CN106669442A - PTFE (Polytetrafluoroethylene) fiber pipe type film - Google Patents

PTFE (Polytetrafluoroethylene) fiber pipe type film Download PDF

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Publication number
CN106669442A
CN106669442A CN201510764582.5A CN201510764582A CN106669442A CN 106669442 A CN106669442 A CN 106669442A CN 201510764582 A CN201510764582 A CN 201510764582A CN 106669442 A CN106669442 A CN 106669442A
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China
Prior art keywords
vestibule
tubular membrane
uniform distribution
polytetrafluoroethylene fibre
porous material
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CN201510764582.5A
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Chinese (zh)
Inventor
叶雷
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Chongqing Runze Pharmaceutical Co Ltd
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Chongqing Runze Pharmaceutical Co Ltd
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Priority to CN201510764582.5A priority Critical patent/CN106669442A/en
Priority to PCT/CN2016/105258 priority patent/WO2017080470A1/en
Publication of CN106669442A publication Critical patent/CN106669442A/en
Pending legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/04Tubular membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/04Tubular membranes
    • B01D69/046Tubular membranes characterised by the cross-sectional shape of the tube
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/364Membrane distillation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/30Polyalkenyl halides
    • B01D71/32Polyalkenyl halides containing fluorine atoms
    • B01D71/36Polytetrafluoroethene

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention provides a PTFE (Polytetrafluoroethylene) fiber pipe type film. The PTFE fiber pipe type film comprises a PTFE material body, wherein PTFE is in a fibrous shape; the fiber diameter is greater than 200 nm and is smaller than or equal to 2000 nm; the PTFE material body is provided with pore cavities of which the pore diameter is 10 to 2000 nm and a cavity wall which is formed by three-dimensionally and spatially surrounding the pore cavities; the pore cavities are in uniform distribution; all the pore cavities are three-dimensionally communicated; the uniform distribution of the pore cavities means that all the pore cavities are in uniform distribution on porous materials under optional unit volume; the porosity is greater than or equal to 75 percent, the light transmittance is 50 percent or more, the tensile strength is 28 N/mm<2> or more, and the waterproof pressure is 4 kg/cm<2> or more. According to the PTFE fiber pipe type film provided by the invention, a specific and clear measurement way is provided for the uniform distribution of the pore cavities of the PTFE fiber pipe type film, the porous materials and the pore distribution uniformity of multi-stage structure of the porous materials are confirmed to be measured under the scale of small unit volume, and the porous structures are highly uniform, so that uniformity and consistency of all properties of the porous materials are ensured.

