KR20130105072A - Manufacturing method of ptfe hollow fiber membrane having porosity - Google Patents

Manufacturing method of ptfe hollow fiber membrane having porosity Download PDF

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KR20130105072A
KR20130105072A KR1020120027198A KR20120027198A KR20130105072A KR 20130105072 A KR20130105072 A KR 20130105072A KR 1020120027198 A KR1020120027198 A KR 1020120027198A KR 20120027198 A KR20120027198 A KR 20120027198A KR 20130105072 A KR20130105072 A KR 20130105072A
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hollow fiber
porous ptfe
fiber membrane
ptfe hollow
ptfe
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KR1020120027198A
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Korean (ko)
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지성대
허현철
양형모
정경학
이세민
한만재
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웅진케미칼 주식회사
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Priority to KR1020120027198A priority Critical patent/KR20130105072A/en
Publication of KR20130105072A publication Critical patent/KR20130105072A/en

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    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
    • D01F6/12—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polymers of fluorinated hydrocarbons
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength

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

Abstract

PTFE hollow fiber separator prepared by the method of manufacturing a PTFE hollow fiber separator of the present invention can be uniformly coated on the coating layer while maximizing the separation through the coating layer.

Description

Manufacturing Method of PTFE Hollow Fiber Membrane with Increased Resolution {Manufacturing method of PTFE hollow fiber membrane having porosity}

The present invention relates to a method for producing a porous PTFE hollow fiber membrane with increased separation ability, and more particularly, to a method for manufacturing a porous PTFE hollow fiber membrane capable of stably forming a coating layer capable of improving the separation performance on a membrane surface. It is.

Conventionally, a porous body made of polytetrafluoroethylene (hereinafter referred to as "PTFE ") not only has excellent chemical resistance, heat resistance, weather resistance, and nonflammability but also has properties such as non-stickiness and low friction coefficient. Moreover, since it is a porous structure, it is also excellent in transparency, flexibility, flexibility, trapping and filtering of fine particles, and the like. Therefore, the material made of PTFE is used in a wide range of fields such as filtration of fine chemicals and filters for wastewater treatment.

Among them, the PTFE filter medium mainly consists of a paste composed of a mixture of PTFE fine powder and a lubricant, which is rolled through a rolling process between the two rollers, formed into a sheet state, and after the lubricant is removed, Technology, that is, a method for producing a PTFE flat membrane, is well known.

Specifically, Japanese Patent Laid-Open Publication Nos. 1980-075433, 1985-104319 and 1991-017136 have been modified to control the pore size of the PTFE porous body in the PTFE porous body manufacturing method. will be. In addition, Japanese Patent Publication Nos. 1991-174452, 1996-174738, 1991-174452, 1995-278331, 2003-080590, 2007-077323 and 2008-119662 are PTFE porous. The sieve method was improved to control pore size and porosity. The PTFE porous body produced by the stretching of PTFE disclosed in the above patent documents has a microstructure composed of a plurality of fine fibrils (fine fibers) and a plurality of nodes (nodules) connected to each other by the fibrils. The microstructure forms a continuous porous porous structure. At this time, the porous PTFE porous body can arbitrarily set the porous structure such as the pore diameter and porosity by controlling the stretching conditions.

Meanwhile, the hollow fiber membrane is usually formed in the form of a hollow, such as macaroni, which is hollowed in the middle, and is mainly used as a permeable membrane for removing fine impurities. It is classified into a polymer hollow fiber membrane, a ceramic hollow fiber membrane, and a metal hollow fiber membrane .

PTFE hollow fiber membrane can be used as a gas separation membrane, in which case the gas separation membrane should exist as a surface layer free of defects on the surface, but in fact the difficulty and limitations of making the membrane surface free of defects during the extrusion step The situation is occurring, and coating is being done to cover and remove defects on the surface of the membrane. In performing the conventional coating step, most of the coating agent uses poly dimethyl siloxane (PDMS).

However, polydimethylsiloxane, which is used as a coating agent to cover defects on the surface of a conventional gas separation membrane, is toxic due to the presence of a heating zone as a thermosetting type that is cured only when a heat source is applied for a predetermined time or more during the coating step. There was a problem in that one organic solvent was generated, and contaminants were inferior and stability was low, and it was difficult to form a coating layer having a predetermined thickness or more on the surface of the film with low viscosity, and it was difficult to form a uniform coating layer.

