C(C(C(C(F)(F)Cl)F)(F)F)(C(C(Cl)Cl)(F)F)F YAUDMZWROUAYDU-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 238000009998 heat setting Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 19
- 239000004744 fabric Substances 0.000 abstract description 9
- 238000001914 filtration Methods 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 7
- 230000015271 coagulation Effects 0.000 abstract 1
- 238000005345 coagulation Methods 0.000 abstract 1
- 238000007865 diluting Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 abstract 1
- 229920001519 homopolymer Polymers 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 10
- 238000009423 ventilation Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 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 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002473 artificial blood Substances 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Abstract
The invention discloses a special fluorine-containing dispersion resin mixture. The special fluorine-containing dispersion resin mixture is prepared through the following steps: blending a tetrafluoroethene homopolymer dispersion emulsion with a fluorine-containing hot-meltable processing dispersion emulsion according to a dry weight ratio of 19: 1 to 3: 7; then diluting an obtained blend with deionized water into a blended emulsion with solid content of 10 to 20%; and successively carrying out demulsification through high-speed stirring, coagulation and drying. The mixture is blended with lubricating oil so as to prepare a fluorine-containing microporous film. The fluorine-containing microporous film has high content of nanometer silk fiber and high physical and mechanical strength; when the microporous film is applied in the industries of filtration and clothes and compounded with a fabric, an obtained composite fabric has high water-pressure resistance, moisture permeability and air permeability and excellent tensile strength and can better realize market acceptance.
Description
Technical field
The present invention relates to fluorine resin, be specifically related to extraordinary fluorine-containing dispersion resin compound and microporous membrane thereof.
Background technology
Fluorine resin, the especially copolymer resins containing tetrafluoroethylene have excellent physical and mechanical properties and chemical stability, in each fields such as chemical materials, mechano-electronic, space flight military project, type material and new forms of energy, all have a wide range of applications.Polytetrafluoroethyldispersion dispersion resin is adopted to the paste extruding and extrudes and de-oiling, pass through again unidirectional or two-way stretch, can obtain the tetrafluoroethylene poromerics with micro-porous permeable, due to its property, this material becomes a kind of functional fluoropolymer material of high-end applications, such as being used as environmental protection filter material, garment material, artificial organ material, electronic material and sealed insulating material etc.
Fluorine-containing microporous membrane is because having good physical and chemical performance, mechanical property, and water-proof breathable properties and chemical stability just have been used to manufacture wire cable insulating material, artificial blood vessel, seal strip, environmental protection filtration and garment material etc. since the seventies.Industrial common employing high purity tetrafluoroethylene monomer, carry out polymerization or copolymerization prepares dispersion resin by dispersion polymerization processes.Tetrafluoroethylene homopolymerization dispersion resin normally pushes by paste, extrude, de-oiling, unidirectional or two-way stretch again, make the microporous membrane material, but this kind of film is not the ventilation property deficiency, be exactly that physical strength is inadequate, its water pressure resistance and filter effect can not meet the high-end applications requirement, and while being applied to the environmental protection filtration, tension stress and Gas permeability still need to improve.
Summary of the invention
In view of this, the object of the invention is to propose the fluorine-containing dispersion resin compound of a kind of special type and microporous membrane thereof, with physical strength or water pressure resistance or the air penetrability that improves fluorine-containing microporous membrane.
Based on above-mentioned purpose, the invention provides the fluorine-containing dispersion resin compound of a kind of special type, the fluorine-containing dispersion resin compound of described special type makes by following operation, comprise: but first proplast dispersion emulsion and fluorine-containing hot melt processibility dispersion emulsion are compared to blend with the dry weight of 19:1～3:7, then with deionized water, blend is diluted to the blending emulsion that solid content is 10～20%, through the high-speed stirring breakdown of emulsion, cohesion, obtain extraordinary fluorine-containing dispersion resin compound after drying again;
Wherein, the solid content of described proplast dispersion emulsion is 20～39%, but the solid content of described fluorine-containing hot melt processibility dispersion emulsion is 10～39%.
