CN114102949A - Preparation method of polytetrafluoroethylene composite microporous membrane and composite microporous membrane - Google Patents
Preparation method of polytetrafluoroethylene composite microporous membrane and composite microporous membrane Download PDFInfo
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- CN114102949A CN114102949A CN202111351838.1A CN202111351838A CN114102949A CN 114102949 A CN114102949 A CN 114102949A CN 202111351838 A CN202111351838 A CN 202111351838A CN 114102949 A CN114102949 A CN 114102949A
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- polytetrafluoroethylene
- microporous membrane
- composite
- stretching
- composite microporous
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Links
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 77
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 53
- 239000012982 microporous membrane Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000005096 rolling process Methods 0.000 claims abstract description 27
- 238000005238 degreasing Methods 0.000 claims abstract description 15
- 230000001007 puffing effect Effects 0.000 claims abstract description 15
- 238000003490 calendering Methods 0.000 claims abstract description 13
- 238000009998 heat setting Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000013329 compounding Methods 0.000 claims abstract description 3
- 238000007493 shaping process Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 28
- 239000010410 layer Substances 0.000 abstract description 18
- 239000011229 interlayer Substances 0.000 abstract description 14
- 239000012528 membrane Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000002585 base Substances 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 238000003466 welding Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229940045860 white wax Drugs 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
- B29C43/24—Calendering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
Abstract
The invention relates to the technical field of preparation of polytetrafluoroethylene membrane materials, in particular to a preparation method of a polytetrafluoroethylene composite microporous membrane and the composite microporous membrane, wherein the preparation method comprises the following steps: composite rolling: compounding at least two layers of polytetrafluoroethylene materials, and then calendering at a certain pressure, wherein the calendering temperature is 35-120 ℃, so as to obtain a polytetrafluoroethylene composite calendering base band; degreasing and puffing: carrying out heat treatment on the polytetrafluoroethylene composite calendered baseband in a degreasing machine, and carrying out puffing to obtain a polytetrafluoroethylene puffed baseband; stretching and shaping: and stretching the polytetrafluoroethylene expanded baseband, and then carrying out heat setting. The preparation method has the advantages of energy consumption saving, simple operation and capability of obtaining the composite microporous membrane with high interlayer bonding fastness.
Description
A preparation method of a polytetrafluoroethylene composite microporous membrane and the composite microporous membrane.
Technical Field
The invention relates to the technical field of preparation of polytetrafluoroethylene membrane materials, in particular to a preparation method of a polytetrafluoroethylene composite microporous membrane and the composite microporous membrane.
Technical Field
Polytetrafluoroethylene, commonly known as "plastic king", is a high molecular polymer prepared by polymerization using tetrafluoroethylene as a monomer. The polytetrafluoroethylene white wax is a semitransparent white wax body, can be used at-180-260 ℃ for a long time, has the characteristics of acid resistance, alkali resistance and various organic solvents resistance, is almost insoluble in all solvents, and has a very low friction coefficient. Due to the beneficial characteristics, the polytetrafluoroethylene serving as a membrane material is widely applied to industries such as national defense, aerospace, electronics, electrical, chemical industry, food, medical treatment, textile and the like.
The polytetrafluoroethylene membrane material usually forms a product in an asymmetric structure, so two or more layers of polytetrafluoroethylene materials are needed to be compounded for use, for example, the Chinese patent with the application number of CN200610145995.6 discloses a processing method of a polytetrafluoroethylene nanometer aperture filter membrane, and the method comprises the steps of material mixing, blank pressing, rolling, double-layer polytetrafluoroethylene tape overlapping degreasing, longitudinal stretching, transverse stretching and heat setting.
In the stretching process of the double-layer base band, the acting force borne in the thickness direction of the base band is small, the defect that the interlayer bonding firmness of the polytetrafluoroethylene microporous film is low can be caused, the defect can cause the problem that a composite microporous film structure is unstable, and in order to solve the problem, the base band is bonded in a welding mode in the prior art.
