CN100519594C - Polymer containing fluorin, and application as material of ion exchange fiber - Google Patents
Polymer containing fluorin, and application as material of ion exchange fiber Download PDFInfo
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- CN100519594C CN100519594C CNB2006101662940A CN200610166294A CN100519594C CN 100519594 C CN100519594 C CN 100519594C CN B2006101662940 A CNB2006101662940 A CN B2006101662940A CN 200610166294 A CN200610166294 A CN 200610166294A CN 100519594 C CN100519594 C CN 100519594C
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Abstract
This invention discloses a fluorine-containing polymer and its application as ion exchange fiber material. The fluorine-containing polymer is a perfluoro resin containing sulfonylfluoride groups, and is shown in formula 1. The fluorine-containing polymer has ion exchange function, and is prepared by free radical copolymerization of perfluorosulfonyl vinyl ether, tetrafluoroethylene and hexafluoropropylene in the presence of dispersant, solvent and initiator. The dispersant/solvent is mixed solution of melamine derivative containing linear perfluoro hydrocarbon and water. The fluorine-containing polymer can be melt-spun into polymer fibers, which can be woven into fiber network that can be used as the reinforcing network material for ion exchange membranes and chlor-alkali ion membrane to reinforce and improve the ion exchange ability.
Description
Technical field
The present invention relates to fluorine-containing fine chemicals technology, relate to a kind of fluoropolymer and as the application of ion exchange fiber material.
Background technology
After E.I.Du Pont Company was processed into perfluorinated sulfonic resin perfluorinated sulfonic acid type ion-exchange membrane and this film and exhibited one's skill to the full in chlorine industry and Proton Exchange Membrane Fuel Cells the seventies in 20th century, perfluorinated sulfonic acid type ion-exchange membrane has obtained extensive studies in countries in the world, but has only " Nafion " type perfluorinated sulfonic resin of du pont company to realize commercialization at present.The data declaration that present import ion composite membrane is provided: the enhancing net materials that uses in these mould materials has two kinds: tetrafluoroethylene and meltable poly, these perfluor type reinforced fabric are a kind of insulating material that do not have ion exchanging function, its volume specific resistance will exceed 1014 times more than than general chlorine industry with the resistivity that the perfluor type strengthens composite membrane, thereby " blind area " will occur at the directed back side that sees through film of positively charged ion.Therefore increase the useful area of cation permeation film, corresponding reduction membrane resistance and bath voltage are the technical barriers of present this area.
Summary of the invention
In order to increase the useful area of cation permeation film, corresponding reduction membrane resistance and bath voltage the invention provides a kind of fluoropolymer, i.e. perfluorinated resin, specifically a kind of perfluorinated resin that has the sulfonic acid fluoride group and preparation method thereof.
The present invention also provides the application of this (per) fluoropolymer as ion exchange fiber material.Promptly be prepared into fluorine-contained polymerisate fibre, in order to enhancing net materials as chlor-alkali ionic membrane and proton exchange membrane with ion exchanging function by melt-spinning.
Technical scheme of the present invention is as follows:
A kind of sulfonic acid fluoride group perfluorinated resin that has has the general structure of formula (I):
In the formula: p, t, q are 10-10000 integer, and p/ (p+t+q)=88～97.5%, q/ (p+t+q)=0.1～7%, t/ (p+t+q)=0.1～7%, n=1 or 2.
Above-mentioned perfluorinated resin has low ion exchange capacity, and the loading capacity value is 0.01～0.45mmol/g.
Above-mentioned perfluorinated resin is 1～50g/10min 372 ℃ melt flow index.
The application of perfluorinated resin of the present invention, this resin can be by melt extruding spinning, prepare the fluorine-contained polymerisate fibre material with ion exchanging function in 200～400 ℃ of scopes.
The application of perfluorinated resin of the present invention wherein melt extrudes at least 400 ℃ of die head temperatures.
The application of perfluorinated resin of the present invention, wherein spinning speed is 1～750m/min.
The application of perfluorinated resin of the present invention, wherein spinning equipment adopts the Langaloy material at high temperature and the part that contacts with resin during spinning, prevents to introduce foreign ion and pollute fiber in resin.
