WO2017080457A1 - Membrane de fibres creuses de polytétrafluoroéthylène - Google Patents

Membrane de fibres creuses de polytétrafluoroéthylène Download PDF

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Publication number
WO2017080457A1
WO2017080457A1 PCT/CN2016/105240 CN2016105240W WO2017080457A1 WO 2017080457 A1 WO2017080457 A1 WO 2017080457A1 CN 2016105240 W CN2016105240 W CN 2016105240W WO 2017080457 A1 WO2017080457 A1 WO 2017080457A1
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WO
WIPO (PCT)
Prior art keywords
cavity
hollow fiber
fiber membrane
mass
polytetrafluoroethylene
Prior art date
Application number
PCT/CN2016/105240
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English (en)
Chinese (zh)
Inventor
叶雷
Original Assignee
重庆润泽医药有限公司
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Publication of WO2017080457A1 publication Critical patent/WO2017080457A1/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 invention is achieved by the following measures:
  • a polytetrafluoroethylene 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 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; the porosity is above 70%.
  • the light transmittance is 50% or more, the tensile strength is 20 N/mm 2 or more, and the water pressure resistance is 4 kg/cm 2 or more.
  • the above polytetrafluoroethylene hollow fiber membrane has a pore diameter of 30 to 1000 nm and is in a three-dimensional space.
  • a lower hole of 10 to 100 nm is disposed on the cavity wall, and each of the holes is three-dimensionally penetrated and the holes of each stage are also mutually connected; the holes are 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 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 holes of each level It is three-dimensionally connected to each other and has good penetration, which can fully meet the functional requirements of materials.
  • 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.
  • Polytetrafluoroethylene film has diffuse reflection phenomenon, polytetrafluoroethylene porous fiber membrane, such as pore distribution, hierarchical structure, porosity, pore shape and other structural characteristics, processes, etc. and transmittance, mechanical strength, water pressure resistance and other films
  • the PTFE hollow fiber membrane of the invention has bright and bright film, bright and smooth luster, no support, stable shape and controllable thickness, and is applied to the membrane distillation process with a flux of >42 L/m 2 ⁇ h, interception The rate is 99.8% or more, the tensile strength can be 32 N/mm 2 or more, and the water pressure resistance is 7 kg/cm 2 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 75%
  • the fiber diameter is 150 ⁇ 20 nm
  • the macroporous average pore diameter is 0.45 ⁇ 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:
  • a polytetrafluoroethylene emulsion having a solid content of 60%, a chitosan having a particle size of 30 nm, a 5% (mass ratio) polyethylene oxide solution, and a 20 wt% starch emulsion are uniformly mixed according to 45:25:3: 3 mass ratio, formulated into a spinning solution;
  • 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 sintering is sequentially sintered by program temperature control, and is heated from room temperature at a rate of 5 ° C/min.
  • Incubate at 160 ° C for 30 min at 180 ° C; heat up to 260 ° C at 5 ° C / min, hold at 260 ° C for 60 min; ramp up to 360 ° C at 2 ° C / min, hold at 360 ° C for 30 min; at 6 ° C /
  • the rate of min is raised to 400 ° C, and kept at 400 ° C for 80 min;
  • the program was temperature-controlled and cooled, and the porous polytetrafluoroethylene hollow fiber membrane having a two-stage pore structure was obtained according to a conventional technique, and the thickness was 165 ⁇ m, and the diameter of the hollow fiber membrane was 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 film water has a contact angle of 168°, a light transmittance of 65%, a tensile strength of 32 N/mm 2 or more, and a water pressure resistance of 5 kg/cm 2 or more.
  • Volatile acid/alcohol separation factor [acid / alcohol mass fraction in distillate ⁇ (1 - raw material acid / alcohol mass fraction)] ⁇ [raw material acid / alcohol mass fraction ⁇ (1- distillate acid / alcohol 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 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 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 sintering is sequentially sintered by program temperature control, and is heated from room temperature at a rate of 5 ° C/min.
  • Incubate at 160 ° C for 30 min at 180 ° C; ramp up to 270 ° C at 5 ° C / min, hold at 270 ° C for 60 min; ramp up to 360 ° C at 2 ° C / min, hold at 360 ° C for 30 min; at 6 ° C /
  • the rate of min is raised to 400 ° C, and kept at 400 ° C for 80 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 162 ⁇ 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 film water had a contact angle of 171°, a light transmittance of 70%, a tensile strength of 29 N/mm 2 , and a water pressure resistance of 7 kg/cm 2 .
  • Acid/alcohol separation factor [acid/alcohol mass fraction in distillate ⁇ (1 - raw material acid / alcohol mass fraction)] ⁇ [raw material acid / alcohol mass fraction ⁇ (1-distillate acid / alcohol 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 de fibres creuses de polytétrafluoroéthylène qui comprend un corps fait d'un matériau de polytétrafluoroéthylène, le matériau de polytétrafluoroéthylène étant fibreux et présentant un diamètre de fibre de 30 à 200 nm. Le corps comporte des cavités de pores présentant un diamètre de pore de 10 nm à 1000 nm, et des parois de cavité formées autour des cavités de pores dans un espace tridimensionnel, les cavités des pores étant réparties de manière uniforme, chacune des cavités de pores étant tridimensionnellement traversante. On entend par cavités de pores réparties de manière uniforme, que les cavités de pores sont réparties uniformément dans le matériau poreux dans un volume d'un quelconque niveau unitaire. La porosité est supérieure ou égale à 70 %, la transmittance est supérieure ou égale à 50 %, la résistance à la traction est supérieure ou égale à 20N/mm2, et la résistance à la pression d'eau est supérieure ou égale à 4 kg/cm2. L'invention propose un procédé de mesure spécifique et défini pour la répartition uniforme des cavités de pores dans la membrane de fibres creuses de polytétrafluoroéthylène, définissant que l'uniformité de la répartition des pores dans le matériau poreux et la structure multiniveau de celle-ci est mesurée à l'échelle d'un volume de petit niveau unitaire. Une telle structure poreuse est très uniforme, ce qui garantit l'uniformité et la régularité des performances du matériau poreux.
PCT/CN2016/105240 2015-11-11 2016-11-09 Membrane de fibres creuses de polytétrafluoroéthylène WO2017080457A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510764577.4 2015-11-11
CN201510764577.4A CN106669450B (zh) 2015-11-11 2015-11-11 一种聚四氟乙烯超细中空纤维膜

