WO2017080474A1 - Membrane de fibre ultrafine de polytétrafluoroéthylène - Google Patents

Membrane de fibre ultrafine de polytétrafluoroéthylène Download PDF

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Publication number
WO2017080474A1
WO2017080474A1 PCT/CN2016/105275 CN2016105275W WO2017080474A1 WO 2017080474 A1 WO2017080474 A1 WO 2017080474A1 CN 2016105275 W CN2016105275 W CN 2016105275W WO 2017080474 A1 WO2017080474 A1 WO 2017080474A1
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WO
WIPO (PCT)
Prior art keywords
cavity
mass
fiber membrane
porous material
membrane
Prior art date
Application number
PCT/CN2016/105275
Other languages
English (en)
Chinese (zh)
Inventor
叶雷
Original Assignee
重庆润泽医药有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 重庆润泽医药有限公司 filed Critical 重庆润泽医药有限公司
Publication of WO2017080474A1 publication Critical patent/WO2017080474A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/542—Adhesive fibres

Definitions

  • the present invention relates to a porous material, in particular a polytetrafluoroethylene fiber membrane, which is particularly suitable for membrane distillation.
  • porous material A solid containing a certain number of pores is called a porous material and is a material that forms a network structure by through or closed pores.
  • porous materials Compared with continuous medium materials, porous materials generally have the advantages of low relative density, high specific strength, high specific surface area, light weight, sound insulation, heat insulation and good permeability.
  • the porous material can be divided into microporous (pore size less than 2 nm) material, mesoporous (pore size 2-50 nm) material and macroporous (pore size greater than 50 nm) material.
  • Porous materials are classified according to their materials and can be classified into metal porous materials and non-metallic porous materials.
  • Non-metallic porous materials generally have the characteristics of large specific surface area, small density, small thermal conductivity, small relative density, and high porosity. They are used in catalysts (including carriers), adsorbents, heat preservation, heat insulation, sewage and waste gas treatment, filtration of liquids, and Gas (even bacteria), lightweight building materials, environmental protection, soil improvement, chemical industry and other fields have broad application prospects.
  • the polytetrafluoroethylene porous membrane material has a wide application range due to its temperature stability, chemical stability, electrical insulation, flame retardancy and self-lubricating properties. However, due to the randomness and irregularity of the pore structure, it still cannot satisfy many application properties.
  • the porous material itself needs to be uniform, its pore size and pore distribution are uniform, so that the performance is uniform, but in fact, many porous materials do not meet this requirement, and their uniformity complements; although some materials claim to be self-proclaimed Achieve higher uniformity, but its uniformity is still uniformity on a large volume scale. If it is measured by a small volume scale, for example, if a plurality of three-dimensional bodies having a volume of not more than one cubic centimeter are taken on the material, respectively, The quality, the degree of uniformity is still very large, thus causing various properties of the polytetrafluoroethylene porous membrane material such as strength, elastic modulus, flux and the like, which seriously affect its function.
  • the object of the present invention is to provide a polytetrafluoroethylene fiber membrane which is structurally suitable, controllable and highly uniform.
  • the object of the invention is achieved by the following measures:
  • a polytetrafluoroethylene fiber membrane comprising a body of polytetrafluoroethylene material, a polytetrafluoroethylene fiber, a fiber diameter of 30-200 nm, a body having a pore diameter of 10 nm to 1000 nm, and a three-dimensional space formed around the cavity
  • the cavity wall has a uniform distribution of pores, and each cavity is three-dimensionally penetrated.
  • the uniform distribution of the cavity means that each cavity has a uniform distribution under arbitrary unit volume on the porous material, and the porosity is more than 65%.
  • the light rate is 45% or more.
  • the polytetrafluoroethylene fiber membrane has a cavity having a pore diameter of 30 to 1000 nm and a cavity wall formed in a three-dimensional space around the cavity, and a lower cavity of 10 to 100 nm is disposed on the cavity wall, and each cavity of each cavity is three-dimensionally Through and holes
  • the cavities are also connected to each other; the cavities are uniformly distributed, and the uniformity of the cavities means that the cavities are uniformly distributed under arbitrary unit volume on the porous material.
