CN1990526A - Method for preparing perfluorinated sulfonic acid ionic membrane by melting-extruding-flattening film - Google Patents
Method for preparing perfluorinated sulfonic acid ionic membrane by melting-extruding-flattening film Download PDFInfo
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- CN1990526A CN1990526A CNA2005101325285A CN200510132528A CN1990526A CN 1990526 A CN1990526 A CN 1990526A CN A2005101325285 A CNA2005101325285 A CN A2005101325285A CN 200510132528 A CN200510132528 A CN 200510132528A CN 1990526 A CN1990526 A CN 1990526A
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- sulfonic acid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a method for preparing perfluorosulfonic acid ion-exchange membrane. The melting extrusion calendaring method is to improve the performance of membrane and increase its production rate. The method comprises following steps: putting perfluorosulfonic acid resin to extrusion machine for melting and extrusion, getting sheet membrane through lamel die head forming, calendaring with three- roll calendar, or compositing with polytetrafluoroethylene net cloth on three- roll calendar directly to produce perfluorosulfonic acid ion-exchange membrane or composite membrane, then forming ionic or acid kind through chemical treatment. The thickness uniformity of membrane is adjusted by thickness moderation screw on slit die, and membrane thickness is controlled by extrusion speed of extrusion machine and drawing velocity of three- roll calendar. The membrane produced with perfluorosulfonic acid resin can be converted into perfluorosulfonic acid ion membrane, and the exchange capacity of membrane IEC is 0.67- 1.5 mmol/ g.
Description
Technical field
The present invention relates to the processing molding method of perfluorinated sulfonic acid ion exchange membrane.Specifically, the present invention relates to a kind of preparation method who is used for the perfluorinated sulfonic acid ion exchange membrane of the electrolysis of solutions of water, acid and salt and battery diaphragm as barrier film.This method be by screw-type extruder with the perfluorinated sulfonic acid fluoro-resin under the fusion plastification state through the extrusion moulding of thin slice head, be film article through three-roll press-polishing again, or via three-roller calendar and base material is compound can directly make the cloth based composites.By the homogeneity that the opening thickness of adjustment sheet mould is regulated film, the extruded velocity of adjustment forcing machine and the speed of three-roller calendar are controlled the thickness of film.The gained film is realized the group conversion through chemical treatment again, finally obtains having the perfluorinated sulfonic acid ionic exchange membrane and the perfluorocarboxylic acid ion membranes of ion exchanging function.
Background technology
Perfluorinated sulfonic acid ion exchange resin, as the Nafion polymkeric substance of E.I.Du Pont Company with various mould material supplies and purposes is very widely arranged.Such as: perfluorinated sulfonic acid ion exchange membrane is used to comprise the barrier film of the various electrolytic preparation devices of fuel cell and chlorine industry and other, in addition, also demonstrate excellent use properties at aspects such as electrodialysis, chemical catalysis, gas delivery, gas drying, sewage disposal, sea water desaltinations.Yet, under these application scenarios, require perfluorinated sulfonic acid ion exchange resin to be shaped to film.This normally by perfluorinated sulfonic acid ionic exchange resin is dissolved in make film-forming soln in the corresponding solvent after, again with this solution deposition on certain matrix or with solution casting on template, volatilization makes film (United States Patent (USP) 4731263 except that desolvating then, 4178218,5643968,3849243 etc.; Chinese patent 1624202 etc.).The film forming of these methods must make the solvent evaporates in the film go out, so the process of film forming desolventizing is longer, and inefficiency, the easy variable color of product, in addition, owing to be that solution casting is difficult to make the uniform film of thickness.The present invention adopts perfluorinated sulfonic acid fluorine type resin, directly uses screw-type extruder extrusion film, or via three-roller calendar and base material is compound can directly make the cloth based composites.By the homogeneity that the opening thickness of adjustment sheet mould is regulated film, the extruded velocity of adjustment forcing machine and the speed of three-roller calendar are controlled the thickness of film.And then be ionic or acid type through chemical treatment transition.It is fast that this method has production rate, and product colour remains unchanged, and film thickness is even, and quality is closely knit, characteristics such as mechanical strength height.