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WO2017080457A1 true WO2017080457A1 (fr) 2017-05-18

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN115845635A (zh) * 2023-02-02 2023-03-28 山东东岳高分子材料有限公司 一种聚四氟乙烯中空纤维膜及其制备方法

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* Cited by examiner, † Cited by third party
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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
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
CN109395604A (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
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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CN101961608A (zh) * 2010-10-12 2011-02-02 浙江理工大学 一种聚四氟乙烯中空纤维膜的孔径控制方法
CN102266725A (zh) * 2011-06-09 2011-12-07 浙江东大环境工程有限公司 一种聚四氟乙烯中空纤维膜及其制备方法
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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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Publication number Priority date Publication date Assignee Title
CN101961608A (zh) * 2010-10-12 2011-02-02 浙江理工大学 一种聚四氟乙烯中空纤维膜的孔径控制方法
CN102266725A (zh) * 2011-06-09 2011-12-07 浙江东大环境工程有限公司 一种聚四氟乙烯中空纤维膜及其制备方法
KR20130109730A (ko) * 2012-03-28 2013-10-08 웅진케미칼 주식회사 다공성 ｐｔｆｅ 중공사 분리막
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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115845635A (zh) * 2023-02-02 2023-03-28 山东东岳高分子材料有限公司 一种聚四氟乙烯中空纤维膜及其制备方法
CN115845635B (zh) * 2023-02-02 2023-07-18 山东东岳高分子材料有限公司 一种聚四氟乙烯中空纤维膜及其制备方法

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CN106669450A (zh) 2017-05-17

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