CN101348574A - Fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film - Google Patents

Fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film Download PDF

Info

Publication number
CN101348574A
CN101348574A CNA2008101384249A CN200810138424A CN101348574A CN 101348574 A CN101348574 A CN 101348574A CN A2008101384249 A CNA2008101384249 A CN A2008101384249A CN 200810138424 A CN200810138424 A CN 200810138424A CN 101348574 A CN101348574 A CN 101348574A
Authority
CN
China
Prior art keywords
fiber
film
resin
linking
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2008101384249A
Other languages
Chinese (zh)
Other versions
CN101348574B (en
Inventor
张永明
王军
唐军柯
王汉利
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
Original Assignee
Shandong Dongyue Shenzhou New Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong Dongyue Shenzhou New Material Co Ltd filed Critical Shandong Dongyue Shenzhou New Material Co Ltd
Priority to CN2008101384249A priority Critical patent/CN101348574B/en
Publication of CN101348574A publication Critical patent/CN101348574A/en
Application granted granted Critical
Publication of CN101348574B publication Critical patent/CN101348574B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Abstract

The invention relates to a fiber reinforcement inorganic substance doping crosslinking fluorine-contained iron exchange membrane and a preparation method thereof, which belong to the field of a functional macromolecular composite material. The fluorine-contained ion exchange membrane has cross linked mesh structures, reinforced fibers and doped inorganic substance. The ion exchange membrane prepared by the invention has higher high-temperature electric conductivity, dimensional stability and good mechanical strength.