The present invention has been made to solve the above-mentioned problems, the problem to be solved by the present invention is to provide a method capable of maintaining the hydrophilicity of the PTFE hollow fiber membranes over time.

Method for producing a porous PTFE hollow fiber membrane of the present invention for solving the above problems (1) preparing a paste by mixing a polytetrafluoroethylene (PTFE) powder and a liquid lubricant; (2) compressing the paste in a compressor to preform the hollow fiber; (3) extruding the preformed hollow fiber in an extruder; (4) heating the extruded hollow fiber to remove a liquid lubricant; And (5) stretching the hollow fiber from which the liquid lubricant is removed to form pores in the hollow fiber; (6) firing the elongated hollow fiber; And (7) coating the calcined hollow fiber in a silicone elastomer coating solution.

According to a preferred embodiment of the present invention, the average particle diameter of the PTFE powder may be 300 ~ 500 ㎛.

According to another preferred embodiment of the present invention, the liquid lubricant may be any one or more selected from the group consisting of liquid paraffin, naphtha, white oil, toluene, xylene, alcohol, ketone and ester.

According to another preferred embodiment of the present invention, the paste may include 10 to 50 parts by weight of the liquid lubricant based on 100 parts by weight of polytetrafluoroethylene (PTFE) powder.

According to another preferred embodiment of the present invention, the step (2) It may be carried out at 18 to 25 ℃ and a pressure of 1 to 3 MPa.

According to another preferred embodiment of the present invention, step (3) may be carried out at a pressure of 60 ~ 85 ℃ and 15 ~ 25MPa.

According to another preferred embodiment of the present invention, the PTFE hollow fiber after the step (3) may be an outer diameter of 1.5 ~ 5mm, the inner diameter of 0.5 ~ 4mm.

According to another preferred embodiment of the present invention, the heating temperature of step (4) may be 120 ~ 130 ℃.

According to another preferred embodiment of the present invention, the firing temperature of step (6) may be 300 ~ 400 ℃.

According to another preferred embodiment of the present invention, the coating liquid of step (7) may include 1 to 10 parts by weight of the two-component silicone elastomer and 1 to 10 parts by weight of the one-component silicone with respect to 100 parts by weight of the solvent.

According to another preferred embodiment of the present invention, the porosity of the porous PTFE hollow fiber membrane is 60% or more and the tensile strength is 60MPa or more.

PTFE hollow fiber separator prepared by the method of manufacturing a PTFE hollow fiber separator of the present invention can be uniformly coated on the coating layer while maximizing the separation through the coating layer.

1 is a flowchart illustrating a method of manufacturing a PTFE hollow fiber membrane according to an embodiment of the present invention.
2 is a schematic diagram of a compressor that can be used in the present invention.
3 is a schematic diagram of an extruder that can be used in the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described in more detail with reference to the accompanying drawings.

As described above, polydimethylsiloxane, which is used as a coating agent to cover defects on the surface of a membrane in the manufacture of a PTFE hollow fiber separator, has a heating zone as a thermosetting type which is cured when a heat source is applied for a predetermined time or more during the coating step. As a result, toxic organic solvents are generated, resulting in the disadvantages of the generation of pollutants and deterioration of stability, and a low viscosity, making it difficult to form a coating layer of a predetermined thickness or more on the surface of the membrane, as well as the difficulty of forming a uniform coating layer.

Thus, the method for producing a porous PTFE hollow fiber membrane of the present invention comprises the steps of: (1) preparing a paste by mixing a polytetrafluoroethylene (PTFE) powder and a liquid lubricant; (2) compressing the paste in a compressor to preform the hollow fiber; (3) extruding the preformed hollow fiber in an extruder; (4) heating the extruded hollow fiber to remove a liquid lubricant; And (5) stretching the hollow fiber from which the liquid lubricant is removed to form pores in the hollow fiber; (6) firing the elongated hollow fiber; And (7) immersing the calcined hollow fiber in a silicone elastomer coating liquid to coat the above-mentioned problem. Through this, the coating layer can be uniformly coated while maximizing resolution.

FIG. 1 is a flow chart showing a method of manufacturing a PTFE hollow fiber membrane according to a preferred embodiment of the present invention, and a method of manufacturing the PTFE hollow fiber membrane of the present invention will be described with reference to FIG.

