CN101330149A - Multilayer cross-linking ionic membrane containing fluorine and preparation method thereof - Google Patents
Multilayer cross-linking ionic membrane containing fluorine and preparation method thereof Download PDFInfo
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- CN101330149A CN101330149A CNA2008101387054A CN200810138705A CN101330149A CN 101330149 A CN101330149 A CN 101330149A CN A2008101387054 A CNA2008101387054 A CN A2008101387054A CN 200810138705 A CN200810138705 A CN 200810138705A CN 101330149 A CN101330149 A CN 101330149A
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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 multi-layer fluorine-containing cross-linked ion membrane and the preparation method thereof, and belongs to the functional polymer composite material field. The fluorine-containing membrane has a multi-layer structure, and is an ion exchange membrane with a network structure, which is formed by adopting the cross-linking site containing fluorine-containing ion exchange resin as the membrane-forming resin; and carrying out the cross-linking reaction under a certain condition. The prepared ion exchange membrane has the advantages of high proton conductivity and dimensional stability.
Description
Technical field
The invention belongs to field of functional polymer composites, relate to a kind of exchange membrane containing fluorine and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells is a kind ofly directly chemical energy to be converted into the Blast Furnace Top Gas Recovery Turbine Unit (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 proton exchange membrane.
Though now the perfluorinated sulfonic acid proton exchange membrane of using is used for many years, but still exists deficiency not reach the commercialization requirement,, poor dimensional stability low as the high temperature proton conductivity, mechanical strength are not high.Especially dimensional stability aspect, film are also different because of the different swelling ratios of water absorption 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 permeability of reduction working media etc. is the key subjects that fuel cell industries faces.
The crosslinked thermal stability that can improve polymer, the swelling of minimizing solvent, the mechanical strength of raising polymer 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 sulfonic acid chloride acid anhydride has been described as US20070031715, formed in the method sulphonyl acid anhydride cross-linked structure can effectively improve the mechanical strength of film, is that sulphonyl acid anhydride unit is unsettled to alkali but this cross-linked structure has significant disadvantages.US20030032739 then reaches crosslinked purpose by connecting at the alkyl between strand of the sulfonyl on the macromolecular chain.This crosslinked solvent swell that can well reduce film.But need a lot of steps to be not suitable for course of industrialization for obtaining this cross-linked structure.The disclosed perfluor sulfonyl fluorine type film that will melt extrude of US6733914 soaks the proton exchange membrane that forms the sulfimide cross-linked structure in ammoniacal liquor, the perfluoro sulfonic acid membrane of Chu Liing has good mechanical 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 sulfuryl fluoride react in the process of infiltration, the sulfuryl fluoride of reaction will stop ammonia further to the diffusion of 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 conductivity of film that makes in surface sharply descends.
The disclosed triazine ring cross-linked structure perfluoro sulfonic acid membrane that contains of CN200710013624.7 and US7259208 has good mechanical strength and dimensional stability equally.
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 properties.Generally speaking, when ion-exchange capacity raise, the equivalent value of (per) fluoropolymer decline (equivalent value EW value reduces, ion exchange capacity IEC=1000/EW) film strength simultaneously also reduced.Therefore, preparation has a macroion exchange capacity, and the ionic membrane that can keep mechanical 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 multilayer fluorine-containing cross-linking ion film and preparation method are provided.The exchanger resin that the present invention adopts forms cross-linked structure can reduce the proton conductive that permeability is improved polymer film, and effectively the damaged while of spreading of block film machinery is further reduced gas permeability to adopt sandwich construction.
The invention provides a kind of multilayer fluorine-containing cross-linking ion film, be to be the multilayer film of the 2-40 layer that forms of the ion exchange fluoro resin of 600～1300mmol/g with the EW value, wherein have at least 1 layer to have cross-linked structure, conductivity 40～150mS/cm, hot strength 10～60Mpa; Gross thickness 10～300 μ m;
Described cross-linked structure is selected from one or more as shown in the formula (I), (II), (III), (IV) and/or in the structure (V):
Wherein, G
1=CF
2Or O, G
2=CF
2Or O, R
fBe C2-C10 perfluor carbochain or chloride perfluor carbochain;
Wherein, R is methylene or perfluor methylene, and n is 0～10 integer;
Following formula formula (I), (II), (III), (IV) and/or (V) in sweep and the fluorine-containing carbochain of broken line representative.
Preferably, the EW value of described ion exchange fluoro resin is 700-1200mmol/g; The number of plies of multilayer film is the 2-10 layer, gross thickness 10-50 μ m.