Description

A kind of fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film
Technical field
The invention belongs to field of functional polymer composites, relate to fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells is a kind ofly directly chemical energy to be converted into the power generation assembly of electric energy by electrochemical means, is considered to the cleaning of 21 century first-selection, generation technology efficiently.(proton exchange membrane PEM) is Proton Exchange Membrane Fuel Cells (proton exchange membrane fuel cell, critical material PEMFC) to proton exchange membrane.
Though the perfluorinated sulfonic acid proton exchange membrane of using is used for many years now, but still exists deficiency not reach the commercialization requirement,, poor dimensional stability low as the high temperature proton conductivity, physical strength are not high.Especially dimensional stability aspect, film are also different because of the different swelling ratios of water-intake rate under different humidity.In addition, when the perfluorinated sulfonic acid exchange membrane is worked under higher temperature,, thereby the efficient of fuel cell is descended greatly because the rapid dehydration of film causes the proton-conducting of film sharply to descend.But high working temperature (being higher than 90 ℃) can improve the anti-carbon monoxide of fuel-cell catalyst greatly.In addition, existing perfluoro sulfonic acid membrane has certain hydrogen or methanol permeability, and especially in direct methanol fuel cell, methanol permeability is very big, becomes fatal problem.Therefore, how to improve perfluorinated sulfonic acid proton exchange film strength, dimensional stability, the perviousness of reduction working medium etc. is the key subjects that fuel cell industries faces.
People have proposed certain methods and have solved these problems at present.Adopt perfluorinated sulfonic resin to flood the porous medium that polytetrafluoroethylene (PTFE) makes as Japanese Patent JP-B-5-75835 and strengthen film strength.Yet the porous medium of this PTFE is because the PTFE material is softer relatively, and enhancement is insufficient, still fails to address the above problem.The Gore-Select series composite membrane liquid of W.L.Gore company exploitation adopts the porous teflon to fill the method (US5547551 of Nafion ionic conductivity liquid, US5635041, US5599614), this film has high proton conductive and bigger dimensional stability, but teflon creep at high temperature is very big, causes degradation.Japanese Patent JP-B-7-68377 also proposed a kind of method, the porous medium made from the proton exchange resins filled polyolefin, but its chemical durability deficiency, thereby permanent stability aspect existing problems.And, make the proton conduction path reduce the proton exchange ability drop of film owing to do not possess the adding of the porous medium of proton conductive ability.
In addition, Japanese Patent JP-A-6-231779 has proposed another kind of Enhancement Method, is to use fluororesin fiber.It adopts the fluorocarbon polymer strongthener enhanced ion-exchange membrane of protofibril form.But this method must add a large amount of relatively strongtheners, and in this case, the processing of film is tending towards difficulty, and the membrane resistance increase takes place possibly.
And European patent EP 0875524B1 discloses, and utilizes the technology of the glass fibre membrane enhancing nafion film of glass fibre non-woven technology preparation, mentions oxide compounds such as silicon-dioxide in this patent simultaneously.But non-woven glass fibre cloth is the base material that must use in this patent, and this will limit the use range of film greatly.
U.S. Pat 6692858 discloses, and polytetrafluoroethylene fiber strengthens the technology of perfluorinated sulfonic resin.In this technology, with perfluor sulfonyl fluoro-resin and polytetrafluoroethylene fiber mix, extrude, making the transition makes fibre-reinforced perfluorinated sulfonic resin.This method can not continuous production because transformation process is consuming time.
The crosslinked thermostability that can improve polymkeric substance, the swelling of minimizing solvent, the physical strength of raising polymkeric substance has been widely used in fields such as separating absorption and various rubber elastomers.At present, for solving the existing problem of perfluorinated sulfonic acid proton exchange membrane, a lot of crosslinking technologicals also are explored.The cross-linking method of the crosslinked generation sulphonyl of SULPHURYL CHLORIDE acid anhydride has been described as US20070031715, formed in the method sulphonyl acid anhydride crosslinking structure can effectively improve the physical strength of film, is that sulphonyl acid anhydride unit is unsettled to alkali but this crosslinking structure has significant disadvantages.US20030032739 then reaches crosslinked purpose by connecting at the alkyl between molecular chain of the alkylsulfonyl on the macromolecular chain.This crosslinked solvent-swollen that can well reduce film.But need a lot of steps to be not suitable for course of industrialization for obtaining this crosslinking structure.The disclosed perfluor sulfonyl fluorine type film that will melt extrude of US6733914 soaks the proton exchange membrane that forms the sulfimide crosslinking structure in ammoniacal liquor, the perfluoro sulfonic acid membrane of Chu Liing has good physical strength and dimensional stability like this.But utilizing the resulting film of this patent will be uneven film, because ammonia enters film by the method for infiltration, ammonia meeting and sulfonic acid fluoride react in the process of infiltration, the sulfonic acid fluoride of reaction will stop ammonia further to the diffusion of film inside, thereby form very high cross-linking density on the surface of film, and that the inside of film does not take place almost is crosslinked.The big crosslinked specific conductivity of film that makes in surface sharply descends.
The disclosed triazine ring crosslinking structure perfluoro sulfonic acid membrane that contains of CN200710013624.7 and US7259208 has good physical strength and dimensional stability equally.
For solving the high temperature proton conduction behavior of sulfonic fluoropolymer film, the inorganic additive that much has the high-temp water-preserving ability is added in the sulfonic fluoropolymer exchange membrane.Choosing these inorganic water conservation machines of inorganic water conservation particle requirement must have: (1) particle has the better water retention capacity that gets, and higher dehydration temperature is just arranged; (2) has intermiscibility preferably with proton exchange resins; (3) particle has certain proton conducting ability; (4) be easy to obtain nanometer particle; (5) particle structure good stability is not accompanied tangible structural changes in suction, dehydration; (6) help keeping or improving the mechanical strength or the physical size stability of proton exchange membrane.Usually the inorganic water conservation particle that adopts is SiO 2, TiO 2, Zr (HPO 4) 2Or ZrO 2Particle, heteropolyacid or solid acid particle, zeolite family mineral particle, stratotype clay mineral such as montmorillonite and intercalation clay mineral thereof etc.
For example Chinese patent CN1862857 discloses in the sulfonic fluoropolymer resin and has added SiO 2Can be etc. inorganic water-holding agent to improve the high-temperature electric conduction performance of proton exchange membrane.
J.Electrochcm.Soc. (V154,2007, p.B288-B295) Nafion resin and zirconium phosphate composite membrane-forming have been described.This film still has very high electric conductivity in relative humidity less than 13%.
But above each patent has only been improved the performance of an aspect of film, does not improve the dimensional stability of film and the electricity under the high temperature low humidity simultaneously and leads.