However, the welding of polytetrafluoroethylene needs to be performed by hot-press welding at 380 ± 5 ℃ and 1-2 Mpa, or welded together by hot-air welding at 420-480 ℃, so that the preparation cost of the polytetrafluoroethylene film material is increased undoubtedly by the harsher welding environment, and the application prospect and the application universality are also limited.
Disclosure of Invention
In order to solve the technical problems, one of the purposes of the application is to provide a preparation method of a polytetrafluoroethylene composite microporous membrane, the preparation method can achieve the technical effect of high interlayer bonding fastness without welding with high energy consumption, and the other purpose is to provide the composite microporous membrane prepared by the method, and the interlayer bonding fastness of the composite microporous membrane can reach about 25N.
The preparation method of the polytetrafluoroethylene composite microporous membrane comprises the following steps:
composite rolling: compounding at least two layers of polytetrafluoroethylene materials, and then rolling, wherein the rolling temperature is 35-120 ℃, the rolling speed is 5-20 m/min, and the thickness of a rolled base band is 100-1000 mu m to obtain a polytetrafluoroethylene composite rolled base band;
degreasing and puffing: carrying out heat treatment on the polytetrafluoroethylene composite calendered baseband in a degreasing machine, and carrying out puffing to obtain a polytetrafluoroethylene puffed baseband;
stretching and shaping: and stretching the polytetrafluoroethylene expanded baseband, and then carrying out heat setting.
As is well known to those skilled in the art, polytetrafluoroethylene (hereinafter referred to as PTFE) materials have extremely high non-tackiness, i.e., the surfaces of two layers of PTFE materials cannot be bonded by direct adhesion, and therefore, the PTFE materials are often bonded by welding, in which the PTFE materials are fusion-welded in a molten state at high temperature.
Based on the above knowledge, the ordinary skilled person would not consider achieving a face bonding of two or even more layers of PTFE material by applying pressure at a lower temperature.
The inventor of the application develops a new method, welding with high energy consumption and high requirements on environment is not adopted, and before the degreasing and puffing step, a calendering mode is adopted, so that the surface and the surface of the adjacent PTFE materials are combined at a low temperature of 35-120 ℃.
Specifically, the inventors considered, after analysis, that: in the rolling step, the extension at least includes the extension meaning, namely, in the rolling process, the PTFE material at least generates extension-type deformation, when the deformation occurs, the movement trends of two contact surfaces between the adjacent PTFE materials are easy to generate difference, the difference causes relative movement between different PTFE layer contact surfaces, the relative movement causes friction of the adjacent PTFE layer contact surfaces, the friction movement further causes the deformation of the PTFE layer contact surfaces, the deformation enables the original surface contact to be converted into the actual structural connection relations of hooking, clamping, embedding and the like among fine structures, and the existence of the connection relations realizes the interlayer connection between two or even multiple layers of PTFE materials with extremely high non-stickiness.
The interlayer connection mode becomes the basis of improving interlayer bonding fastness of the PTFE composite microporous membrane, in the subsequent degreasing and puffing step, the multilayer structure of the PTFE composite microporous membrane is not easy to separate along with the progress of puffing, on the contrary, the structure connection relation between adjacent PTFE layers can expand locally along with the puffing, the bonding structure becomes tighter, namely, the interlayer bonding fastness of the PTFE composite microporous membrane can be improved in the puffing process.
The calendering temperature is low, the energy consumption cannot be only considered, the loss of auxiliary agents such as extrusion aids and the like is also considered, the auxiliary agents are contained in the PTFE material before degreasing and puffing, and the excessive calendering temperature can cause the volatilization loss of the auxiliary agents and generate adverse effects on subsequent steps, so that,as a preferenceAnd in the step of composite rolling, the rolling temperature is 35-60 ℃.