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 copolymer;
Fluorine containing olefine is selected from: tetrafluoroethene, and chlorotrifluoroethylene, trifluoro-ethylene, hexafluoropropylene, and/or in the vinylidene one or more, preferred, Fluorine containing olefine is selected from tetrafluoroethene or chlorotrifluoroethylene;
The fluorine-containing alkene monomer that contains functional group is selected from one or more as shown in the formula (VI), (VII) and/or in the structure (VIII):
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 dichlorodifluoromethan base respectively;
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 or NR
1R
2Described R is selected from methyl, ethyl or 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 one or more as shown in the formula (IX) and/or in the structure (X):
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 Br, F, Cl, Br, or I;
N ' is 0 or 1;
R
F4, R
F5, R
F6Be selected from perfluoroalkyl respectively;
Preferably, the EW value of described ion exchange fluoro resin is 700-1200mmol/g; The number of plies of multilayer film is the 2-10 layer, gross thickness 10-50 μ m.
In the multilayer fluorine-containing cross-linking ion film each layer can all form cross-linked structure and also allow part layer not form cross-linked structure, also can form cross-linked structure with interlayer by layer.Because layer and interlayer form crosslinked active force between making layer by layer and greatly strengthen, thereby difficult the disengaging.Preferred two skins have cross-linked structure.
The present invention also provides a kind of preparation method of multilayer fluorine-containing cross-linking ion film, each monofilm utilize solution or fused mass casting, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology make; The preparation of multilayer film is by compound between monofilm, compound between compound or multilayer film and multilayer film between multilayer film and monofilm, also can directly on monofilm that has made or multilayer film, utilize solution or fused mass casting, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology preparation.
Preferably, the step of solution casting, solution casting, silk-screen printing technique, spin coating, spraying or dipping is as follows:
(1) with ion exchange fluoro resin, crosslinking agent, additives such as acid or radical initiator are distributed to solvent and form mixture; Ion exchange fluoro resin content is 1～80% in the mixture, weight ratio; Used solvent is one or more in dimethyl formamide, dimethylacetylamide, methylformamide, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, hempa acid amide, acetone, water, ethanol, methyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol or the glycerol; Described crosslinking agent is selected from the described material of formula (XI), ammonia, hydrazine, organic diamine or can discharge ammonia through chemical treatment, the material of hydrazine, organic diamine;
(2) utilize the mixture of preparation in the step (1) passing through solution casting, solution casting, silk-screen printing technique, spin coating, spraying or impregnation technology film forming on the flat board or on the single or multiple lift film that has prepared; Will be under 30～300 ℃ temperature during film forming heat 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 cross-linked structure.
Preferably, the used solvent of step (1) is one or more in dimethyl formamide, dimethylacetylamide, methylformamide, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, hempa acid amide, acetone, water, ethanol, methyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol or the glycerol; Described crosslinking agent is selected from the described material of formula (XI), ammonia, hydrazine, organic diamine or can discharge ammonia through chemical treatment, the material of hydrazine, organic diamine;
Preferably, will be under 80～250 ℃ temperature during film forming in the step (2) heat treatment 20～60 minutes.
The method that forms the cross-linked structure shown in the formula (I) comprises heat, light, electron radiation, plasma, X ray or radical initiator, also can pass through heat, light, electron radiation, plasma, X ray or action of free radical initiator and form cross-linked structure when one or more crosslinking agents exist.Wherein the structure of employed crosslinking 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 dichlorodifluoromethan base;
Described radical initiator is organic peroxide, azo-initiator etc., and wherein the general formula of peroxide initiator can be expressed as (XII) and (XIII):
R
1, R
2, can be respectively from following groups but be not limited only to choose arbitrarily these groups:
R
1, R
2, can be respectively from following groups but be not limited only to choose these groups: the alkyl that the aroyl of the alkyl that the alkyl or aryl of H, C1～C20 replaces, the acyl group of C1～C20, C1～C20, the fluorine-containing or perfluoroalkyl of C1～C20 or aryl replace, the fluorine-containing or perfluoro acidyl of C1～C20, the fluorine-containing or perfluor aroyl of C1～C20; But R
1, R
2Can not select H simultaneously;
R
3, R
4Can be respectively from following groups but be not limited only to choose arbitrarily these groups:
The alkyl that the alkyl that the alkyl or aryl of C1～C20 replaces, the fluorine-containing or perfluoroalkyl of C1～C20 or aryl replace;
Azo-initiator is but is not limited only to following several:
Azo-initiator is but is not limited only to following several: Celogen Az, azodiisobutyronitrile, AMBN, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, 1-((cyano group-1-Methylethyl) azo) formamide, 1,1 '-azo (cyclohexyl-1-cyano group), 2,2 '-azo (2-methyl-propyl amidine) dihydrochloride, 4,4 '-azo two (4-cyanopentanoic acid) or 3-hydroxyl-4-nitrobenzoic acids.
