WO2017080417A1 - Membrane à fibres creuses super-fines de polytétrafluoroéthylène - Google Patents

Membrane à fibres creuses super-fines de polytétrafluoroéthylène Download PDF

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Publication number
WO2017080417A1
WO2017080417A1 PCT/CN2016/104854 CN2016104854W WO2017080417A1 WO 2017080417 A1 WO2017080417 A1 WO 2017080417A1 CN 2016104854 W CN2016104854 W CN 2016104854W WO 2017080417 A1 WO2017080417 A1 WO 2017080417A1
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WO
WIPO (PCT)
Prior art keywords
cavity
hollow fiber
mass
fiber membrane
polytetrafluoroethylene
Prior art date
Application number
PCT/CN2016/104854
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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 WO2017080417A1 publication Critical patent/WO2017080417A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • 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

Definitions

  • the present invention relates to a porous material, in particular to a polytetrafluoroethylene hollow fiber membrane.
  • 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 hollow fiber membrane which is structurally suitable, controllable and highly uniform.
  • the object of the invention is achieved by the following measures:
  • a polytetrafluoroethylene ultrafine hollow 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 surrounding the hole
  • the cavity wall formed by the cavity is formed, the pore cavity is uniformly distributed, and each cavity is three-dimensionally penetrated, and the uniformity distribution of the cavity means that the cavity is uniformly distributed under arbitrary unit volume on the porous material; porosity ⁇ 70%.
  • the polytetrafluoroethylene hollow fiber membrane has a pore cavity with a pore diameter of 30 to 1000 nm and a cavity wall formed around the pore cavity in a three-dimensional space, and a lower cavity of 10 to 100 nm is disposed on the cavity wall, and each cavity of each cavity has a respective cavity.
  • Three-dimensional and each The stages of the cavities are also mutually connected; the cavities are uniformly distributed, and the uniformity of the cavities means that the cavities are uniformly distributed at any 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 hollow 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,
  • Each of the cavities of each stage is three-dimensionally penetrated and the cavities of the respective 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 hollow 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 hollow fiber membrane, and clarifies the pore distribution uniformity of the porous material and its multi-stage structure on the scale of the small unit volume.
  • Such a porous structure is highly uniform, thereby ensuring uniformity of properties of the porous material.
  • the polytetrafluoroethylene hollow fiber membrane of the present invention is three-dimensionally penetrated, including three-dimensional communication of each stage of the hole, and the three-holes of each level are mutually penetrated, and the penetration is good, and the functional requirements of the material can be fully satisfied.
  • the polytetrafluoroethylene hollow 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 hollow fiber membrane of the invention does not need support, has stable shape and controllable thickness, and is applied to a membrane distillation process with a flux of >42 L/m 2 ⁇ h and a rejection of 99.8% or more.
  • the polytetrafluoroethylene hollow 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 interpenetrating, and two stages The holes also penetrate 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 80%
  • the fiber diameter is 150 ⁇ 20 nm
  • the macroporous average pore diameter is 0.45 ⁇ m
  • the preparation method of the polytetrafluoroethylene porous material is:
  • a polytetrafluoroethylene emulsion having a solid content of 60%, a chitosan having a particle size of 30 nm, and a 5% (mass ratio) polyvinyl alcohol solution are uniformly mixed, and a spinning solution is prepared in a mass ratio of 50:30:4. ;
  • the precursor film is wound into 5 layers on a cylindrical support mold, sent to a tube furnace for sintering in a vacuum or a protective atmosphere, and the sintering is sequentially sintered by program temperature control, and is heated from room temperature at a rate of 4 ° C/min.
  • the temperature was raised to 180 ° C for 60 min at 180 ° C; the temperature was raised to 250 ° C at a rate of 4 ° C / min, held at 250 ° C for 60 min; the temperature was raised to 400 ° C at a rate of 4 ° C / min, and held at 400 ° C for 60 min.
  • the program is temperature-controlled and cooled, and a porous polytetrafluoroethylene hollow fiber membrane having a two-stage pore structure is obtained according to a conventional technique, and has a thickness of 156 ⁇ m and a fiber membrane diameter of less than 3 mm.
  • the PTFE hollow fiber membrane does not need support, 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 165°.
  • 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 hollow 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 two stages The holes also penetrate 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 on a cylindrical support mold, sent to a tube furnace for sintering in a vacuum or a protective atmosphere, and the sintering is sequentially sintered by program temperature control, and is heated from room temperature at a rate of 6 ° C/min.
  • the temperature was raised to 160 ° C, heated at 160 ° C for 100 min; the temperature was raised from room temperature to 280 ° C at a rate of 6 ° C / min, held at 280 ° C for 60 min; the temperature was raised to 400 ° C at a rate of 6 ° C / min, and incubated at 400 ° C for 100 min.
  • the program is temperature-controlled and cooled, and a porous polytetrafluoroethylene hollow film having a three-stage pore structure is obtained according to a conventional technique, and has a thickness of 160 ⁇ m and a hollow fiber membrane diameter of less than 3 mm.
  • the PTFE hollow fiber membrane does not need support, 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 168°.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne une membrane à fibres creuses super-fines de polytétrafluoroéthylène comprenant un corps d'un matériau de polytétrafluoroéthylène, le matériau de polytétrafluoroéthylène étant fibreux avec un diamètre de fibre de 30 à 200 nm, le corps comprenant des cavités de pore présentant un diamètre de pore de 10 nm à 1000 nm et des parois de cavité formées autour des cavités de pore dans un espace en trois dimensions, les cavités de pore étant réparties uniformément avec une porosité égale ou supérieure à 70%.
PCT/CN2016/104854 2015-11-11 2016-11-07 Membrane à fibres creuses super-fines de polytétrafluoroéthylène WO2017080417A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510767128.5A CN106669464A (zh) 2015-11-11 2015-11-11 一种聚四氟乙烯超细中空纤维膜
CN201510767128.5 2015-11-11

