CN101745321B - Micro-porous membrane reinforced perfluorinated cross-linking ion exchange membrane and preparation method thereof - Google Patents
Micro-porous membrane reinforced perfluorinated cross-linking ion exchange membrane and preparation method thereof Download PDFInfo
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- CN101745321B CN101745321B CN2009102311343A CN200910231134A CN101745321B CN 101745321 B CN101745321 B CN 101745321B CN 2009102311343 A CN2009102311343 A CN 2009102311343A CN 200910231134 A CN200910231134 A CN 200910231134A CN 101745321 B CN101745321 B CN 101745321B
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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
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- 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 micro-porous membrane compounded perfluorinated cross-linking ion exchange membrane and a preparation method thereof, which belongs to the field of functional polymer composite material. The ion exchange membrane adopts the micro-porous membrane as the reinforce, and uses fluoride bearing ion exchange resin to form a membrane with a diplex cross-linking reticular structure of triazine ring cross-linking and the physical bonding cross-linking of high valence metallic compound and acid exchange base group. The ion exchange membrane prepared in the invention has high dimension stability and good mechanical strength, and particularly has superior gas permeation resistance.
Description
Technical field
The invention belongs to field of functional polymer composites, relate to the perfluor cross-linking amberplex that a kind of microporous barrier strengthens.
Background technology
Proton Exchange Membrane Fuel Cells is a kind ofly directly chemical energy to be converted into the TRT 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 PEM.
Now the perfluorinated sulfonic acid PEM that uses have good proton-conducting and chemical stability under (80 ℃) and the higher humidity at a lower temperature.But they also have a lot of defectives:, poor chemical stability not high as poor dimensional stability, mechanical strength etc.Film water absorption rate and size of causing because of suction under different humidity expand also different, and when film during at different operating mode down conversion, the size of film also will so change.Finally cause PEM generation mechanical damage so repeatedly.In addition, the reaction of the positive pole of fuel cell usually produces the material that a large amount of hydroxyl free radicals and hydrogen peroxide etc. have strong oxidizing property, and non-fluorin radical on these materials meeting attack film-forming resin molecules causes film generation chemical degradation and damaged, foaming.At last, when the operating temperature of perfluorinated sulfonic acid exchange membrane is higher than 90 ℃,, thereby the efficient of fuel cell is descended greatly owing to the rapid dehydration of film causes the proton-conducting of film sharply to descend.But high operating temperature can improve the anti-carbon monoxide of fuel-cell catalyst greatly.Be exactly that existing perfluoro sulfonic acid membrane all has certain hydrogen or methanol permeability in addition, especially in DMFC, methanol permeability is very big, and this becomes fatal problem.Therefore, how to improve the proton conduction efficient under perfluorinated sulfonic acid proton exchange film strength, dimensional stability and the high temperature, the permeability of reduction working media etc. and become the key subjects that fuel cell industries faces.
In the U.S. Pat 5834523 (Ballard company) the α of sulfonation, β, β-trifluorostyrene sulfonic acid and m-trifluoromethyl-α, β, methyl alcohol/the propanol solution of β-trifluorostyrene copolymer is immersed in the hole of porous PTFE film of swelling, under 50 ℃ of conditions, dry then, obtain composite membrane.But this method need repeat repeatedly, and polymer fully is filled in the hole of PTFE microporous barrier.
In US5547551, the employing mass concentration is 5% perfluor sulfoacid resin solution, and strengthens the wetability of solution to wherein adding a certain amount of non-ionic surface active agent, thereby promotes the immersion of perfluorinated resin to fenestra in the PTFE microporous barrier.Mixed solution is brushed on the thick polytetrafluoroethylene (PTFE) varicosity of 20 μ m with brush, after handling under 140 ℃, composite membrane is immersed in the activating agent that removes in the isopropyl alcohol in the striping.Resin can be blocked the micropore among the PTFE fully in this composite membrane.
In WO98/51733, by hot pressing under 310 ℃ of vacuum states together the PTFE film of the film of the thick sulfuryl fluoride type of 25 μ m and Gore company.Then film is hydrolyzed in the KOH of dimethyl sulfoxide (DMSO) solution, makes in the film-SO
2The F group changes into-SO
3 -At last be coated with three times 5% sulfonate resin solution, in 150 ℃ of vacuum drying ovens, make film become as a whole in the one side of porous PTFE film.This method is too consuming time, and microporous barrier is difficult to be filled by sulfonate resin full.