Alternatively, but the dry weight of described proplast dispersion emulsion and fluorine-containing hot melt processibility dispersion emulsion than being 7:3～2:3.
Alternatively, the manufacture method of described proplast dispersion emulsion comprises: add deionized water and perfluorinated surfactant in autoclave, vacuumize deoxygenation in still, and heat up, open and stir to form emulsion; When temperature in the kettle rises to 65～75 ℃, in still, pass into tetrafluoroethylene gas; The still internal pressure adds radical initiator after reaching 18～25 kilograms, starts homopolymerization, and temperature in the kettle maintains 70～110 ℃; Sustained reaction reaches 20～39% to emulsion solid content, after temperature in the kettle is down to room temperature, stops stirring, and reaction terminating, make tetrafluoroethylene homopolymerization dispersion emulsion, and the median size of its primary particle is 180～300nm approximately.
Preferably, described polytetrafluoroethyl-ne polyamino alkenyl dispersion emulsion is through breakdown of emulsion, and cohesion, obtain polytetrafluoroethyl-ne polyamino alkenyl dispersion resin after drying, and the standard specific gravity of this resin is 2.14～2.22g/cm
3, fusing point is 300～360 ℃.
Alternatively, but the manufacture method of described fluorine-containing hot melt processibility dispersion emulsion comprises: add deionized water and perfluorinated surfactant in autoclave, vacuumize deoxygenation in still, and heat up, open and stir to form emulsion; Temperature in the kettle rises to 65～75 ℃, then in still, take tetrafluoroethylene as main mixed gas, and the still internal pressure adds radical initiator after reaching 10～15 kilograms, the started copolymer reaction, and temperature in the kettle maintains 20～120 ℃; Sustained reaction reaches approximately 10～39% to emulsion solid content, after temperature in the kettle is down to room temperature, stops stirring, and reaction terminating, but making fluorine-containing hot melt processibility dispersion emulsion, the median size of its primary particle is 60～250nm approximately.
Preferably, described take tetrafluoroethylene gas in main mixed gas containing volume percent as 30～40% and can with the fluoro-gas of tetrafluoroethylene copolymerization, described fluoro-gas is selected from perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, vinylidene, vinyl fluoride, trifluoro-ethylene, trifluorochloroethylene, difluoro Ethylene Dichloride, 3, any one or its combination in the rare and R 1216 of 3,3-trifluoropropyl.
Preferably, but described fluorine-containing hot melt processibility dispersion emulsion through breakdown of emulsion, the cohesion, but obtain fluorine-containing hot melt processibility dispersion resin after drying, the standard specific gravity of this resin is 2.08～2.22g/cm
3, fusing point is 220～320 ℃.
Alternatively, described fluorochemical surfactant is the organic fluorocompound containing 6～14 carbon, and at least contains the functional group of a carboxylic acid or sulfonic acid.
Preferably, described perfluorinated surfactant is ammonium perfluorocaprylate.
Alternatively, described radical initiator is selected from any one or its combination in persulphate, hydrogen peroxide or organo-peroxide.
Alternatively, in homopolymerization and copolyreaction process, the still internal pressure at least maintains 10 kilograms.
The invention provides the fluorine-containing microporous membrane of a kind of special type, the fluorine-containing microporous membrane of described special type makes by following operation, comprising:
1) the fluorine-containing dispersion resin compound of above-mentioned special type mixed and stirs according to weight ratio 4～5:1 with lubricating oil, then being pressed into columned paste mixture;
2) by the pushing machine, described paste mixture is pushed and extruded under 20～120 ℃, then described paste is rolled into to band, then at the temperature of 100～300 ℃ or with volatile organic solvent, sloughed the lubricating oil in described band; With
3) by the unidirectional or two-way stretch under 100～390 ℃ of the described band after de-oiling, finally carry out heat setting type, be made for the fluorine-containing microporous membrane of described special type.