Publications (1)

Publication Number Publication Date
WO2017080417A1 true WO2017080417A1 (fr) 2017-05-18

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Citations (5)

* 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
CN101543734A (zh) * 2008-11-21 2009-09-30 任正善 一种聚四氟乙烯纳米纤维膜及制备方法
CN102151493A (zh) * 2011-03-18 2011-08-17 上腾新材料科技（苏州）有限公司 一种纳米级聚四氟乙烯微孔膜的制备方法
WO2013005430A1 (fr) * 2011-07-05 2013-01-10 日東電工株式会社 Film poreux de polytétrafluoroéthylène et matériau filtrant pour filtre à air
CN103191653A (zh) * 2012-01-10 2013-07-10 杭州科百特过滤器材有限公司 一种形成非对称聚四氟乙烯多孔膜的方法

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Publication number Priority date Publication date Assignee Title
US5476589A (en) * 1995-03-10 1995-12-19 W. L. Gore & Associates, Inc. Porpous PTFE film and a manufacturing method therefor
CN102351563B (zh) * 2011-07-06 2013-04-24 武汉理工大学 具有多级孔径结构的高孔隙率氮化硅多孔陶瓷的制备方法
CN102701778B (zh) * 2012-06-01 2013-10-16 清华大学 一种多级孔结构陶瓷膜的制备方法
CN107670514B (zh) * 2014-03-13 2020-02-07 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
CN103894077B (zh) * 2014-04-10 2016-02-24 江南大学 一种多维度孔隙结构复合过滤膜及其制备方法
CN104529505A (zh) * 2014-12-24 2015-04-22 东北大学 一种定向多级孔过滤器及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101543734A (zh) * 2008-11-21 2009-09-30 任正善 一种聚四氟乙烯纳米纤维膜及制备方法
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
CN102151493A (zh) * 2011-03-18 2011-08-17 上腾新材料科技（苏州）有限公司 一种纳米级聚四氟乙烯微孔膜的制备方法
WO2013005430A1 (fr) * 2011-07-05 2013-01-10 日東電工株式会社 Film poreux de polytétrafluoroéthylène et matériau filtrant pour filtre à air
CN103191653A (zh) * 2012-01-10 2013-07-10 杭州科百特过滤器材有限公司 一种形成非对称聚四氟乙烯多孔膜的方法

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