But there is defective in these methods, only use perfluoro sulfonic acid membrane that microporous barrier strengthens often, always have some micropores can not be by complete filling, thereby cause film to have very high gas permeability.
Crosslinking technological can improve the mechanical strength of the heat endurance of polymer, the swelling that reduces solvent, raising polymer.Therefore, crosslinking technological 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 PEM, explored and studied multiple crosslinking technological.
US20070031715 has described the cross-linking method of the crosslinked generation sulphonyl of sulfonic acid chloride acid anhydride, formed in the method sulphonyl acid anhydride cross-linked structure can improve the mechanical strength of film effectively, but this cross-linked structure has significant disadvantages: sulphonyl acid anhydride unit is unsettled to alkali.
US20030032739 reaches crosslinked purpose by connecting at the alkyl between strand of the sulfonyl on the macromolecular chain.This crosslinked solvent swell that can reduce film well.But for obtaining not suitability for industrialized process of the required a lot of steps of this cross-linked structure.
US6733914 discloses the perfluor sulfonyl fluorine type film that will melt extrude and has soaked in ammoniacal liquor, forms the PEM of sulfimide cross-linked structure, and so the perfluoro sulfonic acid membrane of handling has excellent mechanical intensity and dimensional stability.But utilizing the resulting film of this method will be uneven film, because ammonia enters film by the method for infiltration, ammonia meeting and sulfuryl fluoride react in the process of infiltration, the sulfuryl fluoride of reaction will stop the further diffusion of ammonia to film inside, thereby form very high crosslink density on the surface of film, and that the inside of film does not take place almost is crosslinked.The big crosslinked electrical conductivity of film that makes in surface sharply descends.
Therefore, only adopt the crosslinked film of chemical bonding, often can not form the very high degree of cross linking, limited to the performance of improving film, cause the performance of telolemma can not reach the requirement of use.
Chinese patent 200810138431.9 discloses the crosslinked and common perfluoro sulfonic acid membrane that strengthens of microporous barrier of a kind of chemical bonding.Chemical bonding is crosslinked to have carried out modification with two kinds of means of microporous barrier though used, and the performance of film is greatly improved on basis in the past, and still there is the not high problem of air-tightness in film.
The perfluorinated sulfonic acid ionic membrane that is used for fuel cell need meet the demands: stable, high conductivity, high mechanical properties.Generally speaking, when ion-exchange capacity raise, the equivalent value of (per) fluoropolymer descends, and (equivalent value EW value reduced, ion exchange capacity IEC=1000/EW), film strength also reduces simultaneously, and the also rising thereupon of the gas permeability of film, and this will produce very fuel cell and seriously influence.Therefore, preparation has the macroion exchange capacity, has good Mechanics of Machinery intensity and air-tightness simultaneously, and the film that also has good stability simultaneously is a fuel cell, and especially the fuel cell that uses on delivery vehicles such as automobile is able to practical key.
Summary of the invention
At the deficiencies in the prior art,, the inventor after having paid creative work, has finished the present invention through further investigation.
The objective of the invention is, provide the compound triazine ring of a kind of microporous barrier cross-linked perfluorinated ionic membrane.
The invention provides the cross-linked perfluorinated ionic membrane of the compound triazine ring of a kind of microporous barrier, it is characterized in that: ion exchange fluoro resin is filled in the microporous barrier, the intermolecular of ion exchange fluoro resin is cross-linked with each other simultaneously, formation has triazine ring chemical crosslinking structure, and acidic-group on this cross-linked structure and high-valency metal compound form the physical bond structure, thereby form crosslinked dual network structure, described chemical crosslinking has the cross-bridge of following (I) structure:
The physical bond structure of formed high-valency metal compound and acidic exchange group [is example with the sulfonate radical] is shown in (II):
Described perfluorinated ion exchange resin is to be formed by tetrafluoroethene, one or more perfluor alkene monomer and one or more fluorine-containing alkene monomer copolymerization that contain crosslink sites that contain the acidic exchange group, or the mixture of one or more above-mentioned copolymers; The EW value of described ion exchange resin is not special to be limited, and for example can be 600～1300, is preferably 700～1200.