Form (II) or (III) method of cross-linked structure be: utilize sulfuryl fluoride, sulfonic acid chloride, sulfonic acid bromide type resin and ammonia, 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) cross-linked structure is that the sulfonic fluoropolymer resin utilizes the chlorosulfonic acid processing to obtain;
The method that forms (V) cross-linked structure is that the fluorine-containing sulfuryl fluoride resin in the sulfonic fluoropolymer resin in nitrile group-containing site, nitrile group-containing site, the sulfonic acid bromide resin that contains that contains sulfonic acid chloride resin or nitrile group-containing site in nitrile group-containing site form under hot or sour effect;
Described acid is strong protonic acid or lewis acid; Wherein strong 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, melt extrude with the step of pressure sintering as follows:
(1). according to the suitable ion exchange fluoro resin of needs preparation of each layer formula in the multilayer fluorine-containing cross-linking ion film, crosslinking agent, acid and/or radical initiator mixture utilize double screw extruder, banbury or mill 200～280 ℃ of mixing; Described ion exchange fluoro resin is selected from sulfuryl fluoride, sulfonic acid chloride or sulfonic acid bromide resin;
(2) resin that step (1) is mixed utilizes screw extruder or vulcanizing press film forming;
(3) crosslinked in the film forming, or after the film forming; Get monofilm;
(4) monofilm is compound, obtains described multilayer film.
Preferably, the film of gained can be converted in advance acid type and other film is compound, also can be earlier and the compound acid type that transfers to again of other film.
Preferably, utilize the extrusion by melting cambium layer to be: to contain the resin that can form identical cross-linked structure with two kinds and at high temperature extrude and use and increase that pressure is compound to make two kinds of resin surfaces merge mutually, utilize cross-linking method to make it crosslinked then with the method for interlayer cross-linked structure.Also can contain the prior film forming of crosslink sites resin with one, and this film is dipped into to contain in the identical crosslink sites chromoresin solution swelling and do crosslinking Treatment obtains crosslinked layer by layer film.
Preferred, when the casting that utilizes solution or fused mass, extrude, when hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology film forming, employed radical initiator is the perfluor organic peroxide, will be under 80～250 ℃ temperature during film forming heat treatment 20～60 minutes.
The use of the crosslinked means of use has improved the mechanical strength of ionic membrane in the present invention-multilayer fluorine-containing cross-linking ion film, has also increased the dimensional stability of film simultaneously greatly.We can also find to compare in the past by the fuel permeability of film, and the result of various technology descends the ionic membrane that its effect is traditional head and shoulders above greatly.Studying carefully its possible reason and be cross-linked structure makes conductive ion bunch be limited at the resistance that has increased fuel infiltration in the very little space, also having our film of invention is a kind of film of sandwich construction, thereby existing the interface between layer and the layer, the existence at interface makes the infiltration of fuel be suppressed.
In general the existence at interface also can reduce the material conductivity simultaneously greatly, because the interface scattering phenomenon can occur to the charge carrier that conducts electricity.But this phenomenon does not have the high temperature or the conductance under the low humidity of appearance and film to improve significantly than traditional monofilm in our technology.This may be because the existence at interface makes the leakage that is kept at the small amount of moisture in the film also be suppressed simultaneously, makes the water holding capacity of film improve greatly compared with simple monofilm.
Embodiment:
By the following examples the present invention is further specified, but the present invention is not limited thereto.
Embodiment 1:
With repetitive be
The polymer of EW=1000 is made the aqueous propanol solution of 5wt%, be disposed at concentration then and be 5% peroxidating perfluor malonyl DMF solution, be cast in the polytetrafluoroethylene mold of horizontal positioned, through 80 ℃ of vacuumizes after 12 hours, film is peeled off, and is the H of 0.5M in molar concentration
2SO
4Boil 1 hour in the solution, and use deionized water wash.Obtaining the individual layer perfluorinated sulfonic acid crosslinked with NaOH solution, sulfuric acid solution processing film successively after the heat treated is that (I) plants ionic membrane (monofilm 1#).Carry out hot pressing with above-mentioned two individual layer perfluor cross-linking ion membranes are stacked, make double-deck perfluor cross-linking ion membrane (multilayer film 1#).