Summary of the invention
The perfluorinated sulfonic acid ionic membrane that is used for fuel cell need meet the demands: stable, high conductivity, high mechanical strength.Generally speaking, when ion-exchange capacity raise, the equivalent value of (per) fluoropolymer decline (equivalent value EW value reduces, loading capacity IEC=1000/EW) film strength simultaneously also reduced.Therefore, preparation has a macroion exchange capacity, and the ionic membrane that can keep physical strength and high proton conductivity simultaneously is very important.
At the deficiencies in the prior art, the objective of the invention is, a kind of fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film and preparation method are provided.The present invention adopts the fiber enhancing body of film in return, it can keep the polymeric film excellent mechanical intensity, exchange resin forms crosslinking structure can reduce the proton conductive that perviousness is improved polymeric film, and the inorganic doping material can make film at high temperature still possess the good proton ability of leading.
The invention provides a kind of fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film, it is characterized in that: this film has cross-linked network structure, with the EW value is that 600～1300 ion exchange fluoro resin is a matrix, adds forming as the fiber of reinforce and the inorganics that mixes; Specific conductivity 40-150ms/cm, tensile strength 10-60MPa.Described ion exchange fluoro resin is to be formed by Fluorine containing olefine, one or more fluorine-containing alkene monomer and one or more fluorine-containing alkene monomer copolymerization that contain crosslink sites that contain functional group, or the mixture of above-mentioned multipolymer.
Described Fluorine containing olefine is selected from: tetrafluoroethylene, and trifluorochloroethylene, trifluoro-ethylene, R 1216, and/or in the vinylidene one or more, preferred, Fluorine containing olefine is selected from tetrafluoroethylene or trifluorochloroethylene;
The described fluorine-containing alkene monomer that contains functional group is selected from as shown in the formula in the structure shown in (VI), (VII), (VIII) one or more:
R f3CF＝CF(CF 2) dY 2
(VII)
Figure A20081013842400082
Wherein, a, b, c are 0～1 integer, but can not be zero simultaneously;
D is 0～5 integer
N is 0 or 1;
R F1, R F2And R F3Be selected from perfluoroalkyl or freon base respectively; Preferred C 1-C 10Perfluoroalkyl or freon base;
X is selected from F, Cl, Br, or I;
Y 1, Y 2, Y 3Be selected from SO 2M, COOR 3, or PO (OR 4) (OR 5), wherein:
Wherein, M is selected from F, Cl, OR, NR 1R 2, R is selected from methyl, ethyl, propyl group, H, Na, Li, K or ammonium root; R 1And R 2Be selected from H, methyl, ethyl or propyl group respectively; R 3Be selected from H, Na, Li, K, ammonium root, methyl, ethyl or propyl group; R 4, R 5Be selected from H, Na, Li, K, ammonium root, methyl, ethyl or propyl group;
The described fluorine-containing alkene monomer that contains crosslink sites is selected from as shown in the formula in the structure shown in (IX), (X) one or more:
F 2C＝CFR f4Y 4
(IX)
Wherein, Y 4, Y 5Can be selected from Cl, Br, I or CN respectively;
A ', b ', c ' are respectively 0 or 1, but a '+b '+c ' ≠ 0;
X 1Be selected from F, Cl, Br, or I;
N ' is 0 or 1;
R F4, R F5, R F6Be selected from perfluoroalkyl respectively, preferred C 1-C 10Perfluoroalkyl or freon base.
Described cross-linked network structure is selected from one or more as shown in the formula (I), (II), (III), (IV) and/or in the structure (V):
Figure A20081013842400084
Wherein, G 1=CF 2Or O, G 2=CF 2Or O, R fBe C2-C60 perfluor carbochain or chloride perfluor carbochain;
Wherein, R is methylene radical or perfluor methylene radical, and n is 0～10 integer;
Figure A20081013842400092
The method that forms the crosslinking structure shown in the formula (I) comprises heat, light, electron radiation, plasma body, X ray or radical initiator, also can pass through heat, light, electron radiation, plasma body, X ray or action of free radical initiator and form crosslinking structure when one or more linking agents exist.Wherein the structure of employed linking agent is as shown in the formula shown in (XI).
X 2R f7X 3
(XI)
X 2, X 3Be selected from Cl, Br, or I; R F7Be selected from perfluoroalkyl or freon base.
Preferably, described radical initiator is organo-peroxide or azo-initiator; Preferably, initiator is an organic peroxide evocating agent; Preferred, initiator is the perfluor organo-peroxide.
The method that forms (II), (III) crosslinking structure is: utilize sulfonic acid fluoride, SULPHURYL CHLORIDE, sulfuryl bromide type resin and ammonia, and hydrazine, organic diamine or can discharge ammonia through chemical treatment, the substance reaction of hydrazine, organic diamine obtains.
Described organic diamine is alkyl or the fluorine-containing alkyl diamine of C1～C10, describedly can discharge ammonia through chemical treatment, and the material of hydrazine, organic diamine includes but not limited to ammonia, organic or inorganic acid hydrochlorate, urea or the guanidine of hydrazine, organic diamine.
The method that forms (IV) crosslinking structure is that the sulfonic fluoropolymer resin utilizes the chlorsulfonic acid processing to obtain.
The method that forms (V) crosslinking structure be the sulfonic fluoropolymer resin in nitrile group-containing site or nitrile group-containing site fluorine-containing sulfonic acid fluoride resin, contain the SULPHURYL CHLORIDE resin, contain the sulfuryl bromide resin and under heat or sour effect, form.
Described acid is strong protonic acid or Lewis acid; Wherein protonic acid is selected from H 2SO 4, CF 3SO 3H or H 3PO 4Lewis acid is selected from ZnCl 2, FeCl 3, AlCl 3, organotin, antimony organic or organic tellurium.
Include but not limited to one or more mixing of following substances as the fiber of reinforce: polymkeric substance, simple substance, oxide compound, oxysalt class, carbide, nitride, boride, sulfide, silicide, phosphide.Preferably, be selected from glass fibre, fluorocarbon polymer fiber, ceramic fiber, mineral fibre or the oxide fibre one or more as the fiber of reinforce.Selected glass fibre is selected from alkali resistant glass fibre or alkali free glass fibre; Described fluorocarbon polymer fiber is selected from fiber (CN101003588A) or the poly-perfluoro propyl vinyl ether fiber that has ion exchanging function as polytetrafluoroethylene fiber, perfluoroethylene-propylene fiber, self-control; Described ceramic fiber is selected from natural coke jewel fiber or aluminum silicate fiber; Described mineral fibre is selected from silica fiber, silicon carbide fiber or basalt fibre.
Preferably have ion-exchange capacity or surperficial fiber with water conservation group.The fiber (CN101003588A) that has ion exchanging function as self-control, the fluorocarbon polymer fiber of surface silicic acid, sulfonation, sulfation, phosphorylation, hydrophilic modifying, silicic acid, sulfonation, sulfation, phosphorylation oxide compound, carbide, oxysalt class etc. are carried out in the surface.Existing surface modifying method for tetrafluoroethylene all is suitable for the modification to the fluorocarbon polymer fiber, comprises reduction modification, laser radiation modification, plasma modification and the silicic acid activation method of sodium naphthalene solution.Its mesosilicic acid activation method is first-selected method, because it can directly deposit the silicon-dioxide of water conservation at the fluorocarbon polymer fiber surface.Other method of modifying by modification after the fluorine carbon fiber surface hydrophilic group has been arranged, but preferably on this basis more further modification as with the fiber of modification at tetraethoxy, ZrOCl 2-H 3PO 4Or further modification in the titanic acid ester etc.