Summary of the invention
Content of the present invention is that the technology of existing solution casting method moulding perfluorinated sulfonic acid ion exchange membrane is improved, and adopts to melt extrude rolling process moulding perfluorinated sulfonic acid ion exchange membrane, with the performance of improving film and improve throughput rate.
The present invention is used for the preparation of the perfluorinated sulfonic acid ion exchange membrane of battery, electrolyzer.
The method for preparing above-mentioned perfluorinated sulfonic acid ion exchange membrane, be perfluorinated sulfonic acid fluorine type resin directly to be added forcing machine 1 from hopper 2 melt extrude, be shaped to sheet film by thin slice head 3, then by three-roller calendar 4 calendering formations, or it is direct and compound on three-roller calendar 4 from the base materials such as graticule cloth from teflon 7 of unwinding device 6, make perfluorinated sulfonic acid fluorine type film or composite membrane 8,, and then handle through chemical process and to be ionic or acidity transition through wrap-up 5 rolling and storage.The thickness evenness of film is adjusted the screw adjustment by the thickness of slit mouth mould, and film thickness is by the pulling speed control of forcing machine extruded velocity and three-roller calendar.
About the used perfluorinated sulfonic acid fluorine of the present invention type ion exchange resin, be by tetrafluoroethylene and following monomer:
Wherein m=0～3 (preferred m=1～3), n 〉=2 (preferred 2 or 3), X=SO
2The F copolymerization obtains.
The film that above-mentioned used perfluorinated sulfonic acid fluorine type resin makes can make the perfluorinated sulfonic acid ionic membrane of following structure after conversion, its chemical structural formula is:
Wherein, m=0～3 (preferred m=1～3), n 〉=2 (preferred 2 or 3), x 〉=1 (preferred 4～12), y 〉=1 (preferred 1 or 2), Y is SO
3M.M is basic metal or alkaline-earth metal such as H, Na, K, Li, Ca, Mg.
The difference of M is little to influential effect of the present invention.
The exchange capacity of the film after transition is IEC=0.67～1.5mmol./g.Can represent that also the pass of EW and IEC is EW=1000/IEC g/mol. with molal weight EW.
Description of drawings
Fig. 1. melt extrude calendering formation perfluorinated sulfonic acid fluorine type ionic membrane
Embodiment
Embodiment one: adopt raw material: the group form is Rf-SO
2F perfluorinated sulfonic acid fluorine type resin, density 1.98g/cm
3, feed particulate material, forcing machine is single screw extrusion machine Φ 30, L/D=25; Thick 1.0mm is adjustable for the sheet die slit, stitches wide 150mm; Enter three-roller calendar calendering rolling after cooling behind the extrudate piece film; Wherein, extruder screw and barrel, the used steel of slit mouth mould are special stainless steel.Each section of forcing machine temperature is 140～190 ℃, and wherein, die temperature is 175 ℃; Three-roller calendar roller temperature≤about 30 ℃.After equipment is heated to design temperature, resin is added through the forcing machine spout, through three-roller calendar calendering cooling, obtain thickness is that 120 ± 5 μ m, width are the apparent flawless perfluorinated sulfonic acid fluorine type film of 140mm to fusion plastification extrudate piece film again.
This film is through NaOH methanol solution saponification 16 hours, and then with the HCl solution reaction, obtain perfluorinated sulfonic acid sodium type and perfluorinated sulfonic acid Hydrogen ion-exchange membrane respectively, its exchange capacity is: 0.95mmol./g.