This copolyreaction is the common practise in the organic chemistry field of polymer technology, as long as clear and definite comonomer specifically, then to those skilled in the art, select suitable copolyreaction condition according to prior art with may be obvious that, as temperature, time, solvent, initator etc., thereby obtain perfluorinated ion exchange resin of the present invention.
The described perfluor alkene monomer that contains the acidic exchange group is selected from as shown in the formula (A) or (B):
CF
2＝CFO[CF
2CF(CF
3)]
fO(CF
2)
gSO
3H
F=0 or 1; The integer of g=2～4 (A)
CF
2＝CFO(CF
2)
3PO
3H
2 (B)
The described fluorine-containing alkene monomer that contains crosslink sites is selected from as shown in the formula (IX) or (X):
F
2C＝CFR
f4Y
4
(IX)
Wherein, Y
4, Y
5Be CN;
A ', b ', c ' they are 0 or 1 independently, but a '+b '+c ' ≠ 0;
X
1Be selected from F or CN; N ' is 0 or 1;
R
F4, R
F5, R
F6Be perfluoroalkyl independently, preferred C
1-C
5Perfluoroalkyl.
The aperture of described microporous barrier is 0.1～5 μ m, is preferably 0.5～4 μ m, most preferably is 1～3 μ m; Thickness is 5～100 μ m, is preferably 10～80 μ m, most preferably is 20～60 μ m; Porosity is 30～99%, is preferably 40～80%, most preferably is 50～70%.
Described microporous barrier is organic micro film or inorganic microporous barrier, and wherein organic micro film is preferably polymer microporous film, as the fluorocarbon polymer film.More preferably, described organic micro film is selected from eptfe film, silica modified porous hexafluoropropene film, porous tetrafluoroethene-perfluoroalkyl ethylene oxy copolymer or porous polyimide film.
Described inorganic microporous barrier especially for example can be ultra-thin ceramic film, ultra-thin molecular screen membrane etc.Preferably, be selected from porous Al
2O
3The ZrO of film, phosphoric acid modification
2Microporous barrier, sulfuric acid modified ZrO
2The ZrO that microporous barrier, improved silica microporous barrier, micropore glass film film, surperficial sulphation are handled
2Microporous barrier or molecular sieve film.
Described microporous barrier preferably carries out hydrophilic modifications such as surface silicon acidifying, sulfonation, sulphation, phosphorylation.
For example concerning the fluorocarbon polymer film, can silicify to the surface, modification such as sulfonation, sulphation, phosphorylation.Existing surface modifying method for polytetrafluoroethylene (PTFE) all is suitable for the modification to the fluorocarbon polymer film, comprises reduction modification method, laser emission modification, plasma modification method and the silicic acid activation method of sodium naphthalene solution.Wherein preferred silicic acid activation method is because it can be at the silica that directly deposits water conservation on the fluorocarbon polymer film surface.By fluorocarbon polymer film surface after the modification hydrophilic group has been arranged, but has preferably further carried out modification on this basis again, as with the fiber of modification at ethyl orthosilicate, ZrOCl
2-H
3PO
4Or carry out further modification in the titanate esters etc.
And, then these inorganic microporous barriers directly can be positioned over ethyl orthosilicate, ZrOCl for the surface modification of inorganic microporous barrier
2-H
3PO
4, titanate esters, H
3PO
4Or H
2SO
4Deng in carry out modification, also can when the synthesizing inorganic microporous barrier, add modifier directly to generate the modified inorganic microporous barrier, for example phosphate and ethyl orthosilicate are mixed, become Modified Membrane with the alkali gel.For example, prepare the concrete grammar of silica modified voided polytetrafluoroethylene film, exactly voided polytetrafluoroethylene film is placed on SiCl
4Be warmed up to 110 ℃ and kept 1 hour in the atmosphere after 1 hour, be cooled to 60 ℃ again after, water spray is handled and is obtained silica modified voided polytetrafluoroethylene film.