Although a press plate or the like can also perform the rolling operation, the rolling operation using a press roll is one of the most common operation methods in the art, and is easy to operate and also convenient to form a band-shaped base material, and therefore,as a preferenceIn the step of composite rolling, at least two layers of polytetrafluoroethylene materials are rolled by a press roll.
When the rolling speed of the compression roller is too high, the friction between adjacent PTFE layers is insufficient, the structural connection relationship between the PTFE material layers is not easy to form, and when the rolling speed is too low, the production efficiency is affected, therefore,as a preferenceAnd the rolling speed is controlled within the range of 5-20 m/min.
As a preferenceIn the degreasing and puffing step, the heat treatment temperature is 100-250 ℃, the heat treatment time is 3-20 min, and the heat treatment temperature can be determined according to the type of the extrusion aid.
As a preferenceIn the stretch-setting step, the stretching treatment includes longitudinal stretching and transverse stretching, wherein the longitudinal direction refers to the extrusion direction of calendering, and on the base tape surface, the direction perpendicular to the longitudinal direction is the transverse direction.Further preferred areThe stretching ratio of the longitudinal stretching is 2-20 times, and the stretching ratio of the transverse stretching is 2-50 times.
The purpose of heat setting is to eliminate the stress and strain accumulated inside the composite membrane structure, to obtain the required form in terms of state, size and structure, and to achieve a certain stability, therefore,as a preferenceIn the step of stretching and setting, the parameters of heat setting can be determined according to the requirements of PTFE composite film products, specifically, the setting temperature is 330-430 ℃, and the setting time is 30-300 s.Further preferred areThe heat setting method is contact setting or non-contact setting.
The composite microporous membrane as a product can be prepared by the preparation method of any one of the technical schemes.
In summary, the main beneficial effects of the invention are as follows:
compared with a preparation method of the polytetrafluoroethylene composite microporous membrane comprising a welding step, the preparation method of the polytetrafluoroethylene composite microporous membrane disclosed by the embodiment of the application has the advantages that the energy consumption is saved, the operation is simple, and meanwhile, higher interlayer bonding fastness can be obtained;
the interlayer bonding fastness of the composite microporous membrane prepared by the method can reach about 25N.
Further or more specific advantages will be described in the detailed description in connection with the specific embodiments.
Detailed Description
The invention is further illustrated below with reference to examples:
the preparation method of the polytetrafluoroethylene composite microporous membrane disclosed by the embodiment 1-3 of the invention comprises the following steps:
s1 mixing: mixing polyvinyl fluoride dispersion resin and extrusion aid, placing the mixture into a mixer, and mixing the mixture under high-speed rotation, wherein the mixing temperature is 2-16 ℃, and the mixing time is 5-100 min;
s2 curing: placing the raw materials subjected to the mixing treatment in the step S1 into an oven for curing treatment, wherein the curing temperature is 30 ℃, and the curing time is 12 hours;
s3 screening: screening the raw material treated in the step S2 to remove lumps generated after curing;
s4 green compact: placing the screened raw materials in a blank presser respectively for prepressing to prepare polytetrafluoroethylene dispersion resin blanks respectively containing different molecular weights, wherein the prepressing speed is 0.2 m/min;
s5 extrusion: pushing and extruding the blank pre-pressed in the step S4 by using a pushing press, wherein the extruded material comprises but is not limited to a sheet shape or other irregular shapes, the extrusion compression ratio is 100, the extrusion speed is 200cm/min, the pressure of the pushing press is 2.0MPa, and for comparison, the extruded material in the step is a sheet shape object with the same specification;
s6 combined rolling: performing double-layer or multi-layer composite calendering on the extrudate obtained in the step S5 by using a roller calender to obtain a PTFE (Polytetrafluoroethylene) composite baseband, wherein the temperature of a roller is set to be 35-120 ℃, the calendering speed is 5-20 m/min, and the thickness of the calendering baseband is 200-400 mu m, wherein the gap of an extrusion opening of the calender can be adjusted, and the width of the gap is expressed as the thickness of the baseband;
s7 degreasing and puffing: carrying out heat treatment on the PTFE composite baseband obtained in the step S6 in a degreasing machine, removing an extrusion aid, and fully expanding, wherein the degreasing temperature is 100-250 ℃;
s8 stretching: stretching the degreased composite baseband obtained in the step S7, wherein the stretching treatment comprises longitudinal stretching and transverse treatment, the longitudinal stretching multiple is 2-20 times, and the transverse stretching multiple is 2-50 times;
s9 heat setting: the setting time is 30-300 s, the setting temperature is 330-430 ℃, and the setting method is contact type setting or non-contact type setting.