Description

A kind of polytetrafluoroethylene fibre tubular membrane
Technical field
The present invention relates to a kind of porous material, specifically a kind of polytetrafluoroethylene fibre tubular membrane.
Background technology
Solid containing certain amount hole, porous material, is a kind of material that network structure is made up of insertion or blind bore hole.For continuous media material, porous material typically has the advantages that relative density is low, specific strength is high, specific surface area is high, lightweight, sound insulation, heat-insulated, good penetrability.According to the difference of pore size, porous material can be divided into micropore again(Aperture is less than 2 nm)It is material, mesoporous(Aperture 2-50 nm)Material and macropore(Aperture is more than 50 nm)Material.
Porous material is distinguished by its material, can be divided into metal polyporous material and non-metal porous material.Non-metal porous material typically has the features such as specific surface area is big, density is little, thermal conductivity is little, relative density is little, porosity is big, in catalyst(Including carrier), adsorbent, insulation, thermal insulation, sewage and exhaust-gas treatment, filter liquid and gas(Or even antibacterial), light building material, the field such as environmental protection, improved soil, chemical industry is with a wide range of applications.Wherein, polytetrafluoroethylporous porous membrane material is with the performance such as its temperature stability, chemical stability, electric insulation, fire-retardant, self-lubricating, and its range of application is extremely wide.However, the randomness, scrambling due to pore structure, it still can not meet many application performances.
In many applications, it is required for its porous material itself uniform, its pore size, hole are evenly distributed so that performance uniformity, but in fact, many porous materials do not reach this requirement, its uniformity supplies;Despite material call oneself and reached higher uniformity, but its uniformity is still the uniformity under large volume yardstick, if being weighed with small size yardstick, such as take up an official post in material and take the said three-dimensional body that polylith volume is not more than a cubic centimetre, its quality is surveyed respectively, its uniformity coefficient difference is still very big, thus result in polytetrafluoroethylporous porous membrane material various performances such as intensity, elastic modelling quantity, flux etc. it is uneven, have a strong impact on its function.
The content of the invention
It is an object of the invention to provide architecture, controllable, high uniformity polytetrafluoroethylene fibre tubular membrane.
The purpose of the present invention is realized by following measures:
A kind of polytetrafluoroethylene fibre tubular membrane, including polytetrafluoroethylmaterial material body, politef is in threadiness, 200nm < fibre diameters are≤2000nm, the cavity wall that body has the vestibule in 10nm~2000nm apertures and formed around vestibule in three dimensions, its vestibule is in uniform distribution, the three-dimensional insertion of each vestibule, and vestibule refers to each vestibule on the porous material under arbitrary unit level volume in uniform distribution in uniform distribution;Porosity more than 75%, light transmittance is more than 50%, tensile strength 28N/mm2More than, water pressure resistance 4kg/cm2More than.
Specifically, above-mentioned polytetrafluoroethylene fibre tubular membrane, vestibule with 200~2000nm apertures and the cavity wall formed around vestibule in three dimensions, arrange subordinate's vestibule of 10~150nm, vestibules at different levels each three-dimensional insertion and vestibule at different levels also insertion each other each other in cavity wall;Vestibule is in uniform distribution, and vestibule refers to each vestibule on the porous material under arbitrary unit level volume in uniform distribution in uniform distribution.
Specifically, above-mentioned unit level volume refers to cubic centimetre level or cubic millimeter level or more subsection level volume.
More specifically, above-mentioned vestibule is referred in uniform distribution be not more than each said three-dimensional body of a cubic centimetre and formed objects in the take up an official post volume that takes of the porous material, their quality is substantially suitable.