Titania modified cellular glass film method is for to place Ti (OEt) with the cellular glass film
4In/the water mixed system, add concentrated ammonia liquor down in stirring, hydrolysis is left standstill and is obtained the cellular glass film that titanium dioxide is modified.
Also can be with inorganic ultrathin membrane (as TiO
2Film, ZrO
2Film) directly at H
3PO
4Or H
2SO
4Soak Deng in the inorganic acid, thereby carry out surface modification.
The preparation method who also has a kind of modified inorganic ultrathin membrane of separating out jointly, as triethyl phosphate is mixed with ethyl orthosilicate (1: 100 mass ratio), add entry and concentrated ammonia liquor then and left standstill gel 12 hours, utilize surfactant such as hexadecyltrimethylammonium chloride to make the lamina membranacea gel then, obtain the ultra-thin silicon dioxide film of phosphoric acid modification.
Ion exchange fluoro resin in the described microporous barrier reinforced perfluoro crosslinked and doped ionic membrane can be at microporous barrier surface-crosslinked, also can be crosslinked in the space of microporous barrier.It also can be the mixing of several structures that cross-linked structure can be a kind of of said structure.
Because perforated membrane carried out the surface active modification, have acidity or functional group and make and to form strong crosslinked action by the physical bond of high-valency metal compound between perforated membrane and the film-forming resin.
The metallic element of described high-valency metal compound is selected from down one of column element or combination: W, Ir, Y, Mn, Ru, Ce, V, Zn or La element, the consumption of these metallic compounds does not limit especially, for example can be perfluorinated ion exchange resin quality 0.001～5%, be preferably 0.01～4%, more preferably 0.1～3%.
Described high-valency metal compound can be selected from a kind of or combination double salt in nitrate, sulfate, carbonate or the acetate of the highest price attitude of these metallic elements and middle valence state.
Described high-valency metal compound can be selected from the highest price attitude of these metallic elements and cyclodextrin, crown ether, acetylacetone,2,4-pentanedione, nitogen-contained crown ether and nitrogen heterocyclic ring, EDTA (ethylenediamine tetra-acetic acid), DMF (N, dinethylformamide) or DMSO (dimethyl sulfoxide (DMSO)) complex compound of middle valence state.
Described high-valency metal compound can be selected from the highest price attitude of these metallic elements and the hydroxide of middle valence state.
Described high-valency metal compound can be selected from the highest price attitude of these metallic elements and the oxide with perovskite structure of middle valence state, for example is Ce
xTi
(1-x)O
2(x=0.25～0.4), Ca0.6La
0.27TiO
3, La
(1-y)Ce
yMnO
3(y=0.1～0.4) or La
0.7Ce
0.15Ca
0.15MnO
3
The present invention also provides the preparation method of the dual cross-linking ion membrane of perfluor of described microporous barrier enhancing, comprises the steps:
(1) with microporous barrier be mixed with the ion exchange fluoro resin solution of high-valency metal compound by casting, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology composite membrane-forming;
(2) between film forming stage or crosslinked after the film forming, form the cross-bridge structure of formula (I).
The method that forms formula (I) cross-bridge is that the fluorine resin in cyano-containing site forms under hot or sour effect.
Described acid is strong protonic acid or lewis acid; Wherein said Bronsted acid for example can be selected from H
2SO
4, CF
3SO
3H or H
3PO
4Described lewis acid is selected from ZnCl
2, FeCl
3, AlCl
3, organo-tin compound, organo-antimony compound or organic tellurium compound.
Wherein, when using casting, spin coating, curtain coating, silk-screen printing technique, spraying or impregnating technology, solvent can be but be not limited only to a kind of of following solvent or combination: dimethyl formamide, dimethylacetylamide, NMF, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, hempa acid amide, acetone, water, ethanol, methyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol or glycerine.Solid masses content in the prepared resin solution is 1～80%, is preferably 5～70%, most preferably is 10～50%.Will be under 30～300 ℃ temperature during film forming heat treatment 10～100 minutes; Described temperature is preferably 80～250 ℃, more preferably 100～200 ℃; Described treatment temperature is preferably 20～60 minutes, most preferably is 30～50 minutes.