Alternatively, the fluorine-containing dispersion resin compound of described special type mixes according to weight ratio 4～5:1 with described lubricating oil.
Alternatively, in described step 1), the fluorine-containing dispersion resin compound of special type, inorganic, metal oxide or gac or carbon black, lubricating oil are mixed and stir with the weight ratio of 4～5:0.4～0.8:1.
Preferably, described inorganic, metal oxide is selected from least one in titanium dioxide and dichloride copper.
As can be seen from above, according to the fluorine-containing microporous membrane of special type provided by the invention, its nanofiber content is higher, physical mechanical strength is as large as the gravity of anti-the ball, water pressure resistance, ventilation property are higher, and its extra small nano thread microporous membrane can meet that ventilation property is higher, physical strength is better, the better application requiring of filter effect.When being applied to fabric, after compound with fabric, the anti-tensile of the composite material of gained, Water Vapour Permeability, ventilation property improve; The face water-sprinkling is good, and filter effect is better, more can be accepted by market.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, the present invention is described in more detail.
The manufacture of embodiment 1(tetrafluoroethylene homopolymerization dispersion emulsion)
Approximately in the horizontal high-pressure reactor of 100 liters, at first add the deionized water of 50L and the ammonium perfluorocaprylate of 15g at one, vacuumizing deoxygenation (until oxygen level<20ppm) in still, and heat up, open and stir to form emulsion; When temperature in the kettle rises to approximately 70 ℃, toward the tetrafluoroethylene gas that passes into volumetric molar concentration>99.99% in still, the still internal pressure reaches approximately 20 kilograms.In still, add 8 gram ammonium persulphates (being dissolved in advance in 500 ml waters) as initiator, start homopolymerization, temperature in the kettle maintains 70～110 ℃, in reaction process, by tetrafluoroethylene gas, makes the still internal pressure maintain approximately 20 kilograms.Sustained reaction reaches approximately 20% to emulsion solid content, after temperature in the kettle is down to room temperature, stops stirring, and reaction terminating, make tetrafluoroethylene homopolymerization dispersion emulsion, the about 280nm of the median size of its primary particle.Get the sample emulsion through breakdown of emulsion, cohesion, after drying, detect the standard specific gravity of polytetrafluoroethyl-ne polyamino alkenyl dispersion resin, is about 2.19g/cm
3, approximately 330 ℃ of fusing points.
But the manufacture of the fluorine-containing hot melt processibility of embodiment 2(dispersion emulsion)
Approximately in the horizontal high-pressure reactor of 100 liters, at first add the deionized water of 50L and the ammonium perfluorocaprylate of 18g at one, vacuumizing deoxygenation (until oxygen level<20ppm) in still, open and stir to form emulsion; Temperature in the kettle is raised to approximately 70 ℃, and then, toward the mixed gas that passes into tetrafluoroethylene and R 1216 in still, tetrafluoroethylene mixes according to mol ratio 13:7 with R 1216, and the still internal pressure reaches approximately 12 kilograms.In still, add 8 gram ammonium persulphates (being dissolved in advance in 500 ml waters) as initiator, the started copolymer reaction, temperature in the kettle maintains 70～110 ℃, in reaction process, by mixed gas, make the still internal pressure maintain approximately 12 kilograms, sustained reaction reaches approximately 30% to emulsion solid content, after temperature in the kettle is down to room temperature, stop stirring, reaction terminating, but make fluorine-containing hot melt processibility dispersion emulsion, the about 150nm of the median size of its primary particle.Get the sample emulsion through breakdown of emulsion, cohesion, after drying, but detect approximately 266 ℃ of the fusing points of fluorine-containing thermally melting dispersion resin, and standard specific gravity is about 2.15g/cm
3.