And this can directly be positioned over tetraethoxy, ZrOCl with these fibers for the surface modification of inorganic fibre 2-H 3PO 4Or carry out modification in the titanic acid ester etc., and also can when fiber, add properties-correcting agent directly to generate modified fibre, as phosphoric acid ester and tetraethoxy are mixed, obtain modified fibre reeling off raw silk from cocoons with the alkali gel.
The concrete grammar of for example silica modified tetrafluoroethylene is placed on SiCl with polytetrafluoroethylene fiber exactly 4Be warmed up to 110 ℃ in the atmosphere after 1 hour and kept 1 hour, be cooled to 60 ℃ again after, water spray is handled and is obtained silica modified polytetrafluoroethylene fiber.
The method of titania modified non-alkali glass is for to place Ti (OEt) with alkali free glass fibre 4Stir in the water mixed system and add the static alkali free glass fibre that obtains the titanium dioxide modification of strong aqua hydrolysis down.
Also have a kind of method triethyl phosphate of modified fibre of separating out jointly to mix to add entry and the static gel of strong aqua 12 hours, utilize this gel to use electrostatic spinning or the technology of reeling off raw silk from cocoons to obtain the phosphoric acid modification silica fiber then with tetraethoxy (1: 100 mass ratio)
The diameter of described fortifying fibre is 0.005 μ m～50 μ m, and length is 0.05 μ m～300mm.The mass ratio of fiber and ion exchange fluoro resin is 0.1～100: 100, preferred 0.5～50: 100, more excellent 1～25: 100.
The inorganic doping thing that is added is selected from: oxide compound, orthophosphoric acid salt and condensed phosphate, polyacid, multi-acid salt, silicate, vitriol selenite and arsenide; Wherein preferred oxides, orthophosphoric acid salt and condensed phosphate, polyacid, multi-acid salt, preferred oxide compound, orthophosphoric acid salt and the condensed phosphate of selecting.The inorganic doping thing is selected from: SiO 2, ZrO 2, TiO 2, BPO 4, Zr 3(PO 4) 4, Zr (HPO 4) 2, H 3PW 12O 40, CsHSO 4, CsH 2PO 4, H-mordenite, H-montmorillonite, HZr 2(PO 4) 3, Zr 3(PO 4) 4, Ce (HPO 4) 2, Ti (HPO 4) 2, and/or Zr 2H (P 3O 10) 2In one or more.
We find unexpectedly, crosslinking structure in inorganic doping thing and the fibre-reinforced fluorine-containing cross-linked doped ion-exchange membrane of the present invention and have synergistic function as the fiber of reinforce, the fuel permeability ratio of the film result of various technology in the past descends greatly, well below traditional ionic membrane.When selecting most preferred inorganic doping thing for use, effect is particularly evident.
The mass ratio of inorganic doping material and ion exchange fluoro resin is 0.1～100: 100, preferred 0.5～50: 100, more excellent 1～25: 100; The particle diameter of the inorganic doping thing that is added is 0.005～50 μ m.
The present invention also provides a kind of preparation method of fibre-reinforced fluorine-containing cross-linked doped ion-exchange membrane, it is characterized in that, utilize solution or melts casting, extrude, hot pressing, curtain coating, silk-screen printing technique, spin coating, spraying or impregnation technology make.
Preferably, the casting of solution or melts, curtain coating,, the step of silk-screen printing technique, spin coating, spraying or dipping is as follows:
(1) ion exchange fluoro resin, fiber, inorganic doping thing, linking agent, acid and/or radical initiator as reinforce are distributed to solvent and form miscellany;
(2) utilize the middle preparation of step (1) solution on flat board, to pass through solution casting, solution casting, silk-screen printing technique, spin coating, spraying or impregnation technology film forming; Will be under 30～300 ℃ temperature during film forming thermal treatment 10～100 minutes;
(3) crosslinked in the film forming, or after the film forming, formation be (I), (II), (III), (IV) and/or (V) shown in crosslinking structure.
Preferably, in the step (1), ion exchange fluoro resin content is 1～80% in the mixture, weight ratio;
Preferably, in the step (1), used solvent is one or more in dimethyl formamide, N,N-DIMETHYLACETAMIDE, methylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, hempa acid amide, acetone, water, ethanol, methyl alcohol, propyl alcohol, Virahol, ethylene glycol or the glycerol; Linking agent described in the step (1) is selected from the described material of formula (XI), ammonia, and hydrazine, organic diamine or can discharge ammonia through chemical treatment, the material of hydrazine, organic diamine,
The method that forms the crosslinking structure shown in the formula (I) comprises heat, light, electron radiation, plasma body, X ray or radical initiator, also can pass through heat, light, electron radiation, plasma body, X ray or action of free radical initiator and form crosslinking structure when one or more linking agents exist.Wherein the structure of employed linking agent is as shown in the formula shown in (XI).
X 2R f7X 3
(XI)
X 2, X 3Be selected from Cl, Br, or I; R F7Be selected from perfluoroalkyl or freon base.
Preferably, described radical initiator is organo-peroxide or azo-initiator; Preferably, initiator is an organic peroxide evocating agent; Preferred, initiator is the perfluor organo-peroxide.
The method that forms (II), (III) crosslinking structure is: utilize sulfonic acid fluoride, SULPHURYL CHLORIDE, sulfuryl bromide type resin and ammonia, and hydrazine, organic diamine or can discharge ammonia through chemical treatment, the substance reaction of hydrazine, organic diamine obtains.
Described organic diamine is alkyl or the fluorine-containing alkyl diamine of C1～C10, describedly can discharge ammonia through chemical treatment, and the material of hydrazine, organic diamine includes but not limited to ammonia, organic or inorganic acid hydrochlorate, urea or the guanidine of hydrazine, organic diamine.
The method that forms (IV) crosslinking structure is that the sulfonic fluoropolymer resin utilizes the chlorsulfonic acid processing to obtain.
The method that forms (V) crosslinking structure be the sulfonic fluoropolymer resin in nitrile group-containing site or nitrile group-containing site fluorine-containing sulfonic acid fluoride resin, contain the SULPHURYL CHLORIDE resin, contain the sulfuryl bromide resin and under heat or sour effect, form.
Described acid is strong protonic acid or Lewis acid; Wherein protonic acid is selected from H 2SO 4, CF 3SO 3H or H 3PO 4Lewis acid is selected from ZnCl 2, FeCl 3, AlCl 3, organotin, antimony organic or organic tellurium.
Preferably, will be under 80～250 ℃ temperature during film forming in the step (2) thermal treatment 20～60 minutes.
Preferably, melt extrude with the step of pressure sintering as follows:
(1). suitable ion exchange fluoro resin, fabric reinforcement, inorganic doping thing, linking agent, acid and/or the radical initiator miscellany of needs preparation according to crosslinked exchange membrane containing fluorine prescription, utilize twin screw extruder, Banbury mixer or mill 200～280 ℃ of mixing; Described ion exchange fluoro resin comprises sulfonic acid fluoride, SULPHURYL CHLORIDE and/or sulfuryl bromide resin;
(2) resin that step (1) is mixed utilizes screw extrusion press or vulcanizing press film forming;
(3) crosslinked in the film forming, or after the film forming; Obtain fibre-reinforced fluorine-containing cross-linked doped ion-exchange membrane;
Preferably, the crosslinked formula described in the step (3) refers to utilize above-mentioned various crosslinked means crosslinked, formation be (I), (II), (III), (IV) and/or (V) shown in crosslinking structure.
