Summary of the invention
In view of this, the object of the invention is to the preparation method proposing the fluorine-containing dispersion resin mixture of a kind of special type and microporous membrane thereof, to improve the physical strength of fluorine-containing microporous membrane or Water Pressure Resistance or air penetrability.
Based on above-mentioned purpose, the invention provides the preparation method of the fluorine-containing dispersion resin mixture of a kind of special type, described preparation method comprise first by proplast dispersion emulsion with fluorine-containing can hot melt processibility dispersion emulsion with the dry weight of 19:1 ~ 3:7 than blended, then with deionized water, blend is diluted to the blending emulsion that solid content is 10 ~ 20%, again through high-speed stirring breakdown of emulsion, cohesion, obtains extraordinary fluorine-containing dispersion resin mixture after drying;
Wherein, the solid content of described proplast dispersion emulsion is 20 ~ 39%, described fluorine-containing can the solid content of hot melt processibility dispersion emulsion be 10 ~ 39%.
Alternatively, described proplast dispersion emulsion with fluorine-containing can the dry weight of hot melt processibility dispersion emulsion than for 7:3 ~ 2:3.
Alternatively, the manufacture method of described proplast dispersion emulsion comprises: in autoclave, add deionized water and perfluorinated surfactant, vacuumize deoxygenation in still, and heat up, and opens and stirs to form emulsion; When temperature in the kettle rises to 65 ~ 75 DEG C, in still, pass into tetrafluoroethylene gas; Still internal pressure adds radical initiator after reaching 18 ~ 25 kilograms, and start homopolymerization, temperature in the kettle maintains 70 ~ 110 DEG C; Sustained reaction reaches 20 ~ 39% to emulsion solid content, after temperature in the kettle is down to room temperature, stops stirring, reaction terminating, obtained tetrafluoroethylene homopolymerization dispersion emulsion, the median size about 180 ~ 300nm of its primary particle.
Preferably, described polytetrafluoroethyl-ne polyamino alkenyl dispersion emulsion is through breakdown of emulsion, and cohesion, obtain polytetrafluoroethyl-ne polyamino alkenyl dispersion resin after drying, the standard specific gravity of this resin is 2.14 ~ 2.22g/cm
3, fusing point is 300 ~ 360 DEG C.
Alternatively, describedly fluorine-containingly can the manufacture method of hot melt processibility dispersion emulsion to comprise: in autoclave, add deionized water and perfluorinated surfactant, in still, vacuumize deoxygenation, and heat up, open and stir to form emulsion; Temperature in the kettle rises to 65 ~ 75 DEG C, the mixed gas then based on tetrafluoroethylene in still, and still internal pressure adds radical initiator after reaching 10 ~ 15 kilograms, and started copolymer reacts, and temperature in the kettle maintains 20 ~ 120 DEG C; Sustained reaction reaches about 10 ~ 39% to emulsion solid content, after temperature in the kettle is down to room temperature, stops stirring, reaction terminating, obtained fluorine-containing can hot melt processibility dispersion emulsion, the median size about 60 ~ 250nm of its primary particle.
Preferably, in the described mixed gas based on tetrafluoroethylene gas containing volume percent be 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, dichlorodifluoroethylene, 3, any one or its combination in the rare and R 1216 of 3,3-trifluoropropyl.
Preferably, described fluorine-containing can hot melt processibility dispersion emulsion through breakdown of emulsion, cohesion, obtain after drying fluorine-containing can hot melt processibility dispersion resin, the standard specific gravity of this resin is 2.08 ~ 2.22g/cm
3, fusing point is 220 ~ 320 DEG C.
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 be selected from persulphate, hydrogen peroxide or organo-peroxide any one or its combination.
Alternatively, in homopolymerization and copolyreaction process, still internal pressure at least maintains 10 kilograms.
The invention provides the preparation method of the fluorine-containing microporous membrane of a kind of special type, described manufacture method comprises following operation:
1) the fluorine-containing dispersion resin mixture of the special type preparation method by the fluorine-containing dispersion resin mixture of above-mentioned special type obtained and lubricating oil mix according to weight ratio 4 ~ 5:1 and stir, and are then pressed into columned paste mixture;
2) by pushing machine, described paste mixture is carried out extruding and extruding at 20 ~ 120 DEG C, then described paste is rolled into band, then at the temperature of 100 ~ 300 DEG C or with volatile organic solvent, slough the lubricating oil in described band; With
3) by the unidirectional or two-way stretch at 100 ~ 390 DEG C 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 mixture of described special type mixes according to weight ratio 4 ~ 5:1 with described lubricating oil.