The preparation of the extraordinary fluorine-containing dispersion resin compound of embodiment 3()
(3A) by the proplast dispersion emulsion of embodiment 1 (solid content approximately 20%) but compare blend with the fluorine-containing hot melt processibility dispersion emulsion of embodiment 2 (solid content approximately 30%) with the weight in wet base of 3:2, with deionized water, blend is diluted to solid content approximately 13% again, then high-speed stirring breakdown of emulsion, cohesion, obtain extraordinary fluorine-containing dispersion resin compound after drying.The fusing point of the fluorine-containing dispersion resin compound of this special type has 2 points: 266 ℃ and 335 ℃, standard specific gravity is about 2.17g/cm
3.The weight in wet base ratio is converted into to the dry weight ratio, is about (20% * 3): (30% * 2)=1:1.
(3B) by the proplast dispersion emulsion of embodiment 1 (solid content approximately 20%) but compare blend with the fluorine-containing hot melt processibility dispersion emulsion of embodiment 2 (solid content approximately 30%) with the weight in wet base of 15:1, with deionized water, blend is diluted to solid content approximately 16% again, then high-speed stirring breakdown of emulsion, cohesion, obtain extraordinary fluorine-containing dispersion resin compound after drying.The fusing point of the fluorine-containing dispersion resin compound of this special type has 2 points: 266 ℃ and 335 ℃, standard specific gravity is about 2.186g/cm
3.The weight in wet base ratio is converted into to the dry weight ratio, is about (20% * 15): (30% * 1)=10:1.
(3C) by the proplast dispersion emulsion of embodiment 1 (solid content approximately 20%) but compare blend with the fluorine-containing hot melt processibility dispersion emulsion of embodiment 2 (solid content approximately 30%) with the weight in wet base of 9:14, with deionized water, blend is diluted to solid content approximately 13.5% again, then high-speed stirring breakdown of emulsion, cohesion, obtain extraordinary fluorine-containing dispersion resin compound after drying.The fusing point of the fluorine-containing dispersion resin compound of this special type has 2 points: 266 ℃ and 335 ℃, standard specific gravity is about 2.178g/cm
3.The weight in wet base ratio is converted into to the dry weight ratio, is about (20% * 9): (30% * 14)=3:7.
The manufacture of the extraordinary fluorine-containing microporous membrane of embodiment 4()
By manufacturing the fluorine-containing dispersion resin compound of special type obtained in embodiment 3A, with U.S. Exxon Mobil senior lubricant (trade mark Isopar M), with the weight ratio of about 4.3:1, mix, the rear elder generation that stirs is pressed into columned paste mixture in advance, approximately by the pushing machine, described paste mixture being pushed and extrudes under 50 ℃, described paste is rolled into to the band of the about 0.25mm of thickness again.The de-oiling in the about baking oven of 260 ℃ of this band is obtained to dry film, by this dry film approximately 9 times of longitudinal stretchings under the about hot conditions of 300 ℃, and then, approximately laterally stretching approximately 9 times under the hot conditions of 300 ℃, obtain extraordinary fluorine-containing microporous membrane.
After testing, the porosity of the extraordinary fluorine-containing microporous membrane of gained is approximately 88～92%, and air penetrability is greater than 900 milliliters of air/minute/square centimeters, and water pressure resistance is greater than 80Pa, and Water Vapour Permeability is greater than 80 kg of water/square metre/day, and the gravity of anti-the ball is greater than 1 kilogram.
By 20g/m
2terylene non-woven fabric and the fluorine-containing microporous membrane direct combination of prepared special type (be mainly by static non-woven fabrics with together with the film suction), the composite material air penetrability of gained is greater than 480 milliliters of air/minute/square centimeters, water pressure resistance is greater than 80Pa, Water Vapour Permeability is greater than 60 kg of water/square metre/day, the gravity of anti-the ball is greater than 2 kilograms, and the high efficiency filter effect is good.According to the ASHRAE52.2 testing method, approximately 16 meters/minutes of wind speed, approximately 13500 liter/mins of air flow quantitys, can filter approximately 90～96% approximately 0.1 micron particle effectively, is applicable to doing Filters, as air filtration, especially makees mouth mask and use.The face water-sprinkling is splendid, and according to AATCC testing method 22-2010, water-sprinkling test can reach 100 minutes, all from its surface, tumbles regardless of different kinds of the globule, also can replace the anti-water-sprinkling aftertreatment of fabric.