More specifically, above-mentioned quality quite refers to the said three-dimensional body for appointing the multiple volumes for taking to be not more than a cubic centimetre and formed objects on the porous material substantially, claim its quality respectively, the meansigma methodss of their quality are obtained, and arbitrary three-dimensional weight is not more than the 4% of said three-dimensional body mass average value relative to the absolute value of the bias of mass average value.
Further, the multistage material take up an official post the volume that takes be not more than one cubic millimeter formed objects said three-dimensional body, their quality are substantially suitable.
More specifically, the quality quite refers to the said three-dimensional body of the formed objects for appointing the multiple volumes for taking to be not more than a cubic millimeter on the porous material substantially, claim its quality respectively, the meansigma methodss of their quality are obtained, and arbitrary three-dimensional weight is not more than the 4% of said three-dimensional body mass average value relative to the absolute value of the bias of mass average value.
Preferably, above-mentioned polytetrafluoroethylene fibre tubular membrane is made up of multistage porous material, body is the vestibule being classified with material pore size, and the cavity wall in three dimensions around vestibule is constituted, subordinate's vestibule, vestibules at different levels each three-dimensional insertion and vestibule at different levels also insertion each other each other are set in cavity wall.More specifically, next stage porous material constitutes the cavity wall of upper level vestibule.The cavity wall of higher level's vestibule is constituted by the multistage porous material of its subordinate is compound, or is constituted by the porous materials at different levels of its subordinate are compound, and material can be caused to meet specific functional requirement.
Specifically, every grade of porous material of material body is a continuous structure body certainly.Maximum external boundary per one-level porous material is suitable with whole material body space boundary.I.e. every grade porous material can be present in body as the porous material of one-level independence, and with its physical and chemical performance alone.Such structure can cause the physical and chemical performance of porous materials at different levels difference, have different physical and chemical performances in the whole space of relatively-stationary material, better meet many functional requirements.
Beneficial effect
1., the invention provides a kind of polytetrafluoroethylene fibre tubular membrane with loose structure, specify that its version, the hierarchy form of its vestibule and its uniformity structure can meet several functions demand.
2. the present invention is evenly distributed to the vestibule of polytetrafluoroethylene fibre tubular membrane and proposes concrete and clear and definite metric form, specify that it is to get off to measure porous material and the pore size distribution uniformity of its multilevel hierarchy with the yardstick of subsection level volume, such loose structure is high uniformity, so as to ensure that the uniformity consistency of each performance of porous material.
3. polytetrafluoroethylene fibre tubular membrane of the present invention is three-dimensional insertion, including every grade of hole three-dimensional communication, and hole at different levels mutually three-dimensional insertion, and connectivity is good, can fully meet the functional requirement of material.
4. the polytetrafluoroethylene fibre tubular membrane of the present invention is the hydrophobic surface with multistage coarse structure.Surface water contact angle can reach more than 165 °.
5. poly tetrafluoroethylene has diffuse-reflectance phenomenon, polytetrafluoroethylstephanoporate stephanoporate fibrous membrane, the such as film properties such as pore size distribution, hierarchy, porosity, hole shape architectural characteristic, technique etc. and light transmittance, mechanical strength, water pressure resistance are relevant, the polytetrafluoroethylene fibre tubular membrane of the present invention, bright cunning that film color is bright, gloss becomes clear, without the need for supporting, form stable, thickness is controllable, is applied to Membrane Materials process, flux>38L/m2H, more than 99.8%, tensile strength can reach 32N/mm to rejection2More than, water pressure resistance 8kg/cm2More than.
Specific embodiment