Alternatively, in described step 1), fluorine-containing for special type dispersion resin mixture, inorganic, metal oxide or gac or carbon black, lubricating oil are mixed with the weight ratio of 4 ~ 5:0.4 ~ 0.8:1 and stirs.
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 that manufacture method provided by the invention obtains, its nanofiber content is higher, physical mechanical strength is as large in the gravity of resistance to 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, with fabric compound after, the anti-tensile of the composite material of gained, Water Vapour Permeability, ventilation property improve; Face water-sprinkling is good, and filter effect is better, more can be accepted by market.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with specific embodiment, the present invention is described in more detail.
The manufacture of embodiment 1(tetrafluoroethylene homopolymerization dispersion emulsion)
In the horizontal high-pressure reactor of about 100 liters, first adding the deionized water of 50L and the ammonium perfluorocaprylate of 15g, vacuumizing deoxygenation (until oxygen level <20ppm) in still, and heating up, open and stir to form emulsion; When temperature in the kettle rises to about 70 DEG C, pass into the tetrafluoroethylene gas of volumetric molar concentration > 99.99% in still, still internal pressure reaches about 20 kilograms.Add 8 grams of ammonium persulphates (being dissolved in advance in 500 ml waters) in still as initiator, start homopolymerization, temperature in the kettle maintains 70 ~ 110 DEG C, makes still internal pressure maintain about 20 kilograms in reaction process by tetrafluoroethylene gas.Sustained reaction reaches about 20% to emulsion solid content, and after temperature in the kettle is down to room temperature, stop stirring, reaction terminating, obtained tetrafluoroethylene homopolymerization dispersion emulsion, the median size of its primary particle is about 280nm.Get sample emulsion through breakdown of emulsion, cohesion, after drying, detect the standard specific gravity of polytetrafluoroethyl-ne polyamino alkenyl dispersion resin, be about 2.19g/cm
3, fusing point about 330 DEG C.
Embodiment 2(is fluorine-containing can the manufacture of hot melt processibility dispersion emulsion)
In the horizontal high-pressure reactor of about 100 liters, first add the deionized water of 50L and the ammonium perfluorocaprylate of 18g, vacuumizing deoxygenation (until oxygen level <20ppm) in still, opening and stirring to form emulsion; Temperature in the kettle is raised to about 70 DEG C, and in still, then pass into the mixed gas of tetrafluoroethylene and R 1216, tetrafluoroethylene mixes according to mol ratio 13:7 with R 1216, and still internal pressure reaches about 12 kilograms.8 grams of ammonium persulphates (being dissolved in advance in 500 ml waters) are added as initiator in still, started copolymer reacts, temperature in the kettle maintains 70 ~ 110 DEG C, make still internal pressure maintain about 12 kilograms by mixed gas in reaction process, sustained reaction reaches about 30% to emulsion solid content, after temperature in the kettle is down to room temperature, stop stirring, reaction terminating, obtained fluorine-containing can hot melt processibility dispersion emulsion, the median size of its primary particle is about 150nm.Get sample emulsion through breakdown of emulsion, cohesion, after drying, detect fluorine-containing can the fusing point about 266 DEG C of thermally melting dispersion resin, standard specific gravity is about 2.15g/cm
3.
The preparation of the extraordinary fluorine-containing dispersion resin mixture of embodiment 3()
(3A) by the proplast dispersion emulsion (solid content about 20%) of embodiment 1 and embodiment 2 fluorine-containing can hot melt processibility dispersion emulsion (solid content about 30%) with the weight in wet base of 3:2 than blended, with deionized water, blend is diluted to solid content about 13% again, then high-speed stirring breakdown of emulsion, cohesion, obtains extraordinary fluorine-containing dispersion resin mixture after drying.The fusing point of this extraordinary fluorine-containing dispersion resin mixture has 2 points: 266 DEG C and 335 DEG C, standard specific gravity is about 2.17g/cm
3.Weight in wet base ratio is converted into dry weight ratio, is about (20% × 3): (30% × 2)=1:1.
(3B) by the proplast dispersion emulsion (solid content about 20%) of embodiment 1 and embodiment 2 fluorine-containing can hot melt processibility dispersion emulsion (solid content about 30%) with the weight in wet base of 15:1 than blended, with deionized water, blend is diluted to solid content about 16% again, then high-speed stirring breakdown of emulsion, cohesion, obtains extraordinary fluorine-containing dispersion resin mixture after drying.The fusing point of this extraordinary fluorine-containing dispersion resin mixture has 2 points: 266 DEG C and 335 DEG C, standard specific gravity is about 2.186g/cm
3.Weight in wet base ratio is converted into dry weight ratio, is about (20% × 15): (30% × 1)=10:1.