Use fiber and crosslinked two kinds of means to act on the physical strength that has improved ionic membrane simultaneously at the present invention-fibre-reinforced fluorine-containing cross-linked doped ion-exchange membrane.We find also that two kinds of means are used has simultaneously not only increased the dimensional stability of film in the length and width direction greatly, but also film is increased greatly in the stability of thickness direction.This point in the past never find; show according to our revision test; though single enhancements can increase the stability of film in the length and width direction to a certain extent; when this stability increases, make very big that the thickness of film increases, even again the film dehydration all can't be returned to original thickness through regular meeting.Our invention has improved this situation.We can also find to compare in the past by the fuel permeability of film, and the result of various technology descends greatly.Though the existence of fiber, inorganic additive can reduce fuel permeability to a certain extent, has synergistic function between fiber of the present invention and the inorganic additive, the ionic membrane that its effect is traditional head and shoulders above.Be higher than general ion-exchange membrane far away owing to have the high-temperature electric conduction of the feasible film that is obtained of existence of water retaining function inorganic doping thing.The conductive ion of the film after simultaneously crosslinked bunch does not have crosslinked ion cluster much smaller because of crosslinked action is limited at a very little space internal ratio, thereby the resistance of the infiltration that reduces to make fuel pass through film of ion cluster increases the energy conversion efficiency that has improved film.But when we adopt surperficial water conservation modification or surface to lead the fiber of proton modification, these fibers not only play mechanical enhanced effect but also play the effect that moisture and proton conduction path are provided for film, the high temperature conductivity of they and water conservation and proton conduction inorganics coupling the raising greatly film.
Embodiment
By the following examples the present invention is further specified, but the present invention is not limited only to following embodiment.
Embodiment 1: with repeating unit be
Figure A20081013842400121
The polymkeric substance of EW=1000 and granularity are the Zr (HPO of 0.005 μ m 4) 2(Zr (HPO 4) 2With the mass ratio of resin be 3: 100) make the aqueous propanol solution of 5wt%, be disposed at concentration then and be 5% peroxidation perfluor malonyl-DMF solution, add polytetrafluoroethylene fiber (diameter 1 μ m, length 50 μ m, with polymer quality than 7: 100), be cast to after the dispersion in the tetrafluoroethylene mold of horizontal positioned, through 80 ℃ of vacuum-dryings after 12 hours, film is peeled off, and is the H of 0.5M in volumetric molar concentration 2SO 4Boil 1 hour in the solution, and use deionized water wash.Obtaining fibre-reinforced individual layer perfluorinated sulfonic acid crosslinked with NaOH solution, sulphuric acid soln processing film successively after the heat treated is (I) species complexity ionic membrane.
Embodiment 2: with repeating unit be
Figure A20081013842400122
The polymkeric substance of EW=800 and granularity are 0.03 μ mSiO 2(SiO 2With the mass ratio of perfluorinated sulfonic resin be 5: 100), alkali free glass fibre (diameter 0.05 μ m length 5um, alkali free glass fibre is 1: 40 with the mass ratio of perfluorinated sulfonic resin) mixes, and extrudes and obtains the film that thickness is 30 μ m.Be soaked in NH 4In the DMF solution of Cl 5 hours.Then the film that soaks is placed triethylamine 2 hours at 200 ℃, get crosslinked film.With this film is the ion-exchange membrane of (11) with the crosslinking structure that KOH solution, hydrochloric acid soln are handled successively.
Embodiment 3: with repeating unit be
Figure A20081013842400123
The polytetrafluoroethylene fiber of the polymkeric substance of EW=1200, silicic acid modification (diameter 0.2 μ m, length 80 μ m, with the weight ratio of polymkeric substance be 7: 100), tin tetraphenyl is extruded into the film of 50 μ m with twin screw extruder, then film is heated to 230 ℃ 10 hours crosslinking structure be the film that (V) plants.This film is used LiOH successively, and salpeter solution is handled and is obtained cross-linking ion membrane.
Embodiment 4: with repeating unit be
Figure A20081013842400131
The polymkeric substance of EW=1100, H 3PW 12O 40(polymkeric substance and H 3PW 12O 40Mass ratio 100: 20), poly-perfluoro propyl vinyl ether fiber (diameter 0.005 μ m length 0.5um, the mass ratio of poly-perfluoro propyl vinyl ether fiber and perfluorinated sulfonic resin is 0.5: 10) and urea obtain the ionic membrane that crosslinking structure is (II) kind with alkali and acid treatment successively behind 170 ℃ of heating 5h after being hot pressed into 100 μ m films.
Embodiment 5: with repeating unit be
Figure A20081013842400132
The polymer weight ratio of the polymkeric substance of EW=700 and embodiment 1 is mixed at 2: 3, adds CsHSO 4(portions of resin CsHSO 4Be 100: 40 mass ratio) and peroxidation perfluor bay two acyls, 1,4-diiodo-Octafluorobutane mixes, be dissolved in the solution of 20% (weight) made among the DMF, with homemade fiber (with reference to the method preparation of CN101003588A) (diameter 5 μ m length 100 μ m with ion exchanging function, fiber is 1: 5 with the mass ratio of resin) mix with it, the thickness that utilizes the method system of curtain coating then is the individual layer perfluorinated sulfonic acid cross-linking ion membrane of 50 μ m.It must crosslinking structure be formula (I) and film (IV) that this ion-exchange membrane be impregnated in the chlorsulfonic acid
Embodiment 6: with repeating unit be
Figure A20081013842400133
The polymkeric substance of EW=1300 and 0.8 μ mZrO 2(with the mass ratio of resin be 2: 100), 2,2'-Azobis(2,4-dimethylvaleronitrile), 1,4-diiodo-Octafluorobutane is dissolved among the DMF, adds 5 μ m H-mordenite powder (mass ratio of H-mordenite and resin is 7: 100) again, ZrO 2-H 3The silicon carbide fiber of PO4 modification (diameter 5 μ m length 100 μ m, the mass ratio of fiber and resin is 1: 100) is mixed in N-Methyl pyrrolidone, and the method for spraying is at 170 ℃, and the crosslinking structure that 60min makes 60 μ m is the perfluoro sulfonic acid membrane of formula (I).
Embodiment 7: with repeating unit be
Figure A20081013842400134
The polymer dissolution of EW=1300 is in the hempa acid amide, add 0.7 μ m H-montmorillonite and silica fiber (diameter 15 μ m length 100 μ m then, the mass ratio of fiber and resin is 3: 100, the H-montmorillonite is 10: 100 with the mass ratio of resin) mix after, by the spraying coating process method, obtain the film that thickness is 40 μ m.Film is handled 100min down at 230 ℃.Obtaining crosslinking structure is the individual layer perfluoro sulfonic acid membrane of formula (I).
Embodiment 8: with repeating unit be
Figure A20081013842400141
The polymkeric substance of EW=1300, benzoyl peroxide, 1,14-diiodo-20 fluorine ten alkane are dissolved in the dimethyl sulfoxide (DMSO), have the fiber (mass ratio of fiber and perfluorinated sulfonic resin is 1: 5) and the 4 μ mTiO of ion exchanging function then with natural coke jewel fiber and self-control 2(is 23: 100 with the weight ratio of polymkeric substance) mixed by the silk-screen printing technique method and obtained the film that thickness is 35 μ m.Film is handled 3min down at 160 ℃.Obtaining crosslinking structure is the inorganic fibre enhancing adulterated full fluorin sulfonate film of formula (I).
Embodiment 9:
With repeating unit be
Figure A20081013842400142
EW=1250 polymkeric substance and CsH 2PO 4Mix by 100: 20 (weight ratio), be dissolved in then and obtain 30% solution in the hempa acid amide, add basalt fibre (diameter 30 μ m length 3mm, the mass ratio of fiber and resin is 0.01: 100) by the pouring technology method, obtain the film that thickness is 40 μ m.Film is handled 100min down at 230 ℃, obtain the fibre-reinforced individual layer adulterated full fluorin sulfonate film of crosslinked formula (I).
