CN103285747A - Three-dimensional PTFE microporous membrane for filtration and preparation method thereof - Google Patents
Three-dimensional PTFE microporous membrane for filtration and preparation method thereof Download PDFInfo
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- CN103285747A CN103285747A CN2013101248781A CN201310124878A CN103285747A CN 103285747 A CN103285747 A CN 103285747A CN 2013101248781 A CN2013101248781 A CN 2013101248781A CN 201310124878 A CN201310124878 A CN 201310124878A CN 103285747 A CN103285747 A CN 103285747A
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Abstract
The present invention relates to a PTFE membrane for filtration and a method for producing the same. A three-dimensional PTFE microporous membrane for filtration is a multilayer membrane; the PTFE microporous membrane has the air permeability of 4-8 cm/s, the elongation at break of 150-180% and the average pore diameter of 0.2-2.5 microns. The three-dimensional PTFE microporous membrane for filtration prepared by the invention not only can simultaneously give consideration to air permeability and tensile fracture strength, but also can form fine bulges by performing active treatment on the surface of the membrane, thereby greatly improving the surface activity and the adhesive force.
Description
Technical field
The present invention relates to a kind of filtration with PTFE film and manufacture method thereof, be specifically related to a kind of filtration with three-dimensional PTFE microporous barrier and manufacture method thereof.
Background technology
Polytetrafluoroethylene (PTFE) has good high and low temperature resistance, and outstanding chemical resistance has " plastics king " title, and excellent dielectric properties and hydrophobicity.Adopt polytetrafluoroethylene (PTFE) as the PTFE film of feedstock production, can protect filtering substrate to prolong its service life better, improve filtering accuracy and the filter efficiency of filtering material, satisfy the requirement of industry environmental protection and cleaner production.Be preparation method and the goods thereof that the Chinese patent of 101920559A (201-12-22) discloses a kind of polytetrafluoroethylene film as patent publication No., though the polytetrafluoroethylene film of this method preparation possesses certain dimensional stability, air penetrability is not high.And at present, the PTFE film is as a kind of filtration of function admirable and the membrane material of separate fine particle, and the important physical parameter of weighing its performance is air penetrability and tensile break strength.The former has determined the complexity of ash-laden gas by filter medium, has showed the transmission of medium to gas; And the latter has determined the service life of film because fracture strength more Gao Ze is more long service life.But air penetrability and tensile break strength are a pair of paradox, and tensile break strength is the tension failure brute force on the unit are, and formula is the powerful F/ sectional area of intensity P=S, thickness is more thick, and S is more little for sectional area, and intensity P is just more big, but the thickness of film is more thick, and air penetrability is just more low, and strainability is just more poor.How to make the good tensile break strength of air penetrability again high PTFE microporous barrier be the technical barrier that the filtrate people explores always.
The PTFE membrane material will be brought into play its superior performance as filtering material simultaneously, and use on the surface that must be attached to filtering substrate.And well-known, PTFE limitation table surface tension is little, and the surface can be low, inertia is bigger, be difficult to the bonding and bonding back of other material firmness not quite, therefore how improve the surface-active of PTFE membrane material, with the filtering substrate good bond also be one of content of studying of the present invention together.
Summary of the invention
First purpose of the present invention is for solving the problems of the technologies described above, and provides a kind of filtration with three-dimensional PTFE microporous barrier.Another object of the present invention provides a kind of preparation method who filters with three-dimensional PTFE microporous barrier.The filtration of the present invention's preparation not only can take into account Air permenbility and tension failure brute force simultaneously with three-dimensional PTFE microporous barrier, and handles by three-dimensional film surface being carried out activity, forms tiny projection, improves surface-active greatly, improves adhesive force.
First purpose of the present invention is achieved by the following technical programs: a kind of filtration is multilayer film with three-dimensional PTFE microporous barrier, described PTFE microporous barrier; The air penetrability of described PTFE microporous barrier is the 4-8 cel, and elongation at break is 150-180%, and average pore size is the 0.2-2.5 micron.
