WO2017080476A1 - Film à base de fibres de polytétrafluoroéthylène - Google Patents

Film à base de fibres de polytétrafluoroéthylène Download PDF

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Publication number
WO2017080476A1
WO2017080476A1 PCT/CN2016/105278 CN2016105278W WO2017080476A1 WO 2017080476 A1 WO2017080476 A1 WO 2017080476A1 CN 2016105278 W CN2016105278 W CN 2016105278W WO 2017080476 A1 WO2017080476 A1 WO 2017080476A1
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WO
WIPO (PCT)
Prior art keywords
cavity
mass
porous material
fiber membrane
polytetrafluoroethylene fiber
Prior art date
Application number
PCT/CN2016/105278
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 WO2017080476A1 publication Critical patent/WO2017080476A1/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

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 hollow fiber of suitable structure, controllability and high uniformity.
  • the object of the invention is achieved by the following measures:
  • a polytetrafluoroethylene fiber membrane comprising a body of polytetrafluoroethylene material, a polytetrafluoroethylene fiber, 200 nm ⁇ fiber diameter ⁇ 2000 nm, a body having a pore diameter of 10 nm to 2000 nm and a three-dimensional space surrounding 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; porosity is ⁇ 80%,
  • the tensile strength is 25 N/mm 2 or more, and the water pressure resistance is 4 kg/cm 2 or more.
  • the above polytetrafluoroethylene fiber membrane has a pore diameter of 200 to 2000 nm and a three-dimensional space
  • the cavity wall formed around the cavity is provided with a lower cavity of 10 to 150 nm, and each cavity of each of the holes is three-dimensionally penetrated and the holes of each stage are also mutually connected; the cavity is uniformly distributed, and the cavity is
  • the uniformity distribution means that the pores 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 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 stage of the hole, and the holes of each level Three-dimensional through, good penetration, can fully meet the functional needs of materials.
  • the polytetrafluoroethylene fiber membrane of the present invention is a hydrophobic surface having a multistage roughness structure.
  • the surface water contact angle can reach 165° or more.
  • Polytetrafluoroethylene porous fiber membrane such as pore distribution, hierarchical structure, porosity, pore shape and other structural characteristics, processes and the like are related to mechanical properties such as mechanical strength and water pressure resistance, and the polytetrafluoroethylene fiber membrane of the present invention No support, stable shape, controllable thickness, applied to membrane distillation process, flux >38L/m 2 ⁇ h, rejection rate above 99.8%, tensile strength up to 30N/mm 2 or more, water pressure resistance 5kg/cm 2 the above.
  • 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 80%
  • the fiber diameter is 500 nm ⁇ 20 nm
  • the macroporous average pore diameter is 1000 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 8 ° C/min.
  • Incubate at 170 ° C for 50 min at 170 ° C; ramp up to 280 ° C at 8 ° C / min, hold at 280 ° C for 60 min; ramp to 360 ° C at 2 ° C / min, hold at 360 ° C for 20 min; at 8 ° C /
  • the rate of min was raised to 400 ° C and incubated at 400 ° C for 100 min.
  • 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 film water has a contact angle of 170°, a tensile strength of 30 N/mm 2 , and a water pressure resistance of 5.5 kg/cm 2 .
  • 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 700 ⁇ 20 nm
  • the macropore has an average pore diameter of 1500 nm
  • there are average secondary pores of 100 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 2 mm diameter 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 a rate of 8 ° C / min.
  • the temperature is raised to 170 ° C at room temperature, 50 min at 170 ° C; the temperature is raised to 290 ° C at a rate of 8 ° C / min, held at 290 ° C for 60 min; the temperature is raised to 360 ° C at a rate of 2 ° C / min, and kept at 360 ° C for 20 min;
  • the rate of °C/min was raised to 400 ° C and incubated at 400 ° C for 100 min.
  • the program was temperature-controlled and cooled, and subjected to a subsequent treatment according to a conventional technique to obtain a porous polytetrafluoroethylene fiber membrane having a three-stage pore structure for membrane distillation, having a thickness of 182 ⁇ m and a hollow fiber membrane diameter of 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 film water contact angle was 172°; the tensile strength was 28 N/mm 2 , and the water pressure resistance was 6 kg/cm 2 .
  • 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