The manufacture of the extraordinary fluorine-containing microporous membrane of embodiment 5()
By manufacturing the fluorine-containing dispersion resin compound of special type obtained in embodiment 3A, with U.S. Exxon Mobil senior lubricant (trade mark Isopar M), with the weight ratio of about 4.5:1, mix, the rear elder generation that stirs is pressed into columned paste mixture in advance, approximately by the pushing machine, described paste mixture being pushed and extrudes under 52 ℃, described paste is rolled into to the band of the about 0.25mm of thickness again.The de-oiling in the about baking oven of 260 ℃ of this band is obtained to dry film, by this dry film approximately 5 times of longitudinal stretchings under the about hot conditions of 300 ℃, and then, approximately laterally stretching approximately 5 times under the hot conditions of 300 ℃, also can obtain extraordinary fluorine-containing microporous membrane.
After testing, the mean porosities of the fluorine-containing microporous membrane of gained is approximately 85～90%, and air penetrability is greater than 500 milliliters of air/minute/square centimeters, and water pressure resistance is greater than 180Pa, and Water Vapour Permeability is greater than 80 kg of water/square metre/day, and the gravity of anti-the ball is greater than 2.5 kilograms.
With polyurethane adhesive by 90g/m
2nylon 6 fabric points be affixed on this microporous teflon membran made, the compound dress fabric air penetrability of gained is greater than 250 milliliters of air/minute/square centimeters, water pressure resistance is greater than 220Pa, Water Vapour Permeability is greater than 40 kg of water/square metre/day, the gravity of anti-the ball is greater than 5 kilograms, be applicable to makeing the water proof wind proof clothes, also be applicable to makeing the dust free chamber vest.
Embodiment 6(is containing the manufacture of the fluorine-containing microporous membrane of special type of titanium dioxide)
By manufacturing the fluorine-containing dispersion resin compound of special type obtained in embodiment 3C, with titania powder and U.S. Exxon Mobil senior lubricant (trade mark Isopar M), with the weight ratio of about 4:0.6:1, mix, the rear elder generation that stirs is pressed into columned paste mixture in advance, approximately by the pushing machine, described paste mixture being pushed and extrudes under 50 ℃, described paste is rolled into to the band of the about 0.25mm of thickness again.The de-oiling in the about baking oven of 260 ℃ of this band is obtained to dry film, by this dry film approximately 9 times of longitudinal stretchings under the about hot conditions of 280 ℃, and then, approximately laterally stretching approximately 9 times under the hot conditions of 280 ℃, obtain the fluorine-containing microporous membrane of special type containing titanium dioxide.
After testing, the porosity of the fluorine-containing microporous membrane of gained is approximately 90～93%, air penetrability is greater than 1200 milliliters of air/minute/square centimeters, water pressure resistance is greater than 50Pa, Water Vapour Permeability is greater than 80 kg of water/square metre/day, the gravity of anti-the ball is greater than 0.5 kilogram, and it is fluorine-containing microporous membrane as thin as a wafer, seem be clear to translucent.
By 20g/m
2terylene non-woven fabric and prepared fluorine-containing microporous membrane direct combination get up, the composite material air penetrability of gained is greater than 800 milliliters of air/minute/square centimeters, water pressure resistance is greater than 70Pa, Water Vapour Permeability is greater than 56 kg of water/square metre/day, the gravity of anti-the ball is greater than 1 kilogram, and the high efficiency filter effect is good, is applicable to doing Filters, as air filtration, especially make mouth mask and use.