Traditional PTFE film production takes batch mixing, beats embryo, extrudes, rolls, vertically draw, horizontal six procedures that draw.In extruding workshop section, cylinder blank enters the preformation die cavity compacting of pushing the cylinder entrance point, is full of gradually to push material chamber, cylinder middle part, at last by pushing cylinder outlet moulding die orifice.The cross-sectional area of this stage blank is referred to as compression ratio (RR) by dwindling greatly, is got by the merchant of the preformation die cavity cross-sectional area S1 that pushes the cylinder entrance point and port of export moulding die orifice cross-sectional area S2.The size of compression ratio directly influences the quality of film product.Compression ratio is more big, and film is more thick, and intensity is more high, and air penetrability is more little.Extruding zone adopts the circular port mould in traditional handicraft, and what push out is the cylinder membranes rod, and compression ratio is higher, fracture strength is better, but because employing is the circular port mould, stretching capability is poor, when calendering, material can be simultaneously to middle and two side flow, intermediate flow speed is often greater than both sides, thus cause the calendering band tear or produce the shirt rim, influence the skewness of finished product film air-vent, produce substandard products, the finished product rate is not high.Change extruding zone mouth mould into pancake by circle in the advanced operation now but be one deck flat-die, improved stretching capability, the film of Sheng Chaning is breathed freely evenly like this, and air penetrability is good, and the finished product rate is higher, but shortcoming is that the fracture strength of film is not high, and service life is influenced.Therefore, the inventor is through studying for a long period of time, change flat mouthful of mould of existing one deck into multilayer flat mouthful of mould, what push out like this is the flat die post of multilayer on the microcosmic, the film of producing after by calendering and longitudinal stretching and horizontal expanding operation is multilayer build-up three-dimensional film together on the microcosmic, has increased the fracture strength of film greatly; In addition, the inventor updates technology, make flat mouthful of molded three-dimensional film that is equipped with of this multilayer when improving fracture strength, keep the high ventilation rate, the air penetrability that obtains PTFE microporous barrier of the present invention is the 4-8 cel, elongation at break is 150-180%, and average pore size is the 0.2-2.5 micron.
In addition, the PTFE membrane material will be brought into play its superior performance as filtering material simultaneously, and use on the surface that must be attached to filtering substrate.And the PTFE film limitation table surface tension of conventional method preparation is little, and the surface can be low, and inertia is bigger, is difficult to the bonding and bonding back of other material firmness little.The present invention carries out plasma treatment for improving the PTFE film ability bonding with other material to three-dimensional PTFE film, forms tiny projection on the surface of film when the joint knot of opening film increases Air permenbility, improves surface-active, promote and base material be laminated with fastness.Plasma technique has simply, fast, the technology dry methodization, modification only relates to material surface and does not influence advantages such as body construction and performance, be various active particles such as the ion that utilizes plasma generation, electronics, free radical, excited atom and molecule are handled material surface, principle is to transmit energy in the plasma during high-energy particle bombardment material surface, its energy generally surpasses C-C, C-F or other contain the bond energy of C key, thereby the interaction of chemistry or physics can take place with material surface, make C-C, C-F key is opened, and produces a large amount of free radicals at material surface.When contacting with nitrogen, form peroxy radical or peroxy-radical rapidly, and can be at room temperature long-time stable existence.Because peroxy radical mainly is present in the PTFE surface, observes under micrometer microscope, there are many tiny projections on the surface, and rough surface is for creating conditions with being laminated with of Woven glass cloth.If but in plasma technique improper process control, as exciting power or frequency is not high or cause the film protrusion of surface inhomogeneous, even can produce the top layer and break, and too lowly can not form effective projection amount; In addition, the too small reaction purity that makes of vacuum is not high, cause finally prepd film quality bad, and the too high back of vacuum cost can increase a lot, and the inventor is by studying for a long period of time, and regulate the cooperation of plasma technique important parameter, and just making microporous barrier is that the surface has even tiny projection, these even tiny projections have improved the surperficial bonding intensity that the PTFE membrane material is attached to filtering substrate greatly.