First, polytetrafluoroethylene (PTFE) powder and a liquid lubricant are mixed as a step (1) to prepare a paste (S1). The PTFE powder contained in the paste of the present invention can be used without limitation as long as it is usually used in a PTFE hollow fiber membrane. Preferably, the PTFE powder may have an average particle size of 300 to 500 탆, but is not limited thereto. The molecular weight and the like are not particularly limited, and commercially available products may be used. Examples thereof include Polyflon F-104 (Daikin Industries) and Fluon CD-123 (Asahi ICI Fluoropolymers Co., Ltd.).

The liquid lubricant included in the paste of the present invention is for performing smooth extrusion and preform formation while wetting the surface of the PTFE fine powder and is not particularly limited as long as it is a material that can be removed by means such as evaporation extraction by heat after forming into a hollow fiber . For example, as the liquid lubricant, various alcohols, ketones, esters, and the like may be used in addition to hydrocarbon oils such as liquid paraffin, naphtha, white oil, toluene, and xylene.

The liquid lubricant included in the paste of the present invention is for performing smooth extrusion and preform formation while wetting the surface of the PTFE fine powder and is not particularly limited as long as it is a material that can be removed by means such as evaporation extraction by heat after forming into a hollow fiber . For example, as the liquid lubricant, various alcohols, ketones, esters, and the like may be used in addition to hydrocarbon oils such as liquid paraffin, naphtha, white oil, toluene, and xylene. According to a preferred embodiment of the present invention, the paste may include 10 to 50 parts by weight of a liquid lubricant based on 100 parts by weight of polytetrafluoroethylene (PTFE) powder.

Next, in step (2), the paste is compressed in a compressor and preformed into a hollow fiber form (S2). Specifically, the compressor that can be used in the present invention can be used without limitation as long as it is usually used for forming a polymer hollow fiber membrane. FIG. 2 is a schematic view of a compressor that can be used in the present invention. When the paste produced in the step (1) is introduced into the compressor 20 for producing a hollow fiber membrane, the external space 22 of the hollow forming part 21 flows At this time, heat and pressure can be applied to preform the paste into a hollow fiber. The cross-sectional shape of the hollow forming portion 21 may be circular, and the diameter may be adjusted according to the hollow size of the desired hollow fiber.

On the other hand, the oxazoline molecules in the paste in the above process has a high molecular weight, so that when the paste solidifies, it is impregnated in the PTFE, and is fixed to the outside when pores are formed. As a result, oxazoline is exposed on the surface of the membrane, which greatly affects the fouling resistance of the membrane.

On the other hand, the temperature and pressure inside the compressor can be set according to the condition of the compressor applied when manufacturing a conventional PTFE hollow fiber membrane, preferably at a temperature of 18 to 25 ° C and a pressure of 1 to 3 MPa.

Next, the preformed hollow fiber is extruded in an extruder as a step (3) (S3). Specifically, the extruder that can be used in the present invention can be used without limitation as long as it is typically used for the film formation of the polymer hollow fiber membrane. Figure 3 is a schematic diagram of an extruder that can be used in the present invention, the hollow fiber 31 pre-formed through the step (2) is a hollow yarn in a state in which the hollow is inserted into the hollow portion 31 inside the extruder (30) The extrusion process may proceed while being transferred. In this case, the extrusion conditions may be carried out under the conditions of the extrusion process of the conventional PTFE hollow fiber membrane, preferably step (3) may be carried out at a pressure of 15 ~ 25MPa at 60 ~ 85 ℃. Meanwhile, the PTFE hollow fiber having been subjected to the step (3) may have an outer diameter of 1.5 to 5 mm and an inner diameter of 0.5 to 4 mm.

Next, in step (4), the extruded hollow fiber is heated to remove the liquid lubricant (S4). Specifically, the heating temperature of the hollow fiber is sufficient if the temperature of the liquid lubricant is removed, but preferably may be 120 ~ 130 ℃. The heating time can be performed for 10 seconds to 10 minutes.

In the next step (5), the hollow fiber having the liquid lubricant removed is stretched to form pores in the hollow fiber (S5). Specifically, a conventional PTFE hollow fiber is fed through a roller. In this case, the PTFE hollow fiber can be stretched in the longitudinal direction by using the speed difference between the rollers, but not limited thereto. The PTFE hollow fiber can be stretched according to a stretching method used in ordinary hollow fiber production. The stretching temperature may also be 250 to 320 ° C, but is not limited thereto, and the stretching ratio may be stretched by 1.2 to 8 times. After the stretching process, pores are formed by forming fibrils and nodes inside the hollow fiber.