  • the above unit-level volume means a cubic centimeter-level or cubic millimeter-level or smaller unit-level volume.
  • the uniform distribution of the above-mentioned cavities means that each of the three-dimensional bodies having a volume of not more than one cubic centimeter and the same size on the porous material is substantially equivalent in mass.
  • the above-mentioned mass is substantially equivalent to a plurality of three-dimensional bodies having a volume of not more than one cubic centimeter and the same size, which are respectively referred to as a mass, and an average value of their masses is obtained, and any three-dimensional mass is relatively
  • the absolute value of the deviation from the mass average is not more than 4% of the average of the three-dimensional body mass.
  • the three-dimensional bodies of the same size having a volume of not more than one cubic millimeter on the multi-stage material are substantially equivalent in mass.
  • the mass is substantially equivalent to a plurality of three-dimensional bodies of the same size having a volume of not more than one cubic millimeter on the porous material, respectively referred to as masses, and an average value of their masses is obtained, and any three-dimensional mass is obtained.
  • the absolute value of the deviation from the mass average is not more than 4% of the average of the three-dimensional body mass.
  • the polytetrafluoroethylene fiber membrane is composed of a multi-stage porous material
  • the body is a cavity which is classified by a material pore size, and a cavity wall which surrounds the cavity in a three-dimensional space, and a lower cavity is arranged on the cavity wall, and each The stages of the cavities are each three-dimensionally penetrated and the cavities of the stages are also connected to each other.
  • the next level of porous material constitutes the wall of the cavity of the upper stage.
  • the cavity wall of the upper cavity is composed of a multi-stage porous material of its lower stage or a composite of porous materials of the lower stage, so that the material can meet specific functional requirements.
  • each stage of the porous material of the material body is self-contained as a continuous structure.
  • the maximum outer boundary of each level of porous material is comparable to the entire material body space boundary. That is, each grade of porous material can exist in the bulk as a first-order independent porous material, and has its own physical and chemical properties. Such a structure can make the physical and chemical properties of the porous materials of different levels different, and have different physical and chemical properties in the entire space of the relatively fixed materials, and better meet various functional requirements.
  • the present invention provides a polytetrafluoroethylene fiber membrane having a porous structure, and the structural form thereof is clarified, and the hierarchical structure of the pore cavity and the uniform structure thereof can satisfy various functional requirements.
  • the present invention provides a specific and clear measurement method for the uniform distribution of the pores of the polytetrafluoroethylene fiber membrane, and clarifies that the pore distribution uniformity of the porous material and its multi-stage structure is measured on the scale of the small unit volume.
  • Such a porous structure is highly uniform, thereby ensuring uniformity of the properties of the porous material.
  • the polytetrafluoroethylene fiber membrane of the present invention is three-dimensionally penetrated, including three-dimensional communication of each level of holes, and three-dimensional through-holes of each level, and good penetration, and can fully meet the functional requirements of the material.
  • the polytetrafluoroethylene fiber membrane of the present invention is a hydrophobic surface having a multistage roughness structure.
  • the surface water contact angle can reach 160° or more.
  • the polytetrafluoroethylene film has a diffuse reflection phenomenon, structural characteristics (such as pore shape, pore distribution, hierarchical structure, porosity, etc.), processes, etc. are all related to the transmittance of the film, and the polytetrafluoroethylene fiber of the present invention Membrane, the film color is translucent, the gloss is bright and smooth, no support is needed, the shape is stable, the thickness is controllable, and it is applied to the membrane distillation process, the flux is >42L/m 2 ⁇ h, and the rejection rate is above 99.8%.
  • the polytetrafluoroethylene fiber membrane of the present invention may be a film of different shapes and specifications such as a flat plate type, a tubular type, a hollow fiber type or a roll type, without support, and has a stable shape and a controllable thickness.