As preferably, described microporous barrier is that to have density be 30000-50000/square centimeter on the surface, and particle diameter is the multilayer film of the projection of 0.1-4 micron.
Another object of the present invention is achieved by the following technical programs: a kind of manufacture method of filtering according to claim 1 with three-dimensional PTFE microporous barrier, and it may further comprise the steps successively:
A, batch mixing: the polytetrafluoroethylene (PTFE) pulvis is mixed with auxiliary agent and stir, obtain intermixture;
B, striking adobe: elder generation inserts above-mentioned intermixture in the baking oven and soaks into size under 40-50 ℃, makes column base post by pre-shaping device again;
C, extrude: adopt the flat unit of multilayer build-up that above-mentioned column base post flat-die is extruded to form and extrude the strap material; Pressure is 3.5～4.5MPa during described extruding, and extruded velocity is 1.5～5m/min, extrudes the wide 200～500mm of being of strap material, and thick is 3.0～5.0mm;
D, calendering: be 20～25 kilograms per centimeter with the above-mentioned strap material of extruding at linear pressure, linear velocity is to press and smooth under the pressure roller effect of 1.5～5m/min to make the broadband that thickness is 400～700 m.
E, longitudinal stretching: above-mentioned broadband longitudinal stretching under 150～250 ℃ temperature is made vertical base band;
F, horizontal expanding: earlier above-mentioned vertical base band horizontal expanding under 150～350 ℃ of temperature is become horizontal width of cloth band, again with described horizontal width of cloth band at 340～370 ℃ of following curing moldings, make PTFE film base;
G, surface modification: earlier place acetone soln to embathe surface contaminant above-mentioned PTFE film base, clean up with deionized water again, enter after the drying in a vacuum then and carry out surface modification treatment in the plasma generator, obtain finished film.
As preferably, auxiliary agent described in the step a is the mixture of emulsifying agent, coupling agent, adhesive and water; The weight ratio of described auxiliary agent and described polytetrafluoroethylene (PTFE) pulvis is 1:0.25.
As preferably, size described in the step b is paraffin or kerosene; The weight ratio of described size and described polytetrafluoroethylene (PTFE) pulvis is 1:1.25.
As preferably, the time of soaking into described in the step b is 11-14 hour.
As preferably, to make the temperature of column base post be 40 ℃ to pre-shaping device among the step b.
As preferably, the time of curing molding is 40-60 second among the step f.
As preferably, to embathe in the acetone soln in the step g and adopt ultrasonic embathing, washed with de-ionized water adopts ultrasonic cleaning in the step g.Ultrasonic embathing can be more efficient, cleans cleaner.
As preferably, charge into purity described in the step g in the plasma generator greater than 99% nitrogen, and to control its pressure be 1.8-2.2Pa, exciting power is 80-120W, frequency 13.30-14.60MHz, vacuum is 65-75Pa.
The preparation method of the three-dimensional PTFE microporous barrier of the present invention also is through inventor's gained that studies for a long period of time, by the cooperation of each processing step and technological parameter, reaches the effect of three-dimensional PTFE microporous barrier of the present invention.
The invention has the beneficial effects as follows:
1, the present invention changes flat mouthful of mould of existing one deck into multilayer flat mouthful of mould, makes flat mouthful of molded three-dimensional film that is equipped with of this multilayer keep the high ventilation rate when improving fracture strength.
2, the present invention carries out plasma treatment for improving the PTFE film ability bonding with other material to three-dimensional PTFE film, forms tiny projection on the surface of film when the joint knot of opening film increases Air permenbility, improves surface-active, promote and base material be laminated with fastness.