The application of perfluorinated resin of the present invention, described fluorine-contained polymerisate fibre material with ion exchanging function, be woven into fibrous reticulum by textile technology,, reach enhancing and improve ion-exchange capacity simultaneously as the enhancing net materials of proton exchange membrane and chlor-alkali ionic membrane.
The preparation method of perfluorinated resin of the present invention is with tetrafluoroethylene, R 1216 and perfluor sulfonyl base vinyl ether, causes the copolymerization preparation and gets through free radical in the presence of dispersion agent, solvent and initiator.
Its unique distinction is, the mixing solutions of selecting the perfluoroalkyl ethers that contains the trimeric cyanamide structure and water for use is as dispersing agent.The fluoropolymer of preparing with this this dispersing agent system has ion exchanging function, can carry out spinning by the mode that melt extrudes and prepare fortifying fibre.
The perfluoroalkyl ethers dispersion agent that contains the trimeric cyanamide structure provided by the present invention is the melamine derivative that a class has the perfluoroalkyl ethers chain link, and its general molecular formula is:
Wherein x+y=2, x are respectively 0,1, and m is 1～10 integer.
The perfluoroalkyl ether solvents that this class contains the trimeric cyanamide structure has very high boiling point, and this kind solvent has good solvability to monomer and product, its decomposition temperature surpasses 350 ℃, can solve having a strong impact on that solvent evaporates causes in the polymerization, and improves monomeric transformation efficiency.
The above-mentioned preparation that has the melamine derivative of perfluoroalkyl ethers chain link can be selected any one method of this area for use, and the preparation of the melamine derivative about the perfluoroalkyl ethers chain link of the present invention is referring to 200510044978.9.
The comonomer that perfluorinated resin of the present invention is adopted in building-up process is tetrafluoroethylene, R 1216 and perfluor sulfonyl base vinyl ether, and wherein the structural formula of perfluor sulfonyl base vinyl ether is:
The preparation of the perfluor sulfonyl base vinyl ether that uses can be selected any one method of this area for use, and the preparation about perfluor sulfonyl base vinyl ether of the present invention will describe by embodiment.
The present invention is prepared go out have a low ion exchange capacity (per) fluoropolymer, can be at present general apparatus for melt spinning extruding spinning, under pressure molten polymer is extruded by the spinning die head after by apparatus for melt spinning and to be formed the fusion tow polymer melt, after drawing-off, oriented crystalline, cooling, formation has low ion exchange capacity, high strength fibre.As the enhancing net materials of proton exchange membrane and chlor-alkali ionic membrane, can increase the useful area of cation permeation film, corresponding reduction membrane resistance and bath voltage have well solved the technical barrier of present this area.
Embodiment
By the following examples the present invention is illustrated further, but do not limit the present invention.
Embodiment 1: the preparation of monomer perfluor sulfonyl base vinyl ether
Perfluor sulfonyl base vinyl ether (n=2, molecular weight are 612g/mol), molecular formula is:
Synthetic method is as follows:
With tetrafluoroethylene and liquid SO
3The prepared in reaction sultone, sultone product behind the purifying is prepared the perfluoroacyl fluoride product of sulfonic acid fluoride end group through compound fluorion catalyst and the addition of hexafluoro epoxy reaction, and this perfluorochemical that has the sulfonic acid fluoride end group at high temperature stands the cracking decarboxylation and can make the perfluor alkenyl ether compound.
Embodiment 2:
Is being furnished with stirring; heating; add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as a minute routine powder/solvent; perfluor sulfonyl base vinyl ether 6.12g (n=2) and 0.2g benzoyl peroxide; with air in the high pure nitrogen replacement reaction kettle; feed tetrafluoroethylene 95g; R 1216 6g; be warming up to 80 ℃ of stirring reaction 6h; reaction finishes postcooling; venting; make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe; filter; get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows that by the test of fluorine nuclear-magnetism perfluor sulfonyl base vinyl ether weight percentage is 5.42%; the R 1216 weight percentage is 5.49%; the tetrafluoroethylene weight percentage is 89.09%, the thermogravimetric analyzer test shows that its heat decomposition temperature is at 378 ℃; DSC tests and tests melting index when its melt temperature is 267 ℃, 272 ℃ under 2.65 kgf effects is 13g/10min;, system viscosity is 5.2 * 10 during melt-processed
5Pool.