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

Abstract

L'invention concerne une membrane à base de fibres de polytétrafluoroéthylène (PTFE) comprenant un corps de matériau en PTFE, le PTFE étant sous la forme de fibres de diamètre > 200 nm et ≤ 2000 nm, le corps étant pourvu d'espaces poreux de diamètre de 10 nm à 2000 nm, et les parois des pores étant formées autour des espaces poreux dans un espace tridimensionnel, les espaces poreux étant uniformément répartis et interconnectés dans les trois dimensions. Les espaces poreux uniformément répartis sont définis dans la présente invention comme chaque espace poreux uniformément réparti dans le matériau poreux dans un volume unitaire arbitraire. La porosité est supérieure ou égale à 80 %, la résistance à la traction est supérieure ou égale à 25 N/mm2 et la résistance à la pression d'eau est supérieure à 4 kg/cm2. L'uniformité de distribution des pores d'un matériau poreux et sa structure multi-niveau sont mesurées à l'échelle d'un petit volume unitaire, assurant ainsi l'uniformité et la régularité de chaque propriété du matériau poreux.
PCT/CN2016/105278 2015-11-11 2016-11-10 Film à base de fibres de polytétrafluoroéthylène WO2017080476A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510764562.8A CN106669444A (zh) 2015-11-11 2015-11-11 一种聚四氟乙烯纤维膜
CN201510764562.8. 2015-11-11

Publications (1)

Publication Number Publication Date
WO2017080476A1 true WO2017080476A1 (fr) 2017-05-18

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN109395596A (zh) * 2017-08-18 2019-03-01 重庆润泽医药有限公司 一种聚四氟乙烯中空纤维膜及其制备方法
CN109395599A (zh) * 2017-08-18 2019-03-01 重庆润泽医药有限公司 一种聚四氟乙烯管式膜及其制备方法
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
CN109395595A (zh) * 2017-08-18 2019-03-01 重庆润泽医药有限公司 一种聚四氟乙烯中空纤维膜及其制备方法
CN109395598A (zh) * 2017-08-18 2019-03-01 重庆润泽医药有限公司 一种聚四氟乙烯管式膜及其制备方法
CN109395606A (zh) * 2017-08-18 2019-03-01 重庆润泽医药有限公司 一种聚四氟乙烯卷式膜及其制备方法

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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
CN102941025A (zh) * 2012-11-20 2013-02-27 浙江理工大学 一种膜蒸馏用聚四氟乙烯中空纤维膜的制备方法
CN104114265A (zh) * 2012-01-27 2014-10-22 宙斯工业产品股份有限公司 电纺丝多孔介质
CN104968422A (zh) * 2013-03-21 2015-10-07 旭化成化学株式会社 多孔性中空纤维膜以及多孔性中空纤维膜的制造方法
CN104998556A (zh) * 2014-04-22 2015-10-28 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

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JP4659241B2 (ja) * 2001-03-19 2011-03-30 ジャパンゴアテックス株式会社 ポリテトラフルオロエチレン膜及びその製造方法
CN107537327B (zh) * 2014-03-13 2020-01-03 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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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
CN104114265A (zh) * 2012-01-27 2014-10-22 宙斯工业产品股份有限公司 电纺丝多孔介质
CN102941025A (zh) * 2012-11-20 2013-02-27 浙江理工大学 一种膜蒸馏用聚四氟乙烯中空纤维膜的制备方法
CN104968422A (zh) * 2013-03-21 2015-10-07 旭化成化学株式会社 多孔性中空纤维膜以及多孔性中空纤维膜的制造方法
CN104998556A (zh) * 2014-04-22 2015-10-28 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

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