Embodiment two: adopt raw material: the group form is Rf-SO
2F perfluorinated sulfonic acid fluorine type resin, density 1.98g/cm
3, feed particulate material, forcing machine is single screw extrusion machine Φ 65, L/D=25; 1.0mm is adjustable for the sheet die slit, stitches wide 300mm; Enter three-roller calendar calendering rolling after cooling behind the extrudate piece film; Wherein, extruder screw and barrel, mouthful used steel of mould are special stainless steel.Each section of forcing machine temperature is 140～205 ℃, and wherein, die temperature is 185 ℃; About 30 ℃ of three-roller calendar roller temperature.The gained film thickness is that 155 μ m, width are the apparent flawless perfluorinated sulfonic acid fluorine type ionic membrane of 260mm.
This film is through NaOH methanol solution saponification 16 hours, and then with the HCl solution reaction, obtain perfluorinated sulfonic acid sodium type and perfluorinated sulfonic acid Hydrogen ion-exchange membrane respectively, its exchange capacity is: 1.05mmol./g.
Embodiment three: adopt raw material: the group form is Rf-SO
2F perfluorinated sulfonic acid fluorine type resin, density 1.98g/cm
3, feed particulate material, forcing machine is twin screw extruder Φ 20, L/D=40; Sheet die slit 1.0mm, wide 150mm; Enter three-roller calendar calendering rolling after cooling behind the extrudate piece film; Wherein, extruder screw and barrel, the used steel of slit mouth mould are special stainless steel.Each section of forcing machine temperature is 140～185 ℃, and wherein, die temperature is 185 ℃; About 30 ℃ of three-roller calendar roller temperature.After equipment is heated to design temperature, resin is fed twin screw extruder through the metering of screw feeding machine, film extrusion, obtaining thickness is that 140 μ m, width are the apparent flawless perfluorinated sulfonic acid fluorine type ionic membrane of 140mm.
This film is through NaOH methanol solution saponification 16 hours, and then with the HCl solution reaction, obtain perfluorinated sulfonic acid sodium type and perfluorinated sulfonic acid Hydrogen ion-exchange membrane respectively, its exchange capacity is: 0.98mmol./g.
Embodiment four: adopt raw material: the group form is Rf-SO
2F type resin, density 1.98g/cm
3, feed particulate material, forcing machine is exhaust list forcing machine Φ 65, L/D=40; Sheet die slit 1.0mm, wide 650mm; Enter three-roller calendar calendering rolling after cooling behind the extrudate piece film; Wherein, extruder screw and barrel, the used steel of slit mouth mould are special stainless steel.Each section of forcing machine temperature is 140～185 ℃, and die temperature is 185 ℃; About 30 ℃ of three-roller calendar roller temperature.The gained film thickness is that 140 μ m, width are the apparent flawless perfluorinated sulfonic acid fluorine type film of 600mm.
This film is through NaOH methanol solution saponification 16 hours, and then with the HCl solution reaction, obtain perfluorinated sulfonic acid sodium type and perfluorinated sulfonic acid Hydrogen ion-exchange membrane respectively, its exchange capacity is: 1.08mmol./g.
Embodiment five: adopting raw material group form is Rf-SO
2F perfluorinated sulfonic acid fluorine type resin, density 1.98g/cm
3, feed particulate material, forcing machine is single screw extrusion machine Φ 30, L/D=25; 1.0mm is adjustable for the sheet die slit, stitches wide 150mm; Enter three-roller calendar calendering rolling after cooling behind the extrudate piece film; Wherein, extruder screw and barrel, the used steel of slit mouth mould are special stainless steel.Each section of forcing machine temperature is 140～190 ℃, and wherein, die temperature is 175 ℃; Three-roller calendar roller temperature≤about 30 ℃.After equipment is heated to design temperature, resin is added through the forcing machine spout, fusion plastification extrudate piece film enters three-roller calendar, introducing the tetrafluoroethylene woven cloth at the three-roller calendar lower roll simultaneously, is that 140 ± 5 μ m, width are the apparent flawless perfluorinated sulfonic acid fluorine type laminated film of 140mm through the compound thickness that obtains of three-roller calendar calendering.