In the perfluoro dual crosslinked ion membrane that microporous barrier of the present invention strengthens, used simultaneously that microporous barrier, triazine ring chemical bonding are crosslinked, multiple means such as high-valency metal compound and acidic exchange group physical bond are crosslinked, thereby performance acts synergistically simultaneously, has improved the mechanical strength of ionic membrane.So the film of modification has had large increase than the microporous barrier enhancing of general chemistry bonding cross-linking in dimensional stability.Solved the gas permeability difficult problem of micropore enhancing perfluoro sulfonic acid membrane simultaneously, trace it to its cause, because employed chemical crosslinking structure and metal-acidic-group physical bond network structure acting in conjunction, especially metal-cation exchange groups physical bond network structure acting in conjunction has improved the degree of cross linking of film greatly.Particularly among the present invention the chemical crosslinking structure-triazine ring that uses also can form coordination cross-linked structure with the high-valency metal compound, thereby further increased the degree of cross linking.Invention also is surprised to find, and the gas permeability of these composite membranes is very low.This may be because following reason: 1, surface-functionalized microporous barrier and film-forming resin adhesion are greatly improved; 2, because lip-deep functional group can form bonding structure with metallic compound, this has further reduced the space between resin and microporous barrier.
The specific embodiment:
By the following examples the present invention is further specified, but those skilled in the art as can be known, the following examples only are used to explain, and are not that the spirit and scope of the present invention are limited.
Embodiment 1:
With repetitive be
, EW=800 fluoropolymer resin and with repetitive be
, EW=1200 fluoropolymer resin mix at 2: 3 by mass ratio, be distributed in propyl alcohol-water with the inferior cerium of tetraphenyltin and carbonic acid (account for resin quality 0.01%) then, make total mass concentration and be propyl alcohol-aqueous solution of 5%, to the thickness that wherein immerses the silicic acid modification is the porous polyhexafluoropropylene film (porosity 94%) of 30 μ m, obtains cross-linking ion membrane.
Embodiment 2:
With repetitive be
, EW=700 fluoropolymer resin and repetitive be
, EW=1300 fluoropolymer resin (two kinds of resin quality ratios are 1: 0.2), phenyl stannic hydroxide and 8-hat-6-Y complex compound (account for resin quality 0.3%) mixed dissolution is in DMF, make total mass concentration and be 20% solution, be that 50 μ m and porosity are that the micropore glass film film of 75% phosphoric acid modification places above-mentioned solution then with thickness, soaked about 3 hours, heating obtains the individual layer perfluorinated sulfonic acid ionic membrane that thickness is 50 μ m.
Embodiment 3:
With repetitive be
, EW=1200 fluoropolymer resin, triphenyl tin hydroxide and the surface by perovskite structure La
0.7Ce
0.15Ca
0.15MnO
3Be scattered among the DMF, place above-mentioned solution to soak half an hour approximately the thick porous polyimide film of 20 μ m, handled 60 minutes down, make the ionic membrane that thickness is 20 μ m at 170 ℃.
Embodiment 4:
With repetitive be
Fluoropolymer resin and repetitive be
Fluoropolymer resin be that 1: 5 ratio is mixed in mass ratio, be scattered in the N-methyl pyrrolidone then with after acetylacetone,2,4-pentanedione-Ir (III) (account for total resin quality 2%) mixes, formation solid masses content is 30% dispersion liquid, in this dispersion liquid, add a spot of organo-antimony compound catalyst, the expanded ptfe film that with the thick and porosity of 80 μ m is 75% sulfonic acid modified then places above-mentioned solution to soak half an hour approximately, handles obtaining ionic membrane down in 230 ℃.
Embodiment 5:
With repetitive be
, the fluoropolymer resin of EW=700 and the resin (two kinds of resin quality ratios are 1: 4) of following embodiment 8, tetraphenyltin, cyclodextrin-La (III) (account for total resin quality 0.2%) is scattered in the dimethyl sulfoxide (DMSO), (diameter is 0.5 μ m to polytetrafluoroethylporous porous membrane by silk-screen printing technique method and phosphoric acid modification, thickness is 20 μ m, porosity is 85%) compound, obtain the film that thickness is 25 μ m, then this film was handled 60 minutes down at 170 ℃ by the method for casting, made the cross linking membrane that thickness is 20 μ m.