Embodiment 3:
Is being furnished with stirring; heating; add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as dispersing agent; perfluor sulfonyl base vinyl ether 6.3g (n=2) and 0.2g benzoyl peroxide; with air in the high pure nitrogen replacement reaction kettle; feed tetrafluoroethylene 100.8g; R 1216 4.84g; be warming up to 80 ℃ of stirring reaction 3h; reaction finishes postcooling; venting; make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe; filter; get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows its heat decomposition temperature at 374 ℃ by the DTA test, and it is 265 ℃ that DSC tests its melt temperature.
Embodiment 4:
Is being furnished with stirring; heating; add 46.4g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 270g distilled water as dispersing agent; perfluor sulfonyl base vinyl ether 9.2g (n=1) and 0.4g benzoyl peroxide; with air in the high pure nitrogen replacement reaction kettle; feed tetrafluoroethylene 65.6g; R 1216 3.7g; be warming up to 80 ℃ of stirring reaction 5h; reaction finishes postcooling; venting; make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe; filter; get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows its heat decomposition temperature at 379 ℃ by the DTA test, and it is 276 ℃ that DSC tests its melt temperature.
Embodiment 5:
Keep temperature of reaction, the reaction pressure among the embodiment 2 and prolong the reaction times to 12h; the stainless steel autoclave reaction volume is 100L; change perfluor sulfonyl base vinyl ether kind (n=1 or n=2); R 1216 proportion mol ratio is 0.1～7%; test shows its heat decomposition temperature between 360～380 ℃ to the full fluorine copolymer material of preparing through DTA, and it is 260～276 ℃ that DSC tests its melt temperature.
Embodiment 6:
(per) fluoropolymer materials among the embodiment 4 has been carried out melt-spinning, adopt the single screw extrusion machine monofilament to extrude, 320 ℃ of melt zone temperature, 350 ℃ of screw extrusion press temperature, 405 ℃ of nozzle plate temperature, 500 meters/minute of drawing speeds adopt traditional batching with winding apparatus to collect the fiber of extruding, the filament strength of fiber surpasses 30MPa, and the control drawing speed makes filament denier between 50～200 dawn.
Embodiment 7:
More than synthetic have the loading capacity fluoropolymer and all can adopt the spinning processes of embodiment 6 to carry out spinning to prepare the polymer fiber that satisfies service requirements, these fibers can further be woven into polymeric web by Weaving method, and various mould materials are strengthened.
Claims (6)
1, a kind of sulfonic acid fluoride group perfluorinated resin that has has the general structure of formula (I):
In the formula: p, t, q are 10-10000 integer, and p/ (p+t+q)=88～97.5%, q/ (p+t+q)=0.1～7%, t/ (p+t+q)=0.1～7%, n=1 or 2;
The loading capacity value of this resin is 0.01～0.45mmol/g.
2, the application of the described perfluorinated resin of claim 1, this resin in 200～400 ℃ of scopes by melt extruding spinning, prepare fluorine-contained polymerisate fibre material with ion exchanging function.
3, the application of perfluorinated resin as claimed in claim 2 is characterized in that wherein melt extruding at least 400 ℃ of die head temperatures.
4, the application of perfluorinated resin as claimed in claim 2 is characterized in that wherein spinning speed is 1～750m/min.
5, the application of perfluorinated resin as claimed in claim 2, spinning equipment adopts the Langaloy material at high temperature and the part that contacts with resin when it is characterized in that wherein spinning, prevents to introduce foreign ion and pollute fiber in resin.