Embodiment 10: with repeating unit be
The polymkeric substance of EW=900 and 0.03 μ mSiO 2(with the mass ratio of perfluorinated sulfonic resin be 5: 100), the modification SiO that etherophosphoric acid and tetraethoxy gel reel off raw silk from cocoons 2Fiber (diameter 0.05 μ m length 5mm, modification SiO 2Fiber is 1: 40 with the mass ratio of perfluorinated sulfonic resin) mix, extrude and obtain the film that thickness is 130 μ m.Soak and NH 3DMF solution in 5 hours.Get the film that (II) plants crosslinking structure at 200 ℃.With this film alkali lye, the cross linking membrane that acid solution is handled.
Embodiment 11
With repeat unit structure be
Figure A20081013842400144
The polymkeric substance of EW=1200,1 micron BPO 4Mix by 100: 12 (weight ratio), add LaMnO 3Oxide fibre (0.07 micron of diameter 0.005 μ m length, the mass ratio of fiber and resin is 25: 100), tin tetraphenyl is extruded into the film of 50 μ m with twin screw extruder, then film is heated to 230 ℃ and obtains the films that (V) plants crosslinking structure in 10 hours.This film was placed 35% hydrazine hydrate kind 10 hours, taking out post-heating was had (V) to plant the film that crosslinking structure and (III) plant crosslinking structure, this film alkali lye, the cross linking membrane of acid solution processing in 5 hours simultaneously again.
Embodiment 12: with repeating unit be
Figure A20081013842400151
The polymkeric substance of EW=700 and repeating unit are
Figure A20081013842400152
The polymkeric substance of EW=1300 (the resin quality ratio is 1: 0.2) and 10nmZrO 2(with the mass ratio of polymkeric substance be 2: 100) and 20% the solution in DMF, made of 2,2'-Azobis(2,4-dimethylvaleronitrile) mixed dissolution, fiber (CN101003588A) (the diameter 15 μ m length 20mm that self-control had ion exchanging function, fiber is 0.5: 5 with the mass ratio of resin) mix with it, then through curtain coating, heat to such an extent that thickness is that the individual layer perfluorinated sulfonic acid of 45 μ m contains (I) and plants crosslinking structure, again this ion-exchange membrane is put in the film that obtains (IV) crosslinking structure in the chlorsulfonic acid again.
Embodiment 13: with repeating unit be
Figure A20081013842400153
The polymkeric substance of EW=1200 and fentin hydroxide and 8 μ mZrO 2(with the mass ratio of resin be 2: 100), be scattered among the DMF, with TiO 2The BN fiber of modification (diameter is 0.01 micron, and length is 120 microns, account for the solution total mass 5%) method by casting is at 170 ℃, 60min makes the perfluorinated sulfonic acid BN fiber reinforced film that the having of 20 μ m (V) planted crosslinking structure.
Embodiment 14: with repeating unit be
Figure A20081013842400154
The TiO of the polymkeric substance of EW=1200 and 0.02 micron 2Mix (mass ratio is: 100: 3), (diameter is 0.21 micron to silicon ester modification SiC fiber, length is 120 microns, accounts for the method that 7% usefulness of solution polymer total mass melt extrudes and prepares unitary film, this film is at high temperature handled obtaining the film that crosslinking structure is formula II in 3 hours then.
Embodiment 15: with repeating unit be
Figure A20081013842400155
Polymkeric substance and repeating unit be:
Figure A20081013842400161
Polymkeric substance be to add Ti (HPO after 2: 3 the mixed with mass ratio 4) 2((particle diameter is 0.05 micron, account for gross weight 12%), SiN (0.1 micron of diameter, length are 300 microns) and SiC fiber (0.5 micron of diameter, length are 3 millimeters), Ce (HPO 4) 2(granularity is 0.5 micron), HTaWO 6(polymkeric substance: SiN: SiC: Ce (HPO 4) 2: HTaWO 6=100: 2: 6: 4: 8, weight ratio), in sieve bar forcing machine mixed melting to extrude and obtain thickness be 50 microns film.Again above-mentioned film was soaked 30 minutes with the tetrafluoro quadrol, and then at 170 ℃ of crosslinked inorganic adulterated full fluorin sulfonate films that add the crosslinked formula of thermosetting (III).
Embodiment 16: with repeating unit be
Polymkeric substance with repeating unit be
Figure A20081013842400163
Polymkeric substance be to be scattered among the DMSO after 1: 5 the mixed by mass ratio, in above-mentioned mixed solution, add particle diameter again and be 0.05 micron Zr 3(PO 4) 4And SiO 2Fiber (0.05 micron of diameter, long 10 microns) and SiN fiber (0.5 micron of diameter, long 50 microns), wherein portions of resin Zr 3(PO 4) 4: SiO2: SiN=100: 12.4: 5: 3. form the inorganics doped film of triazine crosslinked ring by the casting method film forming and with film at 230 ℃ after adding a spot of antimony organic catalyzer again.
Embodiment 17: with repeating unit be
Figure A20081013842400164
EW=1250 polymkeric substance and particle diameter are 10 microns BPO 4Mix by 100: 12 (weight ratio), be scattered in then and obtain 19% solution in the hempa acid amide, add LaMnO 3Oxide fibre (0.07 micron of diameter 0.005 μ m length, the mass ratio of fiber and resin is 25: 100) passes through the silk-screen printing technique method, and handles 300min under the irradiation of UV-light, and obtaining crosslinking structure is the fibre-reinforced adulterated full fluorin sulfonate film of I.
Embodiment 18: with repeating unit be
Figure A20081013842400165
Polymkeric substance, tertbutanol peroxide, 1,4-diiodo-octafluoro fourth is dissolved in fiber (mass ratio of fiber and perfluorinated sulfonic resin is 1: 5) and the Ti0 that has ion exchanging function among the DMF with natural coke jewel fiber and self-control 2Mixing obtains the film that thickness is 25 μ m by the silk-screen printing technique method.Film is handled 3min down at 160 ℃.Obtain the inorganic fibre enhancing adulterated full fluorin sulfonate film of crosslinked formula for (I).
Embodiment 19: with repeating unit be
Figure A20081013842400171
The polymkeric substance of EW=700 and repeating unit are
Figure A20081013842400172
The polymkeric substance of EW=1300 (the resin quality ratio is 1: 0.5) and 50nmZrO 2(with the mass ratio of polymkeric substance be 2: 100) be dissolved in 22% the solution of making among the DMF, fiber (CN101003588A) (the diameter 15 μ m length 20mm that self-control had ion exchanging function, fiber is 0.5: 5 with the mass ratio of resin) mix with it, then through curtain coating, heating and X ray are handled to such an extent that thickness is that the individual layer perfluorinated sulfonic acid of 45 μ m contains (I) and plants crosslinking structure, again this ion-exchange membrane are put in the film that obtains (IV) crosslinking structure in the chlorsulfonic acid again.
Embodiment 20: with repeating unit be
Figure A20081013842400173
The polymkeric substance of EW=900 and 0.03 μ mSiO 2(with the mass ratio of perfluorinated sulfonic resin be 5: 100), alkali free glass fibre (diameter 0.05 μ m length 5um, alkali free glass fibre is 1: 40 with the mass ratio of perfluorinated sulfonic resin) mixes, and extrudes and obtains the film that thickness is 30 μ m.Soaked in the DMF solution with 15 hours.Get the film that (III) plants crosslinking structure at 200 ℃.With this film alkali lye, the cross linking membrane that acid solution is handled.
Comparative example 21: utilize 10%nafion DMF solution adds 0.03 μ mSiO 2(SiO 2With the mass ratio of perfluorinated sulfonic resin be 5: 100) utilize the method for cast to obtain the inorganics doped ion-exchange membrane of 60 micron thickness 170 ℃ of processing.
Experimental example 22
Performance to various films characterizes, and the results are shown in Table 1.As can be seen from Table 1, performance such as 100 of fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film ℃ of specific conductivity, tensile strength, hydrogen permeate electric current all is better than common inorganics doped ion-exchange membrane.
The various films of table 1 characterize
Figure A20081013842400181