Specific embodiment gives detailed embodiment premised on technical solution of the present invention, but protection scope of the present invention is not limited only to following embodiments.Without departing from change above-mentioned technological thought of the invention in the case of, according to the ordinary technical knowledge and/or customary means of this area, it is clear that the replacement or change of various ways can also be made, and all should be included within the scope of the present invention.
Embodiment 1
The polytetrafluoroethylene fibre tubular membrane of the present invention, with second hole structure, wherein, there is the second level vestibule for being uniformly distributed, being mutually communicated in the cavity wall of the first order vestibule be uniformly distributed, being mutually communicated, and the also insertion each other each other of two-stage hole, the insertion is three-dimensional insertion.Every grade of porous material of material body is a continuous structure body certainly.Total effective drainage porosity is 75%, and fibre diameter is 500nm ± 20 nm, and macropore average pore size is 1000nm, there is the insertion aperture of average pore size 50nm in the cavity wall of macropore.
It is machined into method to take up an official post in the porous material said three-dimensional body of the same size for taking 9 10mm × 10mm × 10mm, its quality is tested with prunus mume (sieb.) sieb.et zucc. Teller-support benefit XP26 Microbalance balances, as a result it is as shown in table 1, wherein, intensive reading is expressed as a percentage with the absolute value of the bias of meansigma methodss, its value be relative to meansigma methodss absolute value of the bias divided by mass average value, as shown in Table 1, its mass deviation is not more than 4%.
Determination of light transmittance:Using LCD5200 photoelectric characteristic testers, scanning 380-780nm wave bands calculate light transmittance of the sample to visible ray according to each wave band distribution character of sunlight that GBT2680-1994 is announced.
Table 1
Piece number Quality(mg) Relative to the absolute value of the bias of meansigma methodss(%)
1 702.041 0.6%
2 718.803 1.8%
3 694.760 1.6%
4 713.819 1.1%
5 692.565 1.9%
6 702.937 0.4%
7 709.609 0.5%
8 702.409 0.5%
9 717.962 1.7%
Mass average value 706.101
The preparation method of the porous polytetrafluoroethylene material is:
(1)By the ptfe emulsion of solid content 60%, particle diameter 50nm shitosans, 9%(Mass ratio)Gelatin solution, 18wt% starch emulsions, uniform mixing, according to 55:30:9:5 mass ratioes, are made into spinning liquid;
(2)Under vacuum, politef precursor film is produced using electrospinning process in orientation electrostatic spinning fiber silk device, under vacuum 110 DEG C of process 20min;
(3)Precursor film is wound into 5 layers to diameter 4-25mm cylinders hold mode, is sent in tube furnace and is sintered in vacuum or protective atmosphere, sintered and sintered using temperature programmed control zonal cooling, with the speed of 8 DEG C/min from room temperature to 170 DEG C, at 170 DEG C 50min is incubated;With the ramp of 8 DEG C/min to 280 DEG C, at 280 DEG C 60min is incubated;With the ramp of 2 DEG C/min to 360 DEG C, at 360 DEG C 15min is incubated;With the ramp of 8 DEG C/min to 400 DEG C, at 400 DEG C 80min is incubated.
(4)Temperature programmed control cooling after sintering, according to routine techniquess subsequent treatment, obtains the porous Teflon Fiber tube type film with two-stage pore structure, and thickness is 176 μm, film diameter 4-25mm.
, without the need for supporting, form stable, thickness is controllable, can be used for gas-liquid separation and Liquid liquid Separation for the polytetrafluoroethylene fibre tubular membrane, realizes that Accurate Classification is filtered, such as it is applied to two-spot or many vigour(Liquid)The filtration of body, its flux is big, and rejection is high, is difficult to be contaminated(Such as the infiltration fouling membrane of multi-component liquid), the advantage with efficient long-acting.169 ° of film water contact angle, light transmittance is 58%, tensile strength 30N/mm2More than, water pressure resistance 5kg/cm2More than.
Such as, in being applied to the Membrane Materials of acid/alcohol-water-non-volatile solute system, total flux can reach 38kg/m2More than h, in system non-volatile solute rejection more than 99.8%, volatilization alcohol/acid separation factor=[alcohol/acid mass fraction in distillate ×(1- material liquids alcohol/acid mass fraction)] ÷ [material liquid alcohol/acid mass fraction ×(1- distillates alcohol/acid mass fraction)] can reach more than 10.