This composite membrane is through NaOH methanol solution saponification 16 hours, and then with the HCl solution reaction, obtain perfluorinated sulfonic acid sodium type and perfluorinated sulfonic acid Hydrogen ion-exchange membrane respectively, its exchange capacity is: 0.95mmol./g.
Claims (6)
1. an employing melt extrudes the method that calendered film prepares the perfluorinated sulfonic acid ionic membrane, it is characterized in that being perfluorinated sulfonic acid fluorine type resin is extruded through forcing machine, by sheet film head film in blocks, roll into perfluorinated sulfonic acid fluorine type ionic membrane or be combined into perfluorinated sulfonic acid fluorine type ion composite membrane with the fabricbase base material through three-roller calendar, the gained film makes the transition through chemistry and is the perfluorinated sulfonic acid ionic membrane.
2. film according to claim 1 is characterized in that the structure of the used perfluorinated sulfonic acid fluorine of film forming type resin is:
Wherein, m=0～3, n 〉=2, x 〉=1, y 〉=1, Y is SO
2F.
3. a kind of preparation method who is used for battery, electrolytic perfluorinated sulfonic acid ion exchange membrane according to claim 1, it is characterized in that it being that perfluorinated sulfonic acid fluorine type resin is directly extruded by screw-type extruder, again by film head film forming, get perfluorinated sulfonic acid fluorine type ionic membrane through the three-roller calendar rolling after cooling, or via three-roller calendar and base material is compound can directly make the cloth based composites.By the homogeneity that the opening thickness of adjustment sheet mould is regulated film, the extruded velocity of adjustment forcing machine and the speed of three-roller calendar are controlled the thickness of film.
4. method according to claim 3 is characterized in that employed substrate material comprises base materials such as tetrafluoroethylene weave mesh cloth.
5. method according to claim 3 is characterized in that the forcing machine that is used to melt extrude is single screw extrusion machine, single screw rod degassing extruder, twin screw extruder, multiple screw extruder, two rank forcing machine, dynamic vibration formula forcing machine etc.
6. film according to claim 1 is characterized in that it is perfluorinated sulfonic acid ionic film that the film that is made by perfluorinated sulfonic acid fluorine type resin makes the transition through chemistry again, and its chemical structural formula is:
Wherein, m=0～3 (preferred m=1～3), n 〉=2 (preferred 2 or 3), x 〉=1 (preferred 4～12), y 〉=1 (preferred 1 or 2), Y is SO
3M.M is basic metal or alkaline-earth metal such as H, Na, K, Li, Ca, Mg.The exchange capacity of its film is 0.67～1.5mmol./g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNA2005101325285A CN1990526A (en) | 2005-12-26 | 2005-12-26 | Method for preparing perfluorinated sulfonic acid ionic membrane by melting-extruding-flattening film |
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| CNA2005101325285A CN1990526A (en) | 2005-12-26 | 2005-12-26 | Method for preparing perfluorinated sulfonic acid ionic membrane by melting-extruding-flattening film |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920549A (en) * | 2009-06-17 | 2010-12-22 | 北京化工大学 | Formula and process for preparing wide chlorinated polyethylene waterproof roll material by extrusion molding method |
| CN102260399A (en) * | 2011-06-07 | 2011-11-30 | 上海三爱富新材料股份有限公司 | Method for producing perfluorosulfonic acid proton exchange film |