6, the application of perfluorinated resin as claimed in claim 2 is characterized in that described fluorine-contained polymerisate fibre material with ion exchanging function, is woven into fibrous reticulum by textile technology, as the enhancing net materials of proton exchange membrane and chlor-alkali ionic membrane.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006101662940A CN100519594C (en) | 2006-12-25 | 2006-12-25 | Polymer containing fluorin, and application as material of ion exchange fiber |
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| CNB2006101662940A CN100519594C (en) | 2006-12-25 | 2006-12-25 | Polymer containing fluorin, and application as material of ion exchange fiber |
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| CN100519594C true CN100519594C (en) | 2009-07-29 |
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Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101451634B1 (en) | 2006-08-09 | 2014-10-16 | 스미토모덴코파인폴리머 가부시키가이샤 | Fluororesin membrane, fluororesin composite, porous fluororesin composite, processes for production of them, fluororesin dispersion and separation membrane element |
| CN101693751B (en) * | 2009-10-26 | 2011-03-09 | 山东东岳神舟新材料有限公司 | Functional fluororesins and application thereof |
| CN101757860B (en) * | 2009-11-13 | 2011-09-28 | 山东东岳高分子材料有限公司 | Ion exchange membrane with interpenetrating network structure and preparation method thereof |
| CN101764234B (en) * | 2009-11-13 | 2011-11-23 | 山东东岳高分子材料有限公司 | Interpenetrating crosslinked perfluorinated sulfonic acid ion exchange membrane and preparation method thereof |
| CN101717465B (en) * | 2009-11-13 | 2012-01-11 | 山东东岳高分子材料有限公司 | Main-chain perfluorinated ion polymer and application of same as proton-exchange fiber material |
| CN101794889B (en) * | 2009-12-09 | 2011-11-23 | 山东东岳高分子材料有限公司 | Interpenetrating network ion exchange membrane based on polyurethane and preparation method thereof |
| CN101733005B (en) * | 2009-12-10 | 2011-03-09 | 山东东岳神舟新材料有限公司 | Modified cross-linked perfluorinated ion-exchange membrane |
| WO2011075877A1 (en) * | 2009-12-25 | 2011-06-30 | 山东东岳神舟新材料有限公司 | Perfluorinated ion exchange resin, preparation method and use thereof |
| US20130330637A1 (en) * | 2011-02-24 | 2013-12-12 | Nec Corporation | Separator for electric storage device and electric storage device |
| CN102872833A (en) * | 2011-07-13 | 2013-01-16 | 冯淑芹 | Novel ion exchange fiber and its application |
| CN102505480B (en) * | 2011-09-26 | 2014-08-06 | 淮海工学院 | Preparation method of super chelating ion exchange fibers |
| DE102011087314A1 (en) * | 2011-11-29 | 2013-05-29 | Henkel Ag & Co. Kgaa | Process for the regeneration of aqueous dispersions and cell pack for electrodialysis |
| JP5830782B2 (en) * | 2012-01-27 | 2015-12-09 | 住友電工ファインポリマー株式会社 | Method for producing modified polytetrafluoroethylene microporous membrane and method for producing modified polytetrafluoroethylene porous resin membrane composite |
| GB2575951B (en) | 2017-04-18 | 2022-07-13 | Zhejiang Hyproof Tech Co Ltd | Preparation method for fluorine- and chlorine-containing conductive polymer resin and single- or double-sided filled composite thin film prepared using same |
| CN106977640B (en) * | 2017-04-18 | 2019-06-28 | 浙江汉丞科技有限公司 | The fluorine-containing single side of conducting polymer containing chlorine filled composite film of one kind and preparation method thereof |
| CN111804348B (en) * | 2020-05-30 | 2023-04-14 | 山东东岳高分子材料有限公司 | Reinforcing net for fluorine-containing cation exchange membrane and application thereof |
| CN113717310B (en) * | 2021-11-03 | 2022-02-08 | 国家电投集团氢能科技发展有限公司 | Perfluoro ion exchange resin with high-efficiency ion transmission channel and preparation method thereof |
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| 全氟磺酸离子交换膜的制备与性能研究. 栾英豪等.功能高分子学报，第18卷第1期. 2005 |
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Owner name: SHANDONG HUAXIA SHENZHOU NEW MATERIAL CO., LTD. Free format text: FORMER NAME: DONGGUE SHENZHOU NEW MATERIAL CO., LTD., SHANDONG |
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Address after: 256401 Tangshan Town, Huantai County, Shandong Province Patentee after: Shandong Dongyue Shenzhou New Material Co., Ltd. Address before: 256401 Tangshan Town, Huantai County, Shandong Province Patentee before: Donggue Shenzhou New Material Co., Ltd., Shandong |
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Granted publication date: 20090729 Termination date: 20171225 |