Embodiment 2
The polytetrafluoroethylene fibre tubular membrane of the present invention, with three-level pore structure, wherein, there is the second level vestibule for being uniformly distributed, being mutually communicated in the cavity wall of the first order vestibule be uniformly distributed, being mutually communicated, and the also insertion each other each other of two-stage hole, the insertion is three-dimensional insertion.Every grade of porous material of material body is a continuous structure body certainly.Total effective drainage porosity is 80%, and fibre diameter is 700 ± 20 nm, and macropore average pore size is 1500nm, there is the insertion second hole of average pore size 100nm in the cavity wall of macropore, there is the third level hole of average pore size 10nm insertion on the hole wall in second level hole.
It is machined into method to take up an official post in the porous material said three-dimensional body of the same size for taking 9 10mm × 10mm × 10mm, its quality is tested with prunus mume (sieb.) sieb.et zucc. Teller-support benefit XP26 Microbalance balances, as a result it is as shown in table 1, wherein, intensive reading is expressed as a percentage with the absolute value of the bias of meansigma methodss, its value be relative to meansigma methodss absolute value of the bias divided by mass average value, as shown in Table 2, its mass deviation is not more than 4%.
Table 2
Piece number Quality(mg) Relative to the absolute value of the bias of meansigma methodss(%)
1 557.800 2.3%
2 548.313 0.5%
3 541.019 0.8%
4 539.175 1.1%
5 543.269 0.4%
6 547.043 0.3%
7 542.618 0.5%
8 540.604 0.9%
9 549.056 0.7%
Mass average value 545.433
The preparation method of the porous polytetrafluoroethylene material is:
(1)By PTFE fine powder end, the Polyethylene Glycol mixing that molecular weight is 1000,380 DEG C are heated with stirring to, persistently stir 60min, be quickly cooled to room temperature and crushed, carried out crushing at subzero degree Celsius and obtain polytetrafluoroethylgranule granule;
(2)Particle diameter is distributed as the emulsion of solid content 60% for 200nm polytetrafluoroethylgranule granules, by its with particle diameter 100nm shitosans, 9%(Mass ratio)Chitosan solution, 15wt% starch emulsions, uniform mixing, according to 55:30:9:5 mass ratioes, are made into spinning liquid;
(3)Under vacuum, politef precursor film is produced using electrospinning process in orientation electrostatic spinning fiber silk device, under vacuum 110 DEG C of process 20min;
(4)Precursor film is wound into 5 layers to diameter 4-25mm cylinders hold mode, is sent in tube furnace and is sintered in vacuum or protective atmosphere, sintered and sintered using temperature programmed control zonal cooling, with the speed of 8 DEG C/min from room temperature to 180 DEG C, at 180 DEG C 60min is incubated;With the ramp of 8 DEG C/min to 300 DEG C, at 300 DEG C 60min is incubated;With the ramp of 2 DEG C/min to 360 DEG C, at 360 DEG C 20min is incubated;With the ramp of 8 DEG C/min to 400 DEG C, at 400 DEG C 80min is incubated.
(5)Temperature programmed control cooling after sintering, according to routine techniquess subsequent treatment, obtains the porous Teflon Fiber tube type film with three-level pore structure, and thickness is 180 μm, Fiber tube type film diameter 4-25mm.
, without the need for supporting, form stable, thickness is controllable, can be used for gas-liquid separation and Liquid liquid Separation for the polytetrafluoroethylene fibre tubular membrane, realizes that Accurate Classification is filtered, such as it is applied to two-spot or many vigour(Liquid)The filtration of body, its flux is big, and rejection is high, is difficult to be contaminated(Such as the infiltration fouling membrane of multi-component liquid), the advantage with efficient long-acting.173 ° of film water contact angle, light transmittance is 60%, tensile strength 28N/mm2More than, water pressure resistance 6kg/cm2More than.
Such as, it is applied to polynary(Or mixing)In the Membrane Materials of alcohol/acid-water-non-volatile solute system, total flux can reach 40kg/m2More than h, in system non-volatile solute rejection more than 99.9%, volatilization alcohol/acid separation factor=[alcohol/acid mass fraction in distillate ×(1- material liquids alcohol/acid mass fraction)] ÷ [material liquid alcohol/acid mass fraction ×(1- distillates alcohol/acid mass fraction)] can reach more than 10.