Embodiment 7(is containing the manufacture of the fluorine-containing microporous membrane of special type of activated carbon)
By manufacturing the fluorine-containing dispersion resin compound of special type obtained in embodiment 3A, with activated carbon powder and U.S. Exxon Mobil senior lubricant (trade mark Isopar M), with the weight ratio of about 4:0.5:1, mix, the rear elder generation that stirs is pressed into columned paste mixture in advance, approximately by the pushing machine, described paste mixture being pushed and extrudes under 50 ℃, described paste is rolled into to the band of the about 0.25mm of thickness again.The de-oiling in the about baking oven of 260 ℃ of this band is obtained to dry film, by this dry film approximately 6 times of longitudinal stretchings under the about hot conditions of 290 ℃, and then, approximately laterally stretching approximately 6 times under the hot conditions of 290 ℃, obtain the fluorine-containing microporous membrane of special type containing activated carbon.
After testing, the mean porosities of the fluorine-containing microporous membrane of gained is approximately 89～92%, and air penetrability is greater than 900 milliliters of air/minute/square centimeters, and water pressure resistance is greater than 75Pa, and Water Vapour Permeability is greater than 80 kg of water/m
2/ day, the gravity of anti-the ball is greater than 0.8 kilogram, its fluorine-containing microporous membrane that is grey.
With polyurethane adhesive by 110g/m
2enlightening human relations weaving face fabric point be affixed on this microporous teflon membran made, the compound dress fabric air penetrability of gained is greater than 600 milliliters of air/minute/square centimeters, water pressure resistance is greater than 120Pa, Water Vapour Permeability is greater than 40 kg of water/square metre/day, the gravity of anti-the ball is greater than 1.5 kilograms, is applicable to makeing water proof wind proof and inhales smelly clothes.
The comparative example of comparative example 1(embodiment 4)
Reference example 4, be about 2.16g/cm by standard specific gravity
3polytetrafluoroethyldispersion dispersion resin (derive from Japan large capital company, resin grade 106) with U.S. Exxon Mobil senior lubricant (trade mark Isopar M), with the weight ratio of about 4.3:1, mix, the rear elder generation that stirs is pressed into columned paste mixture in advance, approximately by the pushing machine, described paste mixture being pushed and extrudes under 50 ℃, described paste is rolled into to the band of the about 0.25mm of thickness again.The de-oiling in the about baking oven of 260 ℃ of this band is obtained to dry film.By this dry film approximately 9 times of longitudinal stretchings under the about hot conditions of 300 ℃, and then, approximately laterally stretching approximately 9 times under the hot conditions of 300 ℃, make polytetrafluoroethylmicroporous microporous membrane.
After testing, the microporous teflon membran that the Japan's large capital resin (trade mark 106) of take obtains as polytetrafluoroethyldispersion dispersion resin, its mean porosities 82～86%, the little 250 milliliters of air/minute/square centimeters of air penetrability, water pressure resistance is greater than 80Pa, and Water Vapour Permeability is greater than 80 kg of water/square metre/day, the gravity of anti-the ball is greater than 1 kilogram, because ventilation property is inadequate, be not suitable for doing Filters, the application such as especially uncomfortable cooperation air filtration.
By 20g/m
2terylene non-woven fabric and prepared fluorine-containing microporous membrane compound upper by static, the composite material air penetrability of gained is less than 150 milliliters of air/minute/square centimeters, water pressure resistance is greater than 80Pa, Water Vapour Permeability is greater than 60 kg of water/m
2/ day, the gravity of anti-the ball is greater than 2 kilograms, and ventilation property is inadequate, is not suitable for doing Filters, as application such as air filtrations.
The comparative example of comparative example 2(embodiment 4)
Reference example 4, be about 2.19g/cm by standard specific gravity
3tetrafluoroethylene homopolymerization dispersion resin (deriving from embodiment 1) with U.S. Exxon Mobil senior lubricant (trade mark Isopar M), with the weight ratio of about 4.3:1, mix, the rear elder generation that stirs is pressed into columned paste mixture in advance, approximately by the pushing machine, described paste mixture being pushed and extrudes under 50 ℃, described paste is rolled into to the band of the about 0.25mm of thickness again.The de-oiling in the about baking oven of 260 ℃ of this band is obtained to dry film.By this dry film approximately 9 times of longitudinal stretchings under the about hot conditions of 300 ℃, and then, approximately laterally stretching approximately 9 times under the hot conditions of 300 ℃, make polytetrafluoroethylmicroporous microporous membrane.