Embodiment 6:
With repetitive be
, EW=1200 fluoropolymer resin, DMF-Y (III) (with the mass ratio of resin be 0.01: 100) and triphenyl tin hydroxide be scattered among the DMF, place above-mentioned solution to soak half an hour approximately the thick porous polyimide film of 20 μ m, handled 60 minutes down at 170 ℃, making thickness is the film with cross-linked structure of 20 μ m.
Embodiment 7:
With repetitive be
, the fluoropolymer resin of EW=600 and the resin (two kinds of resin quality ratios are 1: 4) of following embodiment 8, tetraphenyltin, 18-hat-6-zinc complex (account for total resin quality 0.2%) is scattered in the dimethyl sulfoxide (DMSO), (diameter is 3 μ m to polytetrafluoroethylporous porous membrane by silk-screen printing technique method and phosphoric acid modification, thickness is that 10 μ m and voidage are 95%) carry out compound, obtain the film that thickness is 25 μ m, then this film was handled 60 minutes down at 170 ℃ by the method for casting, made the cross linking membrane that thickness is 40 μ m.
Embodiment 8
With repetitive be
Fluoropolymer resin and pyridine-Ru complex solution (account for resin quality 0.63%) fully mix, be scattered in then in the N-methyl pyrrolidone, formation solid masses content is 30% dispersion liquid, in this dispersion liquid, add a spot of antimony organic catalyst, the porosity that 50 μ m are thick is that the expanded ptfe film of 80% sulfonic acid modified places above-mentioned solution to soak half an hour approximately, in 230 ℃ of following film forming.
Embodiment 9:
With repetitive be
Fluoropolymer resin with repetitive be
Fluoropolymer resin be that 1: 2 ratio is mixed in mass ratio, after nitogen-contained crown ether-Ce complex compound (account for total resin quality 1%) mixes, be scattered in the N-methyl pyrrolidone that to form solid masses content be 30% dispersion liquid, in this dispersion liquid, add a spot of antimony organic catalyst again, the expanded ptfe film that with the thick and porosity of 30 μ m is 75% sulfonic acid modified places above-mentioned solution to soak half an hour approximately, in 230 ℃ of following film forming.
Embodiment 10:
With repetitive be
Fluoropolymer resin with repetitive be
Fluoropolymer resin be that 1: 2 ratio is mixed in mass ratio, be scattered in then in the N-methyl pyrrolidone that to form gross mass content be 30% dispersion liquid, in this dispersion liquid, add a spot of antimony organic catalyst again, the expanded ptfe porous membrane that with the thick and porosity of 30 μ m is 75% sulfonic acid modified places above-mentioned solution to soak half an hour approximately, in 230 ℃ of following film forming.
Comparative example 11
Utilizing mass concentration is 10% nafion
Solution, the expanded PTFE porous membrane that 30 μ m are thick (porosity is 70%) place above-mentioned solution to soak about 1 hour, and the film that will soak carries out the drying processing on 170 ℃ of heating plates then, obtain the thick microporous barrier of 30 μ m and strengthen amberplex.
Experimental example 12
Performance to various films characterizes, and the results are shown in Table 1.As can be seen from Table 1, be added with 95 ℃ of electrical conductivity, hot strength, the hydrogen permeate electric current of the triazine ring cross-linked doped ion-exchange membrane that the microporous barrier of high-valency metal compound strengthens, performances such as size changing rate all are better than the film that common microporous barrier strengthens amberplex and do not increase divalent metal compound, and especially the performance aspect gas barrier has had highly significant and significantly improved and improve.
