WO2017080465A1 - Membrane tubulaire à fibres ultra-fines de polytétrafluoroéthylène - Google Patents

Membrane tubulaire à fibres ultra-fines de polytétrafluoroéthylène Download PDF

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Publication number
WO2017080465A1
WO2017080465A1 PCT/CN2016/105253 CN2016105253W WO2017080465A1 WO 2017080465 A1 WO2017080465 A1 WO 2017080465A1 CN 2016105253 W CN2016105253 W CN 2016105253W WO 2017080465 A1 WO2017080465 A1 WO 2017080465A1
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WO
WIPO (PCT)
Prior art keywords
cavity
mass
tubular membrane
polytetrafluoroethylene
fiber tubular
Prior art date
Application number
PCT/CN2016/105253
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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 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 WO2017080465A1 publication Critical patent/WO2017080465A1/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
    • B01D69/04—Tubular 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 fiber tubular 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 fiber tubular membrane which is structurally suitable, controllable and highly uniform.
  • the object of the invention is achieved by the following measures:
  • a polytetrafluoroethylene fiber tubular membrane comprising a body of polytetrafluoroethylene material, a polytetrafluoroethylene fiber, a fiber diameter of 30-200 nm, a body having a pore size of 10 nm to 1000 nm, and a three-dimensional space surrounding the cavity
  • the cavity wall is formed with uniform distribution, 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 transmittance is 45% or more.
  • the polytetrafluoroethylene fiber tubular 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 pore cavity of 10 to 100 nm is disposed on the cavity wall, and each cavity of each cavity is provided.
  • Each three-dimensionally 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 fiber tubular 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.
  • the cavities of each stage are each three-dimensionally penetrated and the cavities of the respective stages are also mutually connected.
  • 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 tubular 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 tubular membrane, and it is clarified that the pores of the porous material and the multi-stage structure are uniformly distributed on the scale of the small unit volume. Sexually, such a porous structure is highly uniform, thereby ensuring uniformity of the properties of the porous material.
  • the polytetrafluoroethylene fiber tubular membrane of the present invention is three-dimensionally penetrated, including three-dimensional communication of each level of pores, and three-dimensional through-holes of each level, and good penetration, and can fully meet the functional requirements of the material.
  • the polytetrafluoroethylene fiber tubular film 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 Tubular film, 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 tubular 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 penetrated, and two The stepped 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 0.40 ⁇ 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:
  • a polytetrafluoroethylene emulsion having a solid content of 65%, a chitosan having a particle size of 30 nm, and a 7% (mass ratio) polyvinyl alcohol solution are uniformly mixed, and a spinning solution is prepared according to a mass ratio of 45:25:3. ;
  • the precursor film obtained in the step (2) is wound up to 5 layers to a cylindrical support mold of 4-25 mm in diameter, sent to a tube furnace for sintering in a vacuum or a protective atmosphere, and the sintering is sequentially sintered by a program temperature control section to The temperature of 3 ° C / min 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 Incubate at 400 ° C for 60 min.
  • the program is controlled by temperature and cooled, and according to the conventional technology, a porous polytetrafluoroethylene fiber tubular membrane having a two-stage pore structure is obtained, the thickness is 158 ⁇ m, the tubular membrane diameter is 4-25 mm, and the light transmittance is 60. %.
  • the PTFE fiber tubular 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 filtration 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 multi-liquid immersion membrane pollution), 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 tubular membrane of the present 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 The stepped 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 to a cylinder support mold of 4-25 mm in diameter, and sent to a tube furnace for sintering in a vacuum or a protective atmosphere.
  • the sintering is sequentially sintered by a program controlled temperature section at 3 ° C/min. The temperature was raised from room temperature to 200 ° C, held at 200 ° C for 60 min; heated to 310 ° C at a rate of 3 ° C / min, held at 310 ° C for 40 min; heated to 400 ° C at a rate of 3 ° C / min, and incubated at 400 ° C for 60 min.
  • the program is temperature-controlled and cooled, and the porous polytetrafluoroethylene fiber tubular membrane having a three-stage pore structure is obtained according to a conventional technique, and has a thickness of 160 ⁇ m and a tubular membrane diameter of 4-25 mm.
  • the PTFE fiber tubular 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 filtration 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 multi-liquid immersion membrane pollution), 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

  • 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)

Abstract

L'invention concerne une membrane tubulaire à fibres de polytétrafluoroéthylène, comprenant un corps de matériau en polytétrafluoroéthylène ; le polytétrafluoroéthylène présente une forme de fibre et la fibre a un diamètre de 30 à 200 nm ; le corps présente des cavités de pores d'un diamètre de pore de 10 à 1 000 nm et des parois de cavités formées par des espaces tridimensionnels entourant les cavités de pores ; les cavités de pores sont réparties uniformément et chaque cavité de pore est ouverte de façon tridimensionnelle ; le fait que les cavités de pores sont réparties uniformément signifie que les cavités de pores sont réparties uniformément sur n'importe quel volume unitaire sur le matériau poreux ; la porosité est supérieure ou égale à 65 %, et la transmittance de la lumière est supérieure ou égale à 45 %.
PCT/CN2016/105253 2015-11-11 2016-11-09 Membrane tubulaire à fibres ultra-fines de polytétrafluoroéthylène WO2017080465A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510767112.4 2015-11-11
CN201510767112.4A CN106669460B (zh) 2015-11-11 2015-11-11 一种聚四氟乙烯超细纤维管式膜

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4043331A (en) * 1974-08-05 1977-08-23 Imperial Chemical Industries Limited Fibrillar product of electrostatically spun organic material
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
CN103212308A (zh) * 2012-08-01 2013-07-24 上海市凌桥环保设备厂有限公司 一种净化pm2.5的聚四氟乙烯微孔膜
CN105013344A (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

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4043331A (en) * 1974-08-05 1977-08-23 Imperial Chemical Industries Limited Fibrillar product of electrostatically spun organic material
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
CN103212308A (zh) * 2012-08-01 2013-07-24 上海市凌桥环保设备厂有限公司 一种净化pm2.5的聚四氟乙烯微孔膜
CN105013344A (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

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CN106669460A (zh) 2017-05-17

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