3, the preparation method of the three-dimensional PTFE microporous barrier of the present invention also is through inventor's gained that studies for a long period of time, by the cooperation of each processing step and technological parameter, reaches the effect of three-dimensional PTFE microporous barrier of the present invention.
The specific embodiment
This specific embodiment only is explanation of the invention; it is not limitation of the present invention; those skilled in the art can make the modification that does not have creative contribution to present embodiment as required after reading this specification, but as long as all are subjected to the protection of Patent Law in claim scope of the present invention.
Embodiment 1
A kind of manufacture method of filtering with three-dimensional PTFE microporous barrier, the polytetrafluoroethylene (PTFE) pulvis is mixed with auxiliary agent and stir, obtain intermixture, described auxiliary agent is the mixture of emulsifier glycerol, silane coupler, silica adhesive and water, wherein, the weight ratio of described auxiliary agent and described polytetrafluoroethylene (PTFE) pulvis is 1:0.25.Then insert above-mentioned intermixture in the baking oven and soaked in paraffin or the kerosene 11 hours with size under 40 ℃, make column base post by pre-shaping device under 40 ℃ again, wherein, the weight ratio of described size and described polytetrafluoroethylene (PTFE) pulvis is 1:1.25.Then, adopt the flat unit of multilayer build-up that above-mentioned column base post flat-die is extruded to form and extrude the strap material, pressure is 3.5MPa when extruding, and extruded velocity is 1.5m/min, extrudes the wide 200mm of being of strap material, and thick is 3.0mm.Be 20 kilograms per centimeter with the above-mentioned strap material of extruding at linear pressure, linear velocity is to press and smooth under the pressure roller effect of 1.5m/min to make the broadband that thickness is 400 m, more above-mentioned broadband longitudinal stretching under 150 ℃ temperature is made vertical base band.Then with above-mentioned vertical base band under 150 ℃ of temperature laterally expanding become horizontal width of cloth band, again with described horizontal width of cloth band at 340 ℃ of following curing moldings, the time of curing molding is 60 seconds, makes PTFE film base behind the curing molding; Earlier place acetone soln to embathe surface contaminant above-mentioned PTFE film base, clean up with deionized water again, enter after the drying in a vacuum then and carry out surface modification treatment in the plasma generator, obtain finished film, wherein, embathe in the acetone soln and adopt ultrasonic embathing, washed with de-ionized water adopts ultrasonic cleaning.Ultrasonic cleaning not only efficient and also clean cleaner.In addition, when carrying out surface modification treatment in the plasma generator, charge into purity greater than 99% nitrogen at plasma generator, PTFE sample with drying places plasma slab again, background pressure 1.8Pa controls nitrogen flow with mass flowmenter, treats that air pressure light discharges after stable, stop discharge after handling certain hour, powered-down also is exposed to sample and carries out oxidation in the atmosphere, wherein, and exciting power 80W, frequency 13.30MHz, vacuum is 65Pa.