  • the polytetrafluoroethylene fiber membrane of the invention has a secondary pore structure, wherein the cavity wall of the first-stage cavity uniformly distributed and interpenetrating has a second-stage cavity uniformly distributed and mutually penetrating, and the two-stage hole The two are also connected to each other, and the through-holes are three-dimensionally penetrated.
  • Each level of porous material of the material body is self-contained as a continuous structure.
  • the total effective porosity is 75%
  • the fiber diameter is 150 ⁇ 20 nm
  • the macroporous average pore diameter is 0.40 ⁇ m
  • the LCD5200 photoelectric characteristic tester was used to scan the 380-780 nm band according to the distribution characteristics of the solar light bands published by GBT2680-1994, and calculate the light transmittance of the sample to visible light.
  • the preparation method of the polytetrafluoroethylene porous material is:
  • the precursor film obtained in the step (2) is wound up to 5 layers on a cylindrical support mold, sent to a tube furnace for sintering in a vacuum or a protective atmosphere, and sintered by program temperature control and continuous sintering at 3 ° C / min.
  • the rate is raised from room temperature to 200 ° C, incubated at 200 ° C for 60 min; at a rate of 3 ° C / min to 300 ° C, at 300 ° C for 40 min; at a rate of 3 ° C / min to 400 ° C, at 400 ° C for 60 min .
  • the program was temperature-controlled and cooled, and after subsequent treatment according to the conventional technique, the cylinder was taken out and cut to obtain a flat porous polytetrafluoroethylene fiber membrane having a two-stage pore structure with a thickness of 160 ⁇ m.
  • the light transmittance is 60%.
  • the PTFE fiber membrane does not need to be supported, has stable shape and controllable thickness, and can be used for gas-liquid separation and liquid-liquid separation to achieve precise grading filtration, for example, it is suitable for filtering of two-component or multi-component gas (liquid) body,
  • the flux is large, the rejection rate is high, and it is not easy to be polluted (such as the contamination of the multi-liquid immersion membrane), and has the advantages of high efficiency and long-term efficiency.
  • the membrane water contact angle is 166°.
  • Volatile alcohol/acid separation factor [alcohol / acid mass fraction in distillate ⁇ (1 - raw material liquid alcohol / acid mass fraction)] ⁇ [raw material liquid alcohol / acid mass fraction ⁇ (1- distillate alcohol / acid mass fraction)] can reach 10 the above.
  • the polytetrafluoroethylene fiber membrane of the invention has a three-stage pore structure, wherein the cavity wall of the first-stage cavity uniformly distributed and interpenetrating has a second-stage cavity uniformly distributed and mutually penetrating, and the two-stage hole The two are also connected to each other, and the through-holes are three-dimensionally penetrated.
  • Each level of porous material of the material body is self-contained as a continuous structure.
  • the total effective porosity is 85%
  • the fiber diameter is 180 ⁇ 20 nm
  • the macropore has an average pore diameter of 1000 nm
  • there are average secondary pores of 60 nm in the cavity wall of the macropores and there is an average on the pore walls of the second-stage pores.
  • a third-stage hole having a pore diameter of 10 nm.
  • the preparation method of the polytetrafluoroethylene porous material is:
  • the precursor film is wound up to 5 layers to a cylindrical support mold of 2 mm in diameter, sent to a tube furnace for sintering in a vacuum or a protective atmosphere, and sintered by program temperature control and continuous sintering at a rate of 3 ° C / min.
  • the temperature was raised from room temperature to 200 ° C, and kept at 200 ° C for 60 min; at a rate of 3 ° C / min to 310 ° C, at 310 ° C for 40 min; at a rate of 3 ° C / min to 400 ° C, at 400 ° C for 60 min.
  • the program was temperature-controlled and cooled, and a porous polytetrafluoroethylene hollow fiber membrane having a three-stage pore structure was obtained according to a conventional technique, and the thickness was 166 ⁇ m, and the membrane diameter was 2 mm.
  • the PTFE fiber membrane does not need to be supported, has stable shape and controllable thickness, and can be used for gas-liquid separation and liquid-liquid separation to achieve precise grading filtration, for example, it is suitable for filtering of two-component or multi-component gas (liquid) body,
  • the flux is large, the rejection rate is high, and it is not easy to be polluted (such as the contamination of the multi-liquid immersion membrane), and has the advantages of high efficiency and long-term efficiency.
  • the membrane water contact angle was 168° and the light transmittance was 68%.
  • Alcohol/acid separation factor [alcohol/acid mass fraction in distillate ⁇ (1 - stock liquid alcohol / acid mass fraction)] ⁇ [feed liquid alcohol / acid mass fraction ⁇ (1-distillate alcohol / acid mass fraction )] can reach more than 10.