(3C) by the proplast dispersion emulsion (solid content about 20%) of embodiment 1 and embodiment 2 fluorine-containing can hot melt processibility dispersion emulsion (solid content about 30%) with the weight in wet base of 9:14 than blended, with deionized water, blend is diluted to solid content about 13.5% again, then high-speed stirring breakdown of emulsion, cohesion, obtains extraordinary fluorine-containing dispersion resin mixture after drying.The fusing point of this extraordinary fluorine-containing dispersion resin mixture has 2 points: 266 DEG C and 335 DEG C, standard specific gravity is about 2.178g/cm
3.Weight in wet base ratio is converted into dry weight ratio, is about (20% × 9): (30% × 14)=3:7.
The manufacture of the extraordinary fluorine-containing microporous membrane of embodiment 4()
Mix manufacturing the fluorine-containing dispersion resin mixture of the special type obtained in embodiment 3A with the weight ratio of about 4.3:1 with U.S. Exxon Mobil senior lubricant (trade mark Isopar M), first columned paste mixture is pressed in advance after stirring, by pushing machine, described paste mixture is carried out extruding and extruding again at about 50 DEG C, described paste is rolled into the band that thickness is about 0.25mm.The de-oiling in the baking oven of about 260 DEG C of this band is obtained dry film, by this dry film longitudinal stretching about 9 times under the hot conditions of about 300 DEG C, and then under the hot conditions of about 300 DEG C cross directional stretch about 9 times, namely obtain extraordinary fluorine-containing microporous membrane.
After testing, the porosity of the extraordinary fluorine-containing microporous membrane of gained is about 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 resistance to ball is greater than 1 kilogram.
By 20g/m
2terylene non-woven fabric and the fluorine-containing microporous membrane direct combination of obtained special type (together with mainly by electrostatic non-woven fabrics being inhaled with film), 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 resistance to ball is greater than 2 kilograms, and high efficiency filter effect is good.According to ASHRAE52.2 testing method, wind speed about 16 meters/point, air flow quantity about 13500 liters/min, effectively can filter about 0.1 micron particle of about 90 ~ 96%, be applicable to doing Filters, as air filtration, especially makees mouth mask and uses.Face water-sprinkling is splendid, and according to AATCC testing method 22-2010, water-sprinkling test can reach 100 points, and the globule all tumbles from its surface whether great or small, also can replace the aftertreatment of fabric spill resistant.
The manufacture of the extraordinary fluorine-containing microporous membrane of embodiment 5()
Mix manufacturing the fluorine-containing dispersion resin mixture of the special type obtained in embodiment 3A with the weight ratio of about 4.5:1 with U.S. Exxon Mobil senior lubricant (trade mark Isopar M), first columned paste mixture is pressed in advance after stirring, by pushing machine, described paste mixture is carried out extruding and extruding again at about 52 DEG C, described paste is rolled into the band that thickness is about 0.25mm.The de-oiling in the baking oven of about 260 DEG C of this band is obtained dry film, by this dry film longitudinal stretching about 5 times under the hot conditions of about 300 DEG C, and then under the hot conditions of about 300 DEG C cross directional stretch about 5 times, also can obtain extraordinary fluorine-containing microporous membrane.
After testing, the mean porosities of the fluorine-containing microporous membrane of gained is about 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 resistance to ball is greater than 2.5 kilograms.
With polyurethane adhesive by 90g/m
2nylon 6 fabric point be affixed on this obtained microporous teflon membran, the composite garment 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 resistance to ball is greater than 5 kilograms, be applicable to making water proof wind proof clothes, be also applicable to making dust free chamber vest.
Embodiment 6(is containing the manufacture of the fluorine-containing microporous membrane of special type of titanium dioxide)
Mix manufacturing the fluorine-containing dispersion resin mixture of the special type obtained in embodiment 3C with the weight ratio of about 4:0.6:1 with titania powder and U.S. Exxon Mobil senior lubricant (trade mark Isopar M), first columned paste mixture is pressed in advance after stirring, by pushing machine, described paste mixture is carried out extruding and extruding again at about 50 DEG C, described paste is rolled into the band that thickness is about 0.25mm.The de-oiling in the baking oven of about 260 DEG C of this band is obtained dry film, by this dry film longitudinal stretching about 9 times under the hot conditions of about 280 DEG C, and then under the hot conditions of about 280 DEG C cross directional stretch about 9 times, namely obtain containing the fluorine-containing microporous membrane of special type of titanium dioxide.
After testing, the porosity of the fluorine-containing microporous membrane of gained is about 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 resistance to ball is greater than 0.5 kilogram, and it is very thin fluorine-containing microporous membrane, seem be clear to translucent.