Embodiment 2
A kind of manufacture method of filtering with three-dimensional PTFE microporous barrier, the polytetrafluoroethylene (PTFE) pulvis is mixed with auxiliary agent and stir, obtain intermixture, described auxiliary agent is emulsifying agent, coupling agent, adhesive and water, wherein, the weight ratio of described auxiliary agent and described polytetrafluoroethylene (PTFE) pulvis is 1:0.25.Then above-mentioned intermixture is inserted in the baking oven and at 45 ℃ and soaked into 12 hours with size paraffin or kerosene down, make column base post by pre-shaping device under 40 ℃ again, wherein, the weight ratio of described size and described polytetrafluoroethylene (PTFE) pulvis is 1:1.25.Adopt the flat unit of multilayer build-up that above-mentioned column base post flat-die is extruded to form and extrude the strap material; Pressure is 4.0MPa during described extruding, and extruded velocity is 3.0m/min, extrudes the wide 250mm of being of strap material, and thick is 4.0mm.Be 22 kilograms per centimeter with the above-mentioned strap material of extruding at linear pressure, linear velocity is to press and smooth under the pressure roller effect of 3m/min to make the broadband that thickness is 550 m.Above-mentioned broadband longitudinal stretching under 200 ℃ temperature is made vertical base band.Then with above-mentioned vertical base band under 220 ℃ of temperature laterally expanding become horizontal width of cloth band, again with described horizontal width of cloth band at 355 ℃ of following curing moldings, the time of curing molding is 50 seconds, makes PTFE film base behind the curing molding; Earlier place acetone soln to embathe surface contaminant above-mentioned PTFE film base, clean up with deionized water again, enter after the drying in a vacuum then and carry out surface modification treatment in the plasma generator, obtain finished film; Wherein, embathe in the acetone soln and adopt ultrasonic embathing, washed with de-ionized water adopts ultrasonic cleaning.Ultrasonic cleaning not only efficient and also clean cleaner.When carrying out surface modification treatment in the plasma generator, charge into purity greater than 99% nitrogen at plasma generator, the PTFE sample of drying is placed plasma slab, background pressure 2.0Pa, control nitrogen flow with mass flowmenter, treat that air pressure light discharges after stable, stop discharge after handling certain hour, powered-down also is exposed to sample and carries out oxidation in the atmosphere.Exciting power 100W, frequency 13.77MHz, vacuum is 70Pa.
Embodiment 3
A kind of manufacture method of filtering with three-dimensional PTFE microporous barrier, the polytetrafluoroethylene (PTFE) pulvis is mixed with auxiliary agent and stir, obtain intermixture, wherein, described auxiliary agent is emulsifying agent, coupling agent, adhesive and water, and the weight ratio of described auxiliary agent and described polytetrafluoroethylene (PTFE) pulvis is 1:0.25.Then above-mentioned intermixture is inserted in the baking oven and at 50 ℃ and soaked into 14 hours with size paraffin or kerosene down, under 40 ℃, make column base post by pre-shaping device again; The weight ratio of described size and described polytetrafluoroethylene (PTFE) pulvis is 1:1.25.Adopt the flat unit of multilayer build-up that above-mentioned column base post flat-die is extruded to form and extrude the strap material; Pressure is 4.5MPa during described extruding, and extruded velocity is 5m/min, extrudes the wide 500mm of being of strap material, and thick is 5.0mm.Be 25 kilograms per centimeter with the above-mentioned strap material of extruding at linear pressure, linear velocity is to press and smooth under the pressure roller effect of 5m/min to make the broadband that thickness is 700 m.Above-mentioned broadband longitudinal stretching under 250 ℃ temperature is made vertical base band.Then with above-mentioned vertical base band under 350 ℃ of temperature laterally expanding become horizontal width of cloth band, again with described horizontal width of cloth band at 340 ℃～370 ℃ following curing moldings, the time of curing molding is 60 seconds, makes PTFE film base behind the curing molding; Earlier place acetone soln to embathe surface contaminant above-mentioned PTFE film base, clean up with deionized water again, enter after the drying in a vacuum then and carry out surface modification treatment in the plasma generator, obtain finished film.Wherein, embathe in the acetone soln and adopt ultrasonic embathing, washed with de-ionized water adopts ultrasonic cleaning.Ultrasonic cleaning not only efficient and also clean cleaner.In addition, when carrying out surface modification treatment in the plasma generator, charge into purity greater than 99% nitrogen at plasma generator, the PTFE sample of drying is placed plasma slab, background pressure 2.2Pa controls nitrogen flow with mass flowmenter, treats that air pressure light discharges after stable, stop discharge after handling certain hour, powered-down also is exposed to sample and carries out oxidation in the atmosphere.Exciting power 120W, frequency 14.60MHz, vacuum is 75Pa.