Landscapes

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

Abstract

La présente invention concerne une membrane de fibre de polytétrafluoroéthylène, comprenant un corps de matériau de polytétrafluoroéthylène ; le polytétrafluoroéthylène présente une forme de fibre et la fibre a un diamètre de 30 à 200 nm ; le corps comporte des cavités de pore d'un diamètre de pore de 10 à 1000 nm et des parois de cavité formées par des espaces tridimensionnels entourant les cavités de pore ; les cavités de pore sont uniformément distribuées et chaque cavité de pore est ouverte de façon tridimensionnelle ; la porosité est de 65 % ou plus, et la transmittance optique est de 45 % ou plus.
PCT/CN2016/105275 2015-11-11 2016-11-10 Membrane de fibre ultrafine de polytétrafluoroéthylène WO2017080474A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510764579.3A CN106669451B (zh) 2015-11-11 2015-11-11 一种聚四氟乙烯超细纤维膜
CN201510764579.3 2015-11-11

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WO2017080474A1 true WO2017080474A1 (fr) 2017-05-18

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WO (1) WO2017080474A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109395607A (zh) * 2017-08-18 2019-03-01 重庆润泽医药有限公司 一种聚四氟乙烯平板膜及其制备方法
CN109395615A (zh) * 2017-08-18 2019-03-01 重庆润泽医药有限公司 一种聚四氟乙烯平板膜及其制备方法
CN109395610A (zh) * 2017-08-18 2019-03-01 重庆润泽医药有限公司 一种聚四氟乙烯分离材料
CN109402873A (zh) * 2017-08-18 2019-03-01 重庆润泽医药有限公司 一种高分子半透材料

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CN105013350A (zh) * 2014-04-22 2015-11-04 成都百途医药科技有限公司 一种超疏水聚四氟乙烯纤维膜的制备方法
CN105013351A (zh) * 2014-04-22 2015-11-04 成都百途医药科技有限公司 一种聚四氟乙烯超疏水膜的制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101530750A (zh) * 2009-04-20 2009-09-16 浙江理工大学 聚四氟乙烯超细纤维多孔膜的制备方法
JP2013052320A (ja) * 2011-08-31 2013-03-21 Daikin Industries Ltd エアフィルタ用濾材及びエアフィルタユニット
JP2014069115A (ja) * 2012-09-28 2014-04-21 Nippon Valqua Ind Ltd フィルター用ろ材およびその製造方法
CN103785249A (zh) * 2014-01-21 2014-05-14 安徽纳微环保科技有限公司 一种过滤pm2.5颗粒物的微滤膜及其制备方法
CN104906968A (zh) * 2014-03-13 2015-09-16 成都百途医药科技有限公司 一种聚四氟乙烯膜及其制备方法
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CN106669451A (zh) 2017-05-17

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