Claims (9)

1. fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film, it is characterized in that: this film has cross-linked network structure, with the EW value is that 600～1300 ion exchange fluoro resin is a matrix, interpolation forms as the fiber of reinforce and the inorganics that mixes, specific conductivity 40-150ms/cm, tensile strength 10-60MPa;
Described ion exchange fluoro resin is to be formed by Fluorine containing olefine, one or more fluorine-containing alkene monomer and one or more fluorine-containing alkene monomer copolymerization that contain crosslink sites that contain functional group, or the mixture of above-mentioned multipolymer;
Described Fluorine containing olefine is selected from: tetrafluoroethylene, and trifluorochloroethylene, trifluoro-ethylene, R 1216, and/or in the vinylidene one or more, preferred, Fluorine containing olefine is selected from tetrafluoroethylene or trifluorochloroethylene;
The described fluorine-containing alkene monomer that contains functional group is selected from as shown in the formula in the structure shown in (VI), (VII), (VIII) one or more:
R f3CF＝CF(CF 2) dY 2
(VII)
Figure A2008101384240002C2
Wherein, a, b, c are 0～1 integer, but can not be zero simultaneously;
D is 0～5 integer
N is 0 or 1;
R F1, R F2And R F3Be selected from perfluoroalkyl or freon base respectively; Preferred C 1-C 10Perfluoroalkyl or freon base;
X is selected from F, Cl, Br, or I;
Y 1, Y 2, Y 3Be selected from SO 2M, COOR 3, or PO (OR 4) (OR 5), wherein:
M is selected from F, Cl, OR, NR 1R 2, R is selected from methyl, ethyl, propyl group, H, Na, Li, K or ammonium root; R 1And R 2Be selected from H, methyl, ethyl or propyl group respectively; R 3Be selected from H, Na, Li, K, ammonium root, methyl, ethyl or propyl group; R 4, R 5Be selected from H, Na, Li, K, ammonium root, methyl, ethyl or propyl group;
The described fluorine-containing alkene monomer that contains crosslink sites is selected from as shown in the formula in the structure shown in (IX), (X) one or more:
F 2C＝CFR f4Y 4
(IX)
Figure A2008101384240002C3
In the tool, Y 4, Y 5Can be selected from Cl, Br, I or CN respectively;
A ', b ', c ' are respectively 0 or 1, but a '+b '+c ' ≠ 0;
X 1Be selected from F, Cl, Br, or I;
N ' is 0 or 1;
R F4, R F5, R F6Be selected from perfluoroalkyl respectively, preferred C 1-C 10Perfluoroalkyl or freon base;
Described cross-linked network structure is selected from one or more as shown in the formula (I), (II), (III), (IV) and/or in the structure (V):
Figure A2008101384240003C1
Wherein, G 1=CF 2Or O, G 2=CF 2Or O, R fBe C2-C60 perfluor carbochain or chloride perfluor carbochain;
Figure A2008101384240003C2
Wherein, R is methylene radical or perfluor methylene radical, and n is 0～10 integer;
Figure A2008101384240003C3
2. fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film as claimed in claim 1 is characterized in that: be selected from glass fibre, fluorocarbon polymer fiber, ceramic fiber, mineral fibre or the oxide fibre one or more as the fiber of reinforce; Described glass fibre is selected from alkali resistant glass fibre or alkali free glass fibre; Described fluorocarbon polymer fiber is selected from fiber (CN101003588A) or the poly-perfluoro propyl vinyl ether fiber that has ion exchanging function as polytetrafluoroethylene fiber, perfluoroethylene-propylene fiber, self-control; Described ceramic fiber is selected from natural coke jewel fiber or aluminum silicate fiber; Described mineral fibre is selected from silica fiber, silicon carbide fiber or basalt fibre;
The diameter of described fortifying fibre is 0.005 μ m～50 μ m, and length is 0.05 μ m～300mm; The mass ratio of fiber and ion exchange fluoro resin is 0.1～100: 100, preferred 0.5～50: 100.
3. fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film as claimed in claim 1, it is characterized in that: the inorganic doping thing that is added is selected from: oxide compound, orthophosphoric acid salt and condensed phosphate, polyacid, multi-acid salt, preferred oxide compound, orthophosphoric acid salt and the condensed phosphate of selecting.Preferably, the inorganic doping thing is selected from: SiO 2, ZrO 2, TiO 2, BPO 4, Zr 3(PO 4) 4, Zr (HPO 4) 2, H 3PW 12O 40, CsHSO 4, CsH 2PO 4, H-mordenite, H-montmorillonite, HZr 2(PO 4) 3, Zr 3(PO 4) 4, Ce (HPO 4) 2, Ti (HPO 4) 2, and/or Zr 2H (P 3O 10) 2In one or more; The mass ratio of inorganic doping material and ion exchange fluoro resin is 0.1～100: 100, preferred 0.5～50: 100; The particle diameter of the inorganic doping thing that is added is 0.005～50 μ m.
4. the preparation method of a fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film as claimed in claim 1, it is characterized in that, utilize solution or melts casting, extrude, hot pressing, curtain coating, silk-screen printing technique, spin coating, spraying or impregnation technology make.
5. the preparation method of a fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film as claimed in claim 4 is characterized in that, the step of the casting of solution or melts, curtain coating, silk-screen printing technique, spin coating, spraying or dipping is as follows:
(1) ion exchange fluoro resin, fiber, inorganic doping thing, linking agent, acid and/or radical initiator as reinforce are distributed to solvent and form miscellany; Described linking agent is selected from the described material of formula (XI), ammonia, hydrazine, organic diamine or can discharges ammonia through chemical treatment, the material of hydrazine, organic diamine; Ion exchange fluoro resin content is 1～80% in the mixture, weight ratio;
(2) utilize the middle preparation of step (1) solution on flat board, to pass through solution casting, solution casting, silk-screen printing technique, spin coating, spraying or impregnation technology film forming; Will be under 30～300 ℃ temperature during film forming thermal treatment 10～100 minutes;
(3) crosslinked in the film forming, or after the film forming, formation be (I), (II), (III), (IV) and/or (V) shown in crosslinking structure.
6. the preparation method of a fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film as claimed in claim 5, it is characterized in that, in the step (1), used solvent is one or more in dimethyl formamide, N,N-DIMETHYLACETAMIDE, methylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, hempa acid amide, acetone, water, ethanol, methyl alcohol, propyl alcohol, Virahol, ethylene glycol or the glycerol; Will be under 80～250 ℃ temperature during film forming in the step (2) thermal treatment 20～60 minutes.
7. the preparation method of a fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film as claimed in claim 5, it is characterized in that, the method that forms the crosslinking structure shown in the formula (I) comprises heat, light, electron radiation, plasma body, X ray or radical initiator, also can pass through heat, light, electron radiation, plasma body, X ray or action of free radical initiator and form crosslinking structure when one or more linking agents exist; Wherein the structure of employed linking agent is as shown in the formula shown in (XI):
X 2R f7X 3
(XI)
X 2, X 3Be selected from Cl, Br, or I; R F7Be selected from perfluoroalkyl or freon base;
Described radical initiator is organo-peroxide or azo-initiator; Preferably, initiator is an organic peroxide evocating agent; Preferred, initiator is the perfluor organo-peroxide;
The method that forms (II), (III) crosslinking structure is: utilize sulfonic acid fluoride, SULPHURYL CHLORIDE, sulfuryl bromide type resin and ammonia, and hydrazine, organic diamine or can discharge ammonia through chemical treatment, the substance reaction of hydrazine, organic diamine obtains;
Described organic diamine is alkyl or the fluorine-containing alkyl diamine of C1～C10, describedly can discharge ammonia through chemical treatment, and the material of hydrazine, organic diamine includes but not limited to ammonia, organic or inorganic acid hydrochlorate, urea or the guanidine of hydrazine, organic diamine;
The method that forms (IV) crosslinking structure is that the sulfonic fluoropolymer resin utilizes the chlorsulfonic acid processing to obtain;
The method that forms (V) crosslinking structure be the sulfonic fluoropolymer resin in nitrile group-containing site or nitrile group-containing site fluorine-containing sulfonic acid fluoride resin, contain the SULPHURYL CHLORIDE resin, contain the sulfuryl bromide resin and under heat or sour effect, form;
Described acid is strong protonic acid or Lewis acid; Wherein protonic acid is selected from H 2SO 4, CF 3SO 3H or H 3PO 4Lewis acid is selected from ZnCl 2, FeCl 3, AlCl 3, organotin, antimony organic or organic tellurium.
8. the preparation method of a fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film as claimed in claim 4 is characterized in that, melt extrudes with the step of pressure sintering as follows:
(1). suitable ion exchange fluoro resin, fabric reinforcement, inorganic doping thing, linking agent, acid and/or the radical initiator miscellany of needs preparation according to crosslinked exchange membrane containing fluorine prescription, utilize twin screw extruder, Banbury mixer or mill 200～280 ℃ of mixing; Described ion exchange fluoro resin comprises sulfonic acid fluoride, SULPHURYL CHLORIDE and/or sulfuryl bromide resin;
(2) resin that step (1) is mixed utilizes screw extrusion press or vulcanizing press film forming;
(3) crosslinked in the film forming, or after the film forming; Obtain fibre-reinforced fluorine-containing cross-linked doped ion-exchange membrane.
9. the preparation method of a fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film as claimed in claim 8, it is characterized in that, crosslinked described in the step (3) is meant that to utilize above-mentioned various crosslinked means crosslinked, formation be (I), (II), (III), (IV) and/or (V) shown in crosslinking structure.
CN2008101384249A 2008-07-22 2008-07-22 Fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film Active CN101348574B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2008101384249A CN101348574B (en) 2008-07-22 2008-07-22 Fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2008101384249A CN101348574B (en) 2008-07-22 2008-07-22 Fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film