Comparative Examples 1
Be the Technology design Comparative Examples of 101920559A (201-12-22) instruction according to patent publication No..A kind of preparation method of polytetrafluoroethylene film, it is characterized in that may further comprise the steps: (1) batch mixing: teflon resin powder and fluid lubricant are 1:(0.2～0.28 by weight) evenly mixed, under 40 ℃～80 ℃ temperature, left standstill 10～16 hours, toner and fluid lubricant are mixed, form the polytetrafluoroethylene (PTFE) material; (2) pressed compact and calendering: described polytetrafluoroethylene (PTFE) material is pressed into cylindrical blank at harder under 30 ℃～50 ℃, blank is extruded club by the pushing machine under 40 ℃～60 ℃ temperature, under 40 ℃～60 ℃, roll into the polytetrafluoroethylene (PTFE) base band through calender then; (3) longitudinal stretching: with described polytetrafluoroethylene (PTFE) base band longitudinal stretching in 180 ℃～300 ℃ baking ovens, obtain the degreasing base band; (4) cross directional stretch and thermal finalization: at 180 ℃～210 ℃ following cross directional stretch, 250 ℃～380 ℃ sintering typings, sintering time 20～80 seconds obtains heat-setting thin-film then with described degreasing base band; (5) cool water shower: with described heat-setting thin-film spraying cooling water, obtain horizontal and vertical size and claim qualitative good polytetrafluoro microporous membrane.
The PTFE film that above-described embodiment and Comparative Examples are made carries out elongation at break, film surface average pore size, air penetrability and detects, elongation at break of the present invention is pressed the GB7689 regulation and is detected, the regulation that air penetrability of the present invention is pressed GB/T5453-1997 detects, and concrete test result is shown in Table 1:
Table 1 embodiment and Comparative Examples experiment test result
Detect data as seen by table 1, the embodiment of the invention is made the PTFE film and be higher than Comparative Examples far away on air penetrability and elongation at break; In addition, the film of Comparative Examples surface average pore size does not almost have, and can't measure.The PTFE film that embodiment of the invention preparation is described not only has good fracture strength and has the high ventilation rate.
Claims (10)
1. a filtration is with three-dimensional PTFE microporous barrier, and it is characterized in that: described PTFE microporous barrier is multilayer film; The air penetrability of described PTFE microporous barrier is the 4-8 cel, and elongation at break is 150-180%, and average pore size is the 0.2-2.5 micron.
2. a kind of filtration is characterized in that with three-dimensional PTFE microporous barrier according to claim 1: described microporous barrier is that to have density be 30000-50000/square centimeter on the surface, and particle diameter is the multilayer film of the projection of 0.1-4 micron.
3. manufacture method of filtering according to claim 1 with three-dimensional PTFE microporous barrier, it is characterized in that: it may further comprise the steps successively:
A, batch mixing: the polytetrafluoroethylene (PTFE) pulvis is mixed with auxiliary agent and stir, obtain intermixture;
B, striking adobe: elder generation inserts above-mentioned intermixture in the baking oven and soaks into size under 40-50 ℃, makes column base post by pre-shaping device again;
C, extrude: adopt the flat unit of multilayer build-up that above-mentioned column base post flat-die is extruded to form and extrude the strap material; Pressure is 3.5～4.5MPa during described extruding, and extruded velocity is 1.5～5.0m/min, extrudes the wide 200～500mm of being of strap material, and thick is 3.0～5.0mm;
D, calendering: be 20～25 kilograms per centimeter with the above-mentioned strap material of extruding at linear pressure, linear velocity is to press and smooth under the pressure roller effect of 1.5～5m/min to make the broadband that thickness is 400～700 m.
E, longitudinal stretching: above-mentioned broadband longitudinal stretching under 150～250 ℃ temperature is made vertical base band;
F, horizontal expanding: earlier above-mentioned vertical base band horizontal expanding under 150～350 ℃ of temperature is become horizontal width of cloth band, again with described horizontal width of cloth band at 340～370 ℃ of following curing moldings, make PTFE film base;
G, surface modification: earlier place acetone soln to embathe surface contaminant above-mentioned PTFE film base, clean up with deionized water again, enter after the drying in a vacuum then and carry out surface modification treatment in the plasma generator, obtain finished film.