| CN101780710B (en) * | 2009-12-07 | 2012-03-07 | 山东东岳高分子材料有限公司 | Continuous preparation method and equipment for enhanced composite ionic membrane |
| CN102675669A (en) * | 2011-03-11 | 2012-09-19 | 北京化工大学 | Method for preparing perfluoro sulfonate ion membranes by utilizing melt extrusion blow molding technique |
| CN108189355A (en) * | 2017-11-24 | 2018-06-22 | 中材科技股份有限公司 | A kind of preparation method of fuel cell barrier film |
| CN109761319A (en) * | 2019-03-08 | 2019-05-17 | 浙江迪萧环保科技有限公司 | A kind of perfluorinated sulfonic acid bipolar membrane and preparation method |
| CN109806772A (en) * | 2019-03-08 | 2019-05-28 | 浙江迪萧环保科技有限公司 | A kind of perfluorinated sulfonic acid anion-exchange membrane and preparation method |
| CN109968575A (en) * | 2019-05-16 | 2019-07-05 | 江苏科润膜材料有限公司 | A kind of steel band casting machine producing enhanced perfluorinated ion-exchange membrane |
| CN111808309A (en) * | 2020-06-22 | 2020-10-23 | 山东东岳高分子材料有限公司 | High proton conduction perfluorosulfonic acid ion exchange membrane and preparation method thereof |
| CN111976173A (en) * | 2019-05-24 | 2020-11-24 | 安徽省众望科希盟科技有限公司 | Preparation process of unidirectional stretching polytetrafluoroethylene film |
| CN113058440A (en) * | 2021-04-09 | 2021-07-02 | 西部宝德科技股份有限公司 | Preparation method of tubular powder mesh composite porous metal film |
| CN113181782A (en) * | 2021-04-09 | 2021-07-30 | 西部宝德科技股份有限公司 | Preparation method of powder mesh composite porous metal film |
-
2005
- 2005-12-26 CN CNA2005101325285A patent/CN1990526A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920549A (en) * | 2009-06-17 | 2010-12-22 | 北京化工大学 | Formula and process for preparing wide chlorinated polyethylene waterproof roll material by extrusion molding method |
| CN101780710B (en) * | 2009-12-07 | 2012-03-07 | 山东东岳高分子材料有限公司 | Continuous preparation method and equipment for enhanced composite ionic membrane |
| CN102675669A (en) * | 2011-03-11 | 2012-09-19 | 北京化工大学 | Method for preparing perfluoro sulfonate ion membranes by utilizing melt extrusion blow molding technique |
| CN102260399A (en) * | 2011-06-07 | 2011-11-30 | 上海三爱富新材料股份有限公司 | Method for producing perfluorosulfonic acid proton exchange film |
| CN102260399B (en) * | 2011-06-07 | 2013-11-20 | 上海三爱富新材料股份有限公司 | Method for producing perfluorosulfonic acid proton exchange film |
| CN108189355A (en) * | 2017-11-24 | 2018-06-22 | 中材科技股份有限公司 | A kind of preparation method of fuel cell barrier film |
| CN109761319A (en) * | 2019-03-08 | 2019-05-17 | 浙江迪萧环保科技有限公司 | A kind of perfluorinated sulfonic acid bipolar membrane and preparation method |
| CN109806772A (en) * | 2019-03-08 | 2019-05-28 | 浙江迪萧环保科技有限公司 | A kind of perfluorinated sulfonic acid anion-exchange membrane and preparation method |
| CN109968575A (en) * | 2019-05-16 | 2019-07-05 | 江苏科润膜材料有限公司 | A kind of steel band casting machine producing enhanced perfluorinated ion-exchange membrane |
| CN109968575B (en) * | 2019-05-16 | 2024-03-29 | 江苏科润膜材料有限公司 | Steel belt casting machine for producing enhanced perfluorinated ion exchange membrane |
| CN111976173A (en) * | 2019-05-24 | 2020-11-24 | 安徽省众望科希盟科技有限公司 | Preparation process of unidirectional stretching polytetrafluoroethylene film |
| CN111808309A (en) * | 2020-06-22 | 2020-10-23 | 山东东岳高分子材料有限公司 | High proton conduction perfluorosulfonic acid ion exchange membrane and preparation method thereof |
| CN113058440A (en) * | 2021-04-09 | 2021-07-02 | 西部宝德科技股份有限公司 | Preparation method of tubular powder mesh composite porous metal film |
| CN113181782A (en) * | 2021-04-09 | 2021-07-30 | 西部宝德科技股份有限公司 | Preparation method of powder mesh composite porous metal film |
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