Publications (2)

Publication Number Publication Date
CN101348574A true CN101348574A (en) 2009-01-21
CN101348574B CN101348574B (en) 2011-06-08

Family

ID=40267564

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008101384249A Active CN101348574B (en) 2008-07-22 2008-07-22 Fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film

Country Status (1)

Country Link
CN (1) CN101348574B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101733014A (en) * 2009-12-10 2010-06-16 山东东岳神舟新材料有限公司 Fiber composite and multi-layer perfluorinated cross-linked doped ion-exchange membrane
CN101851382A (en) * 2010-05-25 2010-10-06 山东东岳高分子材料有限公司 Fiber and modified silica-doped fluorine-containing ion film and preparation method thereof
CN101733006B (en) * 2009-12-10 2011-01-26 山东东岳神舟新材料有限公司 Doped and fiber-modified imide cross-linking perfluorinated ion exchange membrane
CN102522574A (en) * 2011-12-24 2012-06-27 山东东岳高分子材料有限公司 Diaphragm for flow battery and preparation method thereof
CN113471464A (en) * 2021-05-19 2021-10-01 深圳先进技术研究院 Material for battery diaphragm, material preparation method and battery diaphragm

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1139472B1 (en) * 2000-03-31 2006-07-05 Asahi Glass Company Ltd. Electrolyte membrane for solid polymer type fuel cell and producing method thereof
US6982303B2 (en) * 2000-05-19 2006-01-03 Jochen Kerres Covalently cross-linked polymers and polymer membranes via sulfinate alkylation
US8993193B2 (en) * 2005-08-05 2015-03-31 GM Global Technology Operations LLC Sulfonated perfluorosulfonic acid polyelectrolyte membranes
CN100588676C (en) * 2007-02-25 2010-02-10 山东东岳神舟新材料有限公司 Crosslinked fluoride proton exchange film, its production and use

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101733014A (en) * 2009-12-10 2010-06-16 山东东岳神舟新材料有限公司 Fiber composite and multi-layer perfluorinated cross-linked doped ion-exchange membrane
CN101733006B (en) * 2009-12-10 2011-01-26 山东东岳神舟新材料有限公司 Doped and fiber-modified imide cross-linking perfluorinated ion exchange membrane
CN101733014B (en) * 2009-12-10 2011-06-08 山东东岳神舟新材料有限公司 Fiber composite and multi-layer perfluorinated cross-linked doped ion-exchange membrane
CN101851382A (en) * 2010-05-25 2010-10-06 山东东岳高分子材料有限公司 Fiber and modified silica-doped fluorine-containing ion film and preparation method thereof
CN102522574A (en) * 2011-12-24 2012-06-27 山东东岳高分子材料有限公司 Diaphragm for flow battery and preparation method thereof
CN102522574B (en) * 2011-12-24 2014-10-01 山东东岳高分子材料有限公司 Diaphragm for flow battery and preparation method thereof
CN113471464A (en) * 2021-05-19 2021-10-01 深圳先进技术研究院 Material for battery diaphragm, material preparation method and battery diaphragm
CN113471464B (en) * 2021-05-19 2022-07-08 深圳先进技术研究院 Material for battery diaphragm, material preparation method and battery diaphragm

Also Published As

Publication number Publication date
CN101348574B (en) 2011-06-08

Similar Documents

Publication Publication Date Title
CN101350418B (en) Microporous-film-and-fiber-reinforced multilayer fluorine-containing cross-linking doping ionic membrane and preparation method thereof
CN100580987C (en) Microporous-film-reinforced fluorine-containing cross-linking ion-exchange membrane and preparation method thereof
CN101320818B (en) Fibre reinforced multi-layer fluorine-contained ionic exchange film
CN101320817B (en) Fibre reinforced multi-layer fluorine-contained cross-linking doping ionic membrane and preparation method thereof
CN101330150B (en) Inorganic doping cross-linking multilayer ion membrane containing fluorine and preparation method thereof
CN101721922B (en) Microporous film enhanced multilayer fluorine-containing crosslinked ion-doped film and preparation method thereof
CN101350420B (en) Inorganics doping multi-layer fluorine-containing ion-exchange film
CN101348574B (en) Fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film
CN101319051B (en) Fibre reinforcement inorganics doped multi-layer fluorine ion exchange containing film
CN100589268C (en) Microporous-film-reinforced multilayer fluorine-containing cross-linking doping ionic membrane and preparation method thereof
CN101350415B (en) Microporous-film-reinforced fluorine-containing cross-linking doping ion-exchange membrane and preparation method thereof
CN101733005B (en) Modified cross-linked perfluorinated ion-exchange membrane
CN101350413B (en) Fiber-reinforced multilayer fluorine-containing cross-linking ionic membrane and preparation method thereof
CN101670246B (en) Multilayer fluorine-contained crosslinking doping ionic membrane with reinforced microporous membrane and preparation method thereof
CN101350419B (en) Fiber-reinforced fluorine-containing cross-linking ionic membrane and preparation method thereof
CN101764232B (en) Fluorinated proton exchange membrane with cross-linked network structure and preparation thereof
CN101733006B (en) Doped and fiber-modified imide cross-linking perfluorinated ion exchange membrane
CN101733004B (en) Doped and fiber-modified cross-linking perfluorinated ion exchange membrane
CN101333322B (en) Mineral-doped fluor-containing cross-linking ion exchanger membrane and method for preparing same
CN100595961C (en) Multilayer cross-linking ionic membrane containing fluorine and preparation method thereof
CN101333323B (en) Mineral-doped fluor-containing cross-linking ion exchanger membrane and method for preparing same
CN101745323B (en) Fiber reinforced composite multi-layer total fluoride crosslinking ionic membrane and preparation method thereof
CN101733014B (en) Fiber composite and multi-layer perfluorinated cross-linked doped ion-exchange membrane
CN101685868B (en) Microporous membrane enhanced multilayer fluorine-containing cross-linked doped ion-exchange membrane and preparation method thereof
CN101685867B (en) Microporous membrane enhanced multilayer fluorine-containing cross-linked doped ion-exchange membrane and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C56 Change in the name or address of the patentee

Owner name: SHANDONG HUAXIA SHENZHOU NEW MATERIAL CO., LTD.

Free format text: FORMER NAME: DONGGUE SHENZHOU NEW MATERIAL CO., LTD., SHANDONG

CP01 Change in the name or title of a patent holder

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

TR01 Transfer of patent right

Effective date of registration: 20201207

Address after: 256401 Zibo Huantai County, Shandong Province, Tangshan town Dongyue Fluorosilicic Industrial Park

Patentee after: Shandong Dongyue future hydrogen energy materials Co., Ltd

Address before: 256401 Tangshan Town, Huantai County, Shandong Province

Patentee before: SHANDONG HUAXIA SHENZHOU NEW MATERIAL Co.,Ltd.

TR01 Transfer of patent right