Next, in step (6), the stretched PTFE hollow fiber membrane is sintered to prevent heat shrinkage (S6). The firing temperature in the step (6) may be performed at 300 to 400 ° C for 10 seconds to 10 minutes.

Next, by immersing the fired PTFE hollow fiber membrane in step (7) in the silicone elastomer coating liquid to coat the surface of the membrane (S7). As described above, in the case of coating the polydimethylsiloxane to increase the conventional resolution, the presence of the heating zone not only increases the amount of pollutants, but also has a low viscosity, making it difficult to form a uniform coating layer. Thus, in the present invention, the fired PTFE hollow fiber separator was immersed in the silicone elastomer coating solution to solve the above problem. The silicone elastomer that can be used at this time may be a two-part type, in which case it may be further added to the thermosetting two-component silicone in order to reduce the heating zone. The solvent may be used without limitation as long as it can carry out the coating process and hexane may be used in the present invention. When the thermosetting two-component silicone is further added, it may include 1 to 10 parts by weight of the two-component silicone elastomer and 1 to 10 parts by weight of the one-component silicone with respect to 100 parts by weight of hexane. When the composition of the two-component silicone elastomer is large, it is difficult to form a coating layer having a predetermined thickness or more when coating the film surface due to the formation of a low viscosity, and the stability is lowered. Due to the formation of viscosity, the surface of the membrane becomes too sticky and thus weakens the adhesive force with the adhesive used in the module work, thereby increasing the likelihood of leakage in the adhesive portion, and the two-component silicone elastomer and room temperature curing agent. It is most preferable to apply the liquid silicone at the same compounding ratio. The application of the coating liquid comprising the two-component silicone elastomer and the one-component silicone for curing at room temperature can easily form the thickness of the coating layer to 1.00 μm or more, as well as to form the coating layer uniformly by forming an appropriate viscosity. It can be expected to improve the resolution of the separation membrane.

After the coating layer is formed on the surface of the film, the coating layer may be cured by heat treatment at a temperature of 50 ° C. to 80 ° C. for 1 hour to 2 hours 30 minutes.

The porous PTFE hollow fiber separator of the present invention prepared by the above-described method may be an inner diameter of 500 ~ 1200㎛ and an outer diameter of 1800 ~ 2500㎛. The porosity is 60% or more and the tensile strength is 60 MPa or more. Silicone elastomer is coated on the surface of the membrane. As a result, the coating layer is uniformly formed, but the resolution is increased.

Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to Examples and Comparative Examples. However, this embodiment is only an example for explaining the present invention more specifically, the scope of the present invention is not limited to these examples.

<Examples>

20 parts by weight of liquid paraffin (Exopon Mobil, product name: Isopar-H) as a liquid lubricant was mixed with 100 parts by weight of a PTFE fine powder having an average diameter of 500 탆 (DF-130, Solvay) to form a PTFE paste. The PTFE paste was compressed at 20 ° C. at 3 MPa pressure to form a pre-form in the form of a hollow fiber, and was extrusion molded into an outer diameter of 3 mm and an inner diameter of 1 mm at a hollow shape of 80 ° C. at a pressure of 20 MPa (200 kg / cm 2). The PTFE hollow fiber formed was heated at 120 ° C. for 5 minutes to remove liquid paraffin. Subsequently, the molded PTFE hollow fiber separator was stretched 1.5 times in the longitudinal direction at 320 ° C. by the speed difference between rollers to form nodes and fibrils to form pores, and then fired at 350 ° C. Thereafter, the fired hollow fiber was immersed in a coating solution in which 2 parts by weight of a two-component silicone elastomer and 2 parts by weight of a one-component silicone were mixed with respect to 100 parts by weight of hexane to form a coating layer, and then cured at 80 ° C. for 3 hours. At an operating pressure of 5 kgf / cm 3, the permeation (cc / min) was 195 and the oxygen concentration (%) was 33.9%.