Claims (11)

1. a kind of polytetrafluoroethylene fibre tubular membrane, including polytetrafluoroethylmaterial material body, politef is in threadiness, 200nm < fibre diameters are≤2000nm, the cavity wall that body has the vestibule in 10nm~2000nm apertures and formed around vestibule in three dimensions, its vestibule is in uniform distribution, the three-dimensional insertion of each vestibule, and vestibule refers to each vestibule on the porous material under arbitrary unit level volume in uniform distribution in uniform distribution;Porosity of=75%, light transmittance is more than 50%, tensile strength 28N/mm2More than, water pressure resistance 4kg/cm2More than.
2. polytetrafluoroethylene fibre tubular membrane as claimed in claim 1, vestibule with 200~2000nm apertures and the cavity wall formed around vestibule in three dimensions, subordinate's vestibule of 10~150nm, vestibules at different levels each three-dimensional insertion and vestibule at different levels also insertion each other each other are set in cavity wall;Vestibule is in uniform distribution, and vestibule refers to each vestibule on the porous material under arbitrary unit level volume in uniform distribution in uniform distribution.
3. polytetrafluoroethylene fibre tubular membrane as claimed in claim 1 or 2, the unit level volume refers to cubic centimetre level or cubic millimeter level or more subsection level volume.
4. the polytetrafluoroethylene fibre tubular membrane as described in claim 1,2 or 3, institute's vestibule is referred in uniform distribution and be not more than each said three-dimensional body of a cubic centimetre and formed objects in the take up an official post volume that takes of the porous material, and their quality is substantially suitable.
5. polytetrafluoroethylene fibre tubular membrane as claimed in claim 4, the quality quite refers to the said three-dimensional body for appointing the multiple volumes for taking to be not more than a cubic centimetre and formed objects on the porous material substantially, claim its quality respectively, the meansigma methodss of their quality are obtained, and arbitrary three-dimensional weight is not more than the 4% of said three-dimensional body mass average value relative to the absolute value of the bias of mass average value.
6. the polytetrafluoroethylene fibre tubular membrane as described in claim 1-5 is arbitrary, the multistage material take up an official post the volume that takes be not more than one cubic millimeter formed objects said three-dimensional body, their quality are substantially suitable.
7. polytetrafluoroethylene fibre tubular membrane as claimed in claim 6, the quality quite refers to the said three-dimensional body of the formed objects for appointing the multiple volumes for taking to be not more than a cubic millimeter on the porous material substantially, claim its quality respectively, the meansigma methodss of their quality are obtained, and arbitrary three-dimensional weight is not more than the 4% of said three-dimensional body mass average value relative to the absolute value of the bias of mass average value.
8. the polytetrafluoroethylene fibre tubular membrane as described in claim 1-7 is arbitrary, it is made up of multistage porous material, body is the vestibule being classified with material pore size, and the cavity wall in three dimensions around vestibule is constituted, subordinate's vestibule, vestibules at different levels each three-dimensional insertion and vestibule at different levels also insertion each other each other are set in cavity wall.
9. the polytetrafluoroethylene fibre tubular membrane as described in claim 1-8 is arbitrary, next stage porous material constitutes the cavity wall of upper level vestibule.
10. the polytetrafluoroethylene fibre tubular membrane as described in claim 1-8 is arbitrary, the cavity wall of higher level's vestibule is constituted by the multistage porous material of its subordinate is compound.
The 11. polytetrafluoroethylene fibre tubular membrane as described in claim 1-8 is arbitrary, the cavity wall of higher level's vestibule is constituted by the porous materials at different levels of its subordinate are compound.
CN201510764582.5A 2015-11-11 2015-11-11 PTFE (Polytetrafluoroethylene) fiber pipe type film Pending CN106669442A (en)

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PCT/CN2016/105258 WO2017080470A1 (en) 2015-11-11 2016-11-09 Polytetrafluoroethylene fiber tubular membranes

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CN109402873A (en) * 2017-08-18 2019-03-01 重庆润泽医药有限公司 A kind of macromolecule semi-permeable material
CN109395600A (en) * 2017-08-18 2019-03-01 重庆润泽医药有限公司 A kind of polytetrafluoroethyltubular tubular membrane and preparation method thereof

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CN103894077A (en) * 2014-04-10 2014-07-02 江南大学 Composite filter membrane with multidimensional pore structure and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN109395598A (en) * 2017-08-18 2019-03-01 重庆润泽医药有限公司 A kind of polytetrafluoroethyltubular tubular membrane and preparation method thereof
CN109402873A (en) * 2017-08-18 2019-03-01 重庆润泽医药有限公司 A kind of macromolecule semi-permeable material
CN109395600A (en) * 2017-08-18 2019-03-01 重庆润泽医药有限公司 A kind of polytetrafluoroethyltubular tubular membrane and preparation method thereof

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Application publication date: 20170517