Examples 1 to 3 and comparative example are methods for producing a polytetrafluoroethylene composite microporous membrane, and relevant parameters are shown in table 1, and performance parameters of the intermediate product and the final product are shown in table 2, wherein for comparison, the comparative example is a production method omitting a composite rolling step with respect to example 1.
Table 1 examples 1 to 3, parameters relating to the preparation method of comparative example
As can be seen from table 1, examples 1 to 3 are preparation methods in which different parameters are selected within a certain range, and the difference between the preparation methods described in example 1 and comparative example is only whether a composite rolling step with a specific timing sequence is included.
Table 2 performance parameters of the products obtained in examples 1 to 3 and comparative examples
The fastness test method in Table 2 is described in GB 8808-1988 Peel test method for soft composite plastic materials.
As can be seen from table 2, after the composite rolling, the polytetrafluoroethylene composite rolled base tapes obtained in examples 1 to 3 already have considerable interlayer bonding fastness, and after the swelling process, the interlayer bonding fastness of the base tape is enhanced, that is, the swelling process strengthens the interlayer bonding fastness of the base tape, and the subsequent stretching step also affects the interlayer bonding fastness of the film, although not necessarily a positive effect, the range of the stretching step is small, and the effect is limited.
In the comparative example, the bonding fastness between the film layers of the final product of the PTFE composite film product prepared without the composite rolling step is only 9N, which is far less than the bonding fastness between the film layers of the PTFE composite film product prepared in the example 1, which is 25N.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. The preparation method of the polytetrafluoroethylene composite microporous membrane is characterized by comprising the following steps:
composite rolling: compounding at least two layers of polytetrafluoroethylene materials, and then rolling at the temperature of 35-120 ℃ to obtain a polytetrafluoroethylene composite rolled base band;
degreasing and puffing: carrying out heat treatment on the polytetrafluoroethylene composite calendered baseband in a degreasing machine, and carrying out puffing to obtain a polytetrafluoroethylene puffed baseband;
stretching and shaping: and stretching the polytetrafluoroethylene expanded baseband, and then carrying out heat setting.
2. The method for preparing a polytetrafluoroethylene composite microporous membrane according to claim 1, wherein the method comprises the following steps: in the composite rolling step, the rolling temperature is 35-60 ℃.
3. The method for preparing a polytetrafluoroethylene composite microporous membrane according to claim 1 or 2, wherein: in the composite rolling step, at least two layers of polytetrafluoroethylene materials are rolled by a press roll.
4. The method for preparing a polytetrafluoroethylene composite microporous membrane according to claim 3, wherein the method comprises the following steps: the rolling speed is 5-20 m/min.
5. The method for preparing a polytetrafluoroethylene composite microporous membrane according to claim 1, wherein the method comprises the following steps: in the degreasing and puffing step, the heat treatment temperature is 100-250 ℃, and the heat treatment time is 3-20 min.
6. The method for preparing a polytetrafluoroethylene composite microporous membrane according to claim 3, wherein the method comprises the following steps: in the step of stretching and setting, the stretching treatment comprises longitudinal stretching and transverse stretching.
7. The method for preparing a polytetrafluoroethylene composite microporous membrane according to claim 6, wherein the method comprises the following steps: the stretching ratio of the longitudinal stretching is 2-20 times, and the stretching ratio of the transverse stretching is 2-50 times.