After testing, its porosity is 88～92%, air penetrability is greater than 800 milliliters of air/minute/square centimeters, water pressure resistance is greater than 80Pa, and Water Vapour Permeability is greater than 80 kg of water/square metre/day, and the gravity of anti-the ball is less than 0.3 kilogram, although ventilation property can manage it, but the gravity of anti-the ball is not good, the expression tension stress can't be withstood collision not, is the defect of doing filtration application.
By 20g/m
2terylene non-woven fabric and prepared fluorine-containing microporous membrane by static compound on, the composite material air penetrability of gained is greater than 420 milliliters of air/minute/square centimeters, water pressure resistance is greater than 80Pa, Water Vapour Permeability is greater than 60 kg of water/square metre/day, but the gravity of anti-the ball is less than 1 kilogram, can't withstand collision, be the defect of doing filtration application.
As can be seen here, the nanofiber content of the fluorine-containing microporous membrane of special type provided by the invention is high, and physical mechanical strength is as higher as tension stress, Gas permeability, and its ultra-fine little nano thread microporous membrane more can meet the better application requiring of filter effect.When being applied to apparel industry, after compound with garment material, the water-sprinkling of the composite material of gained, Water Vapour Permeability, ventilation property improve, and more can be accepted by market.
The testing method and the instrument that in above embodiment, adopt are respectively:
The testing method of porosity is to detect according to ASTM standard D6093 method;
Tensile strength utilizes tension intensity machine (Instron) to detect;
Watertight testing method detects according to ISO811 testing standard method;
The testing method of Water Vapour Permeability is according to JIS standard L1099-B1 method;
The testing method of air penetrability is described as follows: a circular flange clamp for sample (14 centimeters of internal diameters) is vised, be placed in an airtight tube type passage, in the tubular type ventilation duct, sample one end dried compressed air, pressure-controlling is at 127Pa, the sample another end is the normal pressure opening, and air penetrability is the transit dose of the sample of how many milliliters of air/minute/square centimeter areas of metering.
The gravity of anti-ball testing method is described as follows: a circular flange clamp for sample (7.6 centimeters of internal diameters) is vised, place the steel ball of 2.5 centimeters diameters on sample, see that sample can sustain how many ball weights.
Those of ordinary skill in the field are to be understood that: the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. the fluorine-containing dispersion resin compound of special type, it is characterized in that, the fluorine-containing dispersion resin compound of described special type makes by following operation, comprise: but first proplast dispersion emulsion and fluorine-containing hot melt processibility dispersion emulsion are compared to blend with the dry weight of 19:1～3:7, then with deionized water, blend is diluted to the blending emulsion that solid content is 10～20%, through the high-speed stirring breakdown of emulsion, cohesion, obtain extraordinary fluorine-containing dispersion resin compound after drying again;
Wherein, the solid content of described proplast dispersion emulsion is 20～39%, but the solid content of described fluorine-containing hot melt processibility dispersion emulsion is 10～39%.
2. the fluorine-containing dispersion resin compound of special type according to claim 1, is characterized in that, but described proplast dispersion emulsion is 7:3～2:3 with the dry weight ratio of fluorine-containing hot melt processibility dispersion emulsion.