<Comparative Example>

A porous PTFE hollow fiber separator was prepared in the same manner as in Example 1 except that a coating solution including 5 parts by weight of polydimethylsiloxane was used based on 100 parts by weight of hexane. At an operating pressure of 5 kgf / cm 3, the permeation (cc / min) was 452 and the oxygen concentration (%) was 28.3%.

PTFE hollow fiber membrane prepared by the manufacturing method of the present invention can be widely used in the field of gas separation membrane because of the excellent resolution.

Claims (14)

(1) preparing a paste by mixing polytetrafluoroethylene (PTFE) powder and liquid lubricant;
(2) compressing the paste in a compressor to preform the hollow fiber;
(3) extruding the preformed hollow fiber in an extruder;
(4) heating the extruded hollow fiber to remove a liquid lubricant; And
(5) stretching the hollow fiber from which the liquid lubricant is removed to form pores in the hollow fiber;
(6) firing the elongated hollow fiber; And
(7) dipping the calcined hollow fiber in a silicone elastomer coating liquid to coat; The method of claim 1,
The average particle diameter of the PTFE powder is a method of manufacturing a porous PTFE hollow fiber membrane with increased resolution, characterized in that 300 ~ 500 ㎛. The method of claim 1,
The liquid lubricant is a liquid paraffin, naphtha, white oil, toluene, xylene, alcohol, ketones and esters, any one or more selected from the group consisting of esters, characterized in that the separation of porous PTFE hollow fiber membrane with increased resolution. The method of claim 1,
The paste is a method for producing a porous PTFE hollow fiber membrane with increased resolution, characterized in that 10 to 50 parts by weight of a liquid lubricant with respect to 100 parts by weight of polytetrafluoroethylene (PTFE) powder. The method of claim 1,
The step (2) is a method for producing a porous PTFE hollow fiber membrane with increased resolution, characterized in that carried out at a pressure of 18 ~ 25 ℃ and 1 ~ 3MPa. The method of claim 1,
The step (3) is a method for producing a porous PTFE hollow fiber membrane with increased resolution, characterized in that carried out at a pressure of 60 ~ 85 ℃ and 15 ~ 25MPa. The method of claim 1,
PTFE hollow fiber after the step (3) has an outer diameter of 1.5 ~ 5mm, the inner diameter of 0.5 ~ 4mm, a method for producing a porous PTFE hollow fiber membrane with increased separation, characterized in that 0.5 ~ 4mm. The method of claim 1,
The heating temperature of the step (4) is a method for producing a porous PTFE hollow fiber membrane with increased resolution, characterized in that 120 ~ 130 ℃. The method of claim 1,
The stretching temperature of the step (5) is 250 ~ 320 ℃ characterized in that the porous PTFE hollow fiber separator with increased resolution, characterized in that the hollow fiber membrane. The method of claim 1,
The firing temperature of the step (6) is a method of manufacturing a porous PTFE hollow fiber membrane with increased resolution, characterized in that 300 ~ 400 ℃. The method of claim 1,
The coating solution of step (7) is prepared from a porous PTFE hollow fiber separator having increased resolution, characterized in that it comprises 1 to 10 parts by weight of two-component silicone elastomer and 1 to 10 parts by weight of one-component silicone with respect to 100 parts by weight of the nucleic acid solvent. Way. A porous PTFE hollow fiber separator prepared by the method of any one of claims 1 to 11. Porous PTFE hollow fiber membrane coated with silicone elastomer on the surface of membrane. The method of claim 13,
The porous PTFE hollow fiber separator is characterized in that the porosity of the porous PTFE hollow fiber membrane is 60% or more and the tensile strength of 60MPa or more.
KR1020120027198A 2012-03-16 2012-03-16 Manufacturing method of ptfe hollow fiber membrane having porosity KR20130105072A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108579432A (en) * 2018-05-21 2018-09-28 宁波通冠电气自动化设备有限公司 A kind of preparation method, filter core and the filtration system of the reverse osmosis PTFE film of ultrafiltration micropore
CN109627652A (en) * 2018-12-26 2019-04-16 江苏金由新材料有限公司 A kind of preparation process of PTFE foamed board

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108579432A (en) * 2018-05-21 2018-09-28 宁波通冠电气自动化设备有限公司 A kind of preparation method, filter core and the filtration system of the reverse osmosis PTFE film of ultrafiltration micropore
CN109627652A (en) * 2018-12-26 2019-04-16 江苏金由新材料有限公司 A kind of preparation process of PTFE foamed board

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