8. The method for preparing a polytetrafluoroethylene composite microporous membrane according to claim 1, wherein the method comprises the following steps: in the step of stretching and setting, the setting temperature of heat setting is 330-430 ℃, and the setting time is 30-300 s.
9. The method for preparing a polytetrafluoroethylene composite microporous membrane according to claim 8, wherein the method comprises the following steps: the heat setting method is contact setting or non-contact setting.
10. The composite microporous membrane is characterized in that: the preparation method of any one of claims 1 to 9.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111351838.1A CN114102949A (en) | 2021-11-16 | 2021-11-16 | Preparation method of polytetrafluoroethylene composite microporous membrane and composite microporous membrane |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111351838.1A CN114102949A (en) | 2021-11-16 | 2021-11-16 | Preparation method of polytetrafluoroethylene composite microporous membrane and composite microporous membrane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116218107A (en) * | 2023-03-15 | 2023-06-06 | 浙江苏泊尔股份有限公司 | Preparation method of non-stick film, non-stick film and cooking utensil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5225131A (en) * | 1989-12-07 | 1993-07-06 | Daikin Industries, Ltd. | Process for producing multilayer polytetrafluoroethylene porous membrane and semisintered polytetrafluoroethylene multilayer structure |
| AU2003200272A1 (en) * | 1995-09-05 | 2003-04-10 | Bio Med Sciences, Inc | Microporous membrane with a stratified pore structure created in situ and process |
| CN101085418A (en) * | 2006-11-30 | 2007-12-12 | 中国人民解放军总后勤部军需装备研究所 | Method of processing polytetrafluoroethene nano-aperture filter membrane |
| CN107277701A (en) * | 2017-08-12 | 2017-10-20 | 施柏德（厦门）科技有限公司 | A kind of preparation method of the waterproof and breathable sound passing membrane compound by lamination |
| CN112044278A (en) * | 2020-09-14 | 2020-12-08 | 浙江格尔泰斯环保特材科技股份有限公司 | Preparation method of PTFE microporous membrane with multilayer structure |
| CN113043632A (en) * | 2021-03-09 | 2021-06-29 | 山东森荣新材料股份有限公司 | Preparation method of polytetrafluoroethylene high-strength microporous membrane |
| CN113043620A (en) * | 2021-03-29 | 2021-06-29 | 浙江格尔泰斯环保特材科技股份有限公司 | Preparation method of polytetrafluoroethylene film with ultrahigh air permeability |
-
2021
- 2021-11-16 CN CN202111351838.1A patent/CN114102949A/en active Pending
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|---|---|---|---|---|
| US5225131A (en) * | 1989-12-07 | 1993-07-06 | Daikin Industries, Ltd. | Process for producing multilayer polytetrafluoroethylene porous membrane and semisintered polytetrafluoroethylene multilayer structure |
| AU2003200272A1 (en) * | 1995-09-05 | 2003-04-10 | Bio Med Sciences, Inc | Microporous membrane with a stratified pore structure created in situ and process |
| CN101085418A (en) * | 2006-11-30 | 2007-12-12 | 中国人民解放军总后勤部军需装备研究所 | Method of processing polytetrafluoroethene nano-aperture filter membrane |
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| CN113043632A (en) * | 2021-03-09 | 2021-06-29 | 山东森荣新材料股份有限公司 | Preparation method of polytetrafluoroethylene high-strength microporous membrane |
| CN113043620A (en) * | 2021-03-29 | 2021-06-29 | 浙江格尔泰斯环保特材科技股份有限公司 | Preparation method of polytetrafluoroethylene film with ultrahigh air permeability |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116218107A (en) * | 2023-03-15 | 2023-06-06 | 浙江苏泊尔股份有限公司 | Preparation method of non-stick film, non-stick film and cooking utensil |
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