3. the fluorine-containing dispersion resin compound of special type according to claim 1 and 2, it is characterized in that, the manufacture method of described proplast dispersion emulsion comprises: add deionized water and perfluorinated surfactant in autoclave, vacuumize deoxygenation in still, and heat up, open and stir to form emulsion; When temperature in the kettle rises to 65～75 ℃, in still, pass into tetrafluoroethylene gas; The still internal pressure adds radical initiator after reaching 18～25 kilograms, starts homopolymerization, and temperature in the kettle maintains 70～110 ℃; Sustained reaction reaches 20～39% to emulsion solid content, after temperature in the kettle is down to room temperature, stops stirring, and reaction terminating, make tetrafluoroethylene homopolymerization dispersion emulsion, and the median size of its primary particle is 180～300nm approximately;
By described polytetrafluoroethyl-ne polyamino alkenyl dispersion emulsion, through breakdown of emulsion, cohesion, obtain polytetrafluoroethyl-ne polyamino alkenyl dispersion resin after drying, and the standard specific gravity of this resin is 2.14～2.22g/cm
3, fusing point is 300～360 ℃.
4. the fluorine-containing dispersion resin compound of special type according to claim 1 and 2, it is characterized in that, but the manufacture method of described fluorine-containing hot melt processibility dispersion emulsion comprises: add deionized water and perfluorinated surfactant in autoclave, vacuumize deoxygenation in still, and heat up, open and stir to form emulsion; Temperature in the kettle rises to 65～75 ℃, then in still, take tetrafluoroethylene gas as main mixed gas, and the still internal pressure adds radical initiator after reaching 10～15 kilograms, the started copolymer reaction, and temperature in the kettle maintains 20～120 ℃; Sustained reaction reaches approximately 10～39% to emulsion solid content, after temperature in the kettle is down to room temperature, stops stirring, and reaction terminating, but making fluorine-containing hot melt processibility dispersion emulsion, the median size of its primary particle is 60～250nm approximately;
But described fluorine-containing hot melt processibility dispersion emulsion, through breakdown of emulsion, is condensed, but obtains fluorine-containing hot melt processibility dispersion resin after drying, and the standard specific gravity of this resin is 2.08～2.22g/cm
3, fusing point is 220～320 ℃.
5. the fluorine-containing dispersion resin compound of special type according to claim 4, it is characterized in that, described take tetrafluoroethylene gas in main mixed gas containing volume percent as 30～40% and can with the fluoro-gas of tetrafluoroethylene copolymerization, described fluoro-gas is selected from perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, vinylidene, vinyl fluoride, trifluoro-ethylene, trifluorochloroethylene, difluoro Ethylene Dichloride, 3, any one or its combination in the rare and R 1216 of 3,3-trifluoropropyl.
6. according to the fluorine-containing dispersion resin compound of the described special type of claim 3 or 5, it is characterized in that, described fluorochemical surfactant is the organic fluorocompound containing 6～14 carbon, and at least contains the functional group of a carboxylic acid or sulfonic acid.
7. according to the fluorine-containing dispersion resin compound of the described special type of claim 3 or 5, it is characterized in that, described radical initiator is selected from any one or its combination in persulphate, hydrogen peroxide or organo-peroxide.
8. the fluorine-containing microporous membrane of special type, is characterized in that, the fluorine-containing microporous membrane of described special type makes by following operation, comprising:
1) the fluorine-containing dispersion resin compound of the described special type of any one in claim 1～7 mixed and stirs according to weight ratio 4～5:1 with lubricating oil, then being pressed into columned paste mixture;
2) described paste mixture is pushed and extruded, then described paste is rolled into to band, then at the temperature of 100～300 ℃ or with volatile organic solvent, sloughed the lubricating oil in described band; With
3) by the unidirectional or two-way stretch under 100～390 ℃ of the described band after de-oiling, finally carry out heat setting type, be made for the fluorine-containing microporous membrane of described special type.
9. microporous teflon membran according to claim 8, it is characterized in that, in described step 1), the fluorine-containing dispersion resin compound of special type, inorganic, metal oxide or gac or carbon black, lubricating oil are mixed and stir with the weight ratio of 4～5:0.4～0.8:1.
10. microporous teflon membran according to claim 9, is characterized in that, described inorganic, metal oxide is selected from least one in titanium dioxide and dichloride copper.
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| CN111378240A (en) * | 2020-03-27 | 2020-07-07 | 山东森荣新材料股份有限公司 | PTFE nanometer mask film and preparation method thereof |
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