The various films of table 1 characterize
Claims (4)
1. compound triazine ring cross-linked perfluorinated ion-exchange membrane of microporous barrier, it is characterized in that: perfluorinated ion exchange resin is filled in the microporous barrier, the intermolecular of perfluorinated ion exchange resin is cross-linked with each other simultaneously, formation has triazine ring chemical crosslinking structure, and acidic-group on this cross-linked structure and high-valency metal compound form the physical bond structure, thereby form crosslinked dual network structure, described chemical crosslinking has the cross-bridge of following (I) structure:
Wherein: described perfluorinated ion exchange resin be by tetrafluoroethene, one or more contain the perfluor alkene monomer of acidic exchange group and perfluor alkene monomer copolymerization that one or more contain crosslink sites forms, or the mixture of multiple above-mentioned copolymer;
The described perfluor alkene monomer that contains the acidic exchange group is selected from (A) or (B) plants:
CF
2＝CFO[CF
2CF(CF
3)]
fO(CF
2)
gSO
3H
F=0 or 1; The integer of g=2～4 (A)
CF
2＝CFO(CF
2)
3PO
3H
2 (B)
The described perfluor alkene monomer that contains crosslink sites is the structure of (X):
Wherein, Y
5Be CN;
A ', b ', c ' they are 0 or 1 independently, but a '+b '+c ' ≠ 0;
X
1Be selected from F or CN
N ' is 0 or 1;
R
F5, R
F6Be selected from perfluoroalkyl respectively;
Wherein: the metallic element of described high-valency metal compound is selected from down one of column element or combination: W, Ir, Y, Mn, Ru, Ce, V, Zn or La element, and
Described high-valency metal compound is selected from the highest price attitude of these metallic elements and the cyclodextrin or the crown ether complex compound of middle valence state; Or
Be selected from the highest price attitude of these metallic elements and the oxide with perovskite structure of middle valence state, described oxide with perovskite structure is following Compound C e
xTi
(1-x)O
2, Ca
0.6La
0.27TiO
3, La
(1-y)Ce
yMnO
3Or La
0.7Ce
0.15Ca
0.15MnO
3, wherein x=0.25～0.4, y=0.1～0.4.
2. amberplex as claimed in claim 1 is characterized in that: R
F5, R
F6Be selected from C respectively
1-C
5Perfluoroalkyl.
3. amberplex as claimed in claim 1 is characterized in that: described microporous barrier is selected from eptfe film, expanded microporous polytetra fluoroethylene-EPTEE-hexafluoropropene film, porous polyimide film, SiO
2Film, TiO
2Film, ZrO
2Film, Al
2O
3Film or cellular glass film.
4. amberplex as claimed in claim 1 is characterized in that: described crown ether is a nitogen-contained crown ether.
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| CZ307270B6 (en) * | 2013-06-27 | 2018-05-09 | Membrain S.R.O. | An asymmetric ion-exchange membrane and the method of its use |
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| WO2018231232A1 (en) * | 2017-06-15 | 2018-12-20 | W. L. Gore & Associates, Inc. | Highly reinforced ionomer membranes for high selectivity and high strength |
| CN113527760A (en) * | 2020-04-20 | 2021-10-22 | 江苏泛亚微透科技股份有限公司 | Method for manufacturing expanded polytetrafluoroethylene (ePTFE) -silicon dioxide aerogel composite heat-insulating film material |
| CN117186476B (en) * | 2023-11-07 | 2024-02-09 | 华中科技大学 | Preparation method of ion-doped filling modified polymer ionic membrane |
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| CN101237054A (en) * | 2008-02-03 | 2008-08-06 | 山东东岳神舟新材料有限公司 | An intercrossed enhanced full fluorin proton adulterated exchange film and its making method |
| CN101290996A (en) * | 2008-02-03 | 2008-10-22 | 山东东岳神舟新材料有限公司 | Fiber reinforced inorganic doped proton exchange film containing fluorine |
| CN101350414A (en) * | 2008-07-22 | 2009-01-21 | 山东东岳神舟新材料有限公司 | Microporous-film-reinforced fluorine-containing cross-linking ion-exchange membrane and preparation method thereof |
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| CN101237054A (en) * | 2008-02-03 | 2008-08-06 | 山东东岳神舟新材料有限公司 | An intercrossed enhanced full fluorin proton adulterated exchange film and its making method |
| CN101290996A (en) * | 2008-02-03 | 2008-10-22 | 山东东岳神舟新材料有限公司 | Fiber reinforced inorganic doped proton exchange film containing fluorine |
| CN101350414A (en) * | 2008-07-22 | 2009-01-21 | 山东东岳神舟新材料有限公司 | Microporous-film-reinforced fluorine-containing cross-linking ion-exchange membrane and preparation method thereof |
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| CZ307270B6 (en) * | 2013-06-27 | 2018-05-09 | Membrain S.R.O. | An asymmetric ion-exchange membrane and the method of its use |
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