By 20g/m
2terylene non-woven fabric and obtained 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 resistance to ball is greater than 1 kilogram, and 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)
Mix manufacturing the fluorine-containing dispersion resin mixture of the special type obtained in embodiment 3A with the weight ratio of about 4:0.5:1 with activated carbon powder and U.S. Exxon Mobil senior lubricant (trade mark Isopar M), first columned paste mixture is pressed in advance after stirring, by pushing machine, described paste mixture is carried out extruding and extruding again at about 50 DEG C, described paste is rolled into the band that thickness is about 0.25mm.The de-oiling in the baking oven of about 260 DEG C of this band is obtained dry film, by this dry film longitudinal stretching about 6 times under the hot conditions of about 290 DEG C, and then under the hot conditions of about 290 DEG C cross directional stretch about 6 times, namely obtain containing the fluorine-containing microporous membrane of special type of activated carbon.
After testing, the mean porosities of the fluorine-containing microporous membrane of gained is about 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/ sky, the gravity of resistance to ball is greater than 0.8 kilogram, and it is the fluorine-containing microporous membrane of grey.
With polyurethane adhesive by 110g/m
2enlightening human relations weaving face fabric point be affixed on this obtained microporous teflon membran, the composite garment 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 resistance to 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, is about 2.16g/cm by standard specific gravity
3polytetrafluoroethyldispersion dispersion resin (derive from Japanese great Jing company, resin grade 106) mix with the weight ratio of about 4.3:1 with U.S. Exxon Mobil senior lubricant (trade mark Isopar M), first columned paste mixture is pressed in advance after stirring, by pushing machine, described paste mixture is carried out extruding and extruding again at about 50 DEG C, described paste is rolled into the band that thickness is about 0.25mm.The de-oiling in the baking oven of about 260 DEG C of this band is obtained dry film.By this dry film longitudinal stretching about 9 times under the hot conditions of about 300 DEG C, and then under the hot conditions of about 300 DEG C cross directional stretch about 9 times, obtained polytetrafluoroethylmicroporous microporous membrane.
After testing, with the microporous teflon membran that Japan's large capital resin (trade mark 106) obtains for 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 resistance to 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 obtained fluorine-containing microporous membrane by electrostatic compound, the composite material air penetrability of gained is less than 150 milliliters of air/minute/square centimeters, and water pressure resistance is greater than 80Pa, and Water Vapour Permeability is greater than 60 kg of water/m
2/ sky, the gravity of resistance to 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, is about 2.19g/cm by standard specific gravity
3tetrafluoroethylene homopolymerization dispersion resin (deriving from embodiment 1) mix with the weight ratio of about 4.3:1 with U.S. Exxon Mobil senior lubricant (trade mark Isopar M), first columned paste mixture is pressed in advance after stirring, by pushing machine, described paste mixture is carried out extruding and extruding again at about 50 DEG C, described paste is rolled into the band that thickness is about 0.25mm.The de-oiling in the baking oven of about 260 DEG C of this band is obtained dry film.By this dry film longitudinal stretching about 9 times under the hot conditions of about 300 DEG C, and then under the hot conditions of about 300 DEG C cross directional stretch about 9 times, obtained 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 resistance to ball is less than 0.3 kilogram, although ventilation property can manage it, but the gravity of resistance to ball is not good, representing that tension stress cannot withstand collision not, is the defect doing filtration application.
By 20g/m
2terylene non-woven fabric and obtained fluorine-containing microporous membrane by electrostatic compound, 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 resistance to ball is less than 1 kilogram, cannot withstand collision, be the defect doing filtration application.
As can be seen here, the present invention first by proplast dispersion resin and fluorine-containing can after the blended obtained compound of hot melt processibility dispersion resin, again it is mixed with lubricating oil, is extruded by paste, de-oiling, unidirectional or two-way stretch, obtained extraordinary fluorine-containing microporous membrane.The nanofiber content of this microporous membrane is high, and physical mechanical strength is as higher in 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, with garment material compound after, 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 adopted in above embodiment and instrument are respectively:
The testing method of porosity detects 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: vised by sample one circular flange clamp (internal diameter 14 centimeters), be placed in an airtight tube type passage, in tubular type ventilation duct, sample one end dried compressed air, pressure-controlling is at 127Pa, sample another end is normal pressure opening, and air penetrability is the transit dose of the sample of metering how many milliliters of air/minute/square centimeter areas.
The gravity of resistance to ball testing method is described as follows: vised by sample one circular flange clamp (internal diameter 7.6 centimeters), sample is placed the steel ball of 2.5 centimeters of diameters, sees that sample can sustain how many ball weight.
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 amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.