4. as a kind of manufacture method of filtering with three-dimensional PTFE microporous barrier as described in the claim 2, it is characterized in that: auxiliary agent described in the step a is the mixture of emulsifying agent, coupling agent, adhesive and water; The weight ratio of described auxiliary agent and described polytetrafluoroethylene (PTFE) pulvis is 1:0.25.
5. as a kind of manufacture method of filtering with three-dimensional PTFE microporous barrier as described in the claim 3, it is characterized in that: size described in the step b is paraffin or kerosene; The weight ratio of described size and described polytetrafluoroethylene (PTFE) pulvis is 1:1.25.
6. as a kind of manufacture method of filtering with three-dimensional PTFE microporous barrier as described in the claim 4, it is characterized in that: the time of soaking into described in the step b is 11-14 hour.
7. as a kind of manufacture method of filtering with three-dimensional PTFE microporous barrier as described in the claim 5, it is characterized in that: to make the temperature of column base post be 40 ℃ to pre-shaping device among the step b.
8. as a kind of manufacture method of filtering with three-dimensional PTFE microporous barrier as described in the claim 6, it is characterized in that: the time of curing molding is 40-60 second among the step f.
9. as a kind of manufacture method of filtering with three-dimensional PTFE microporous barrier as described in the claim 7, it is characterized in that: embathe in the acetone soln in the step g and adopt ultrasonic embathing; Washed with de-ionized water adopts ultrasonic cleaning in the step g.
10. as a kind of manufacture method of filtering with three-dimensional PTFE microporous barrier as described in the claim 9, it is characterized in that: charge into purity described in the step g in the plasma generator greater than 99% nitrogen, and to control its pressure be 1.8-2.2Pa, exciting power is 80-120W, frequency 13.30-14.60MHz, vacuum is 65-75Pa.
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| CN107277701A (en) * | 2017-08-12 | 2017-10-20 | 施柏德（厦门）科技有限公司 | A kind of preparation method of the waterproof and breathable sound passing membrane compound by lamination |
| CN108568220A (en) * | 2018-04-26 | 2018-09-25 | 杭州科百特过滤器材有限公司 | The preparation method of polytetrafluorethylenano nano filter membrane |
| CN111077292A (en) * | 2019-12-23 | 2020-04-28 | 上海微谱化工技术服务有限公司 | Pretreatment method for analysis of artificial leather material for vehicle |
| CN111361171A (en) * | 2019-11-19 | 2020-07-03 | 南京玻璃纤维研究设计院有限公司 | Preparation method of asymmetric structure film |
| CN113043632A (en) * | 2021-03-09 | 2021-06-29 | 山东森荣新材料股份有限公司 | Preparation method of polytetrafluoroethylene high-strength microporous membrane |
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| CN108568220A (en) * | 2018-04-26 | 2018-09-25 | 杭州科百特过滤器材有限公司 | The preparation method of polytetrafluorethylenano nano filter membrane |
| CN111361171A (en) * | 2019-11-19 | 2020-07-03 | 南京玻璃纤维研究设计院有限公司 | Preparation method of asymmetric structure film |
| CN111077292A (en) * | 2019-12-23 | 2020-04-28 | 上海微谱化工技术服务有限公司 | Pretreatment method for analysis of artificial leather material for vehicle |
| CN113043632A (en) * | 2021-03-09 | 2021-06-29 | 山东森荣新材料股份有限公司 | Preparation method of polytetrafluoroethylene high-strength microporous membrane |
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Address after: Zhejiang anjifeng Huzhou Glass Industry Co., Ltd Patentee after: Zhejiang Shengfeng Filtration Technology Co.,Ltd. Address before: Zhejiang anjifeng Huzhou Glass Industry Co., Ltd Patentee before: ANJI SHENGFENG FIBERGLASS Co.,Ltd. |
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