Embodiment 2:
With repetitive be
The polymer of EW=800 is extruded for 250 ℃ and is obtained the film that thickness is 15 μ m.With above-mentioned two film high-temp. hot pressing together and 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 amberplex (duplicature 2#) of (II) with the cross-linked structure layer by layer that KOH solution, hydrochloric acid solution are handled successively.
Place repetitive to be above-mentioned ionic membrane
The polymer of EW=1200 and tetraphenyltin be with 200 ℃ of films that are extruded into 50 μ m of double screw extruder, then film is heated to 230 ℃ 10 hours cross-linked 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.(monofilm 3#) with duplicature 2#, 3#, hot pressing obtain cross-linked three-layer film (multilayer film 2#), and thickness is 80 μ m.
Embodiment 3:
With repetitive be
The polymer of EW=1100 and urea are by after being hot pressed into 100 μ m films, and obtaining cross-linked structure with alkali and acid treatment successively behind 170 ℃ of heating 5h is the ionic membrane that (II) plants.(monofilm 4#)
With repetitive be
The polymer of EW=940 is made 30% DMSO solution, by the casting method at 170 ℃, 60min makes the film (monofilm 5#) of 10 μ m.
With monofilm 4,5# perfluorinated sulfonic acid ionic membrane is stacked to carry out hot pressing, then with multilayer film 2# hot pressing, obtains six layers of cross-linking ion membrane (multilayer film 3#).
Embodiment 4:
With repetitive be
The solution of 20% (weight) that the polymer dissolution of EW=700 is made in DMF, the method for utilizing curtain coating then are in 230 ℃, and the thickness of 20min system is the individual layer perfluorinated sulfonic acid cross-linking ion membrane of 50 μ m.It must cross-linked structure be the film (monofilm 6#) of real (IV) that this amberplex be impregnated in the chlorosulfonic acid.
Above-mentioned ionic membrane is placed polymer and peroxidating perfluor bay two acyls of embodiment 1 once more, 1, soaked 0.5 hour in the DMF solution of 4-diiodo-octafluorobutane, then film is taken out dryly, repeat above-mentioned steps, film is handled 300min down at 120 ℃.Two above-mentioned films are hot pressed into crosslinked six tunics (multilayer film 4#).
Embodiment 5:
With repetitive be
The polymer of EW=1300, AMBN, 1,4-diiodo-octafluorobutane is dissolved among the DMF, by the casting method at 270 ℃, 10min makes the film of 20 μ m.Re-use perfluorinated sulfonic resin among the embodiment 4 and be dissolved in the N-methyl pyrrolidone and become the film of 30 μ m, prepare three layers of perfluorinated ion-exchange membrane (multilayer film 5#) in the spin coating of the both sides of above-mentioned film.Film is handled 2.4h down at 69 ℃.The cross-linked structure that obtains three layers is the perfluoro sulfonic acid membrane of formula (II).
Above-mentioned ionic membrane is placed above-mentioned polymer, AMBN once more, 1, soaked 0.5 hour in the DMF solution of 4-diiodo-octafluorobutane, then film is taken out dry, repeat above-mentioned steps, film is handled 300min, the five layers of perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 6#) that obtain down at 120 ℃.
Embodiment 6:
With repetitive be
By the spraying coating process method, 200 ℃, 30min obtains the film that thickness is 40 μ m to the polymer dissolution of EW=1300 in hempa acid amide (solid content 5%).Film is handled 100min down at 230 ℃.Obtaining cross-linked structure is the individual layer perfluoro sulfonic acid membrane (monofilm 7#) of formula (II).
Both sides at crosslinked perfluoro sulfonic acid membrane are passed through the spraying coating process method once more, make three layers of crosslinked perfluoro sulfonic acid membrane of 60 μ m.At its both sides hot pressing monofilm 7#, make crosslinked five layers of perfluorinated sulfonic acid doping (multilayer film 7#).
Embodiment 7:
With repetitive be
The polymer of EW=1300, benzoyl peroxide, 1,14-diiodo-20 fluorine ten alkane are dissolved in the dimethyl sulfoxide (DMSO) and obtain the film that thickness is 25 μ m by the silk-screen printing technique method.Film is handled 3min down at 160 ℃.Obtain crosslinked perfluoro sulfonic acid membrane.(monofilm 8#)
Above-mentioned ionic membrane is placed the same polymer of formula once more, zeolite and benzoyl peroxide, 1, soaked 0.5 hour in the dimethyl sulphoxide solution of 14-diiodo-20 fluorine ten alkane, then film is taken out dry, repeat above-mentioned steps, film is handled 300min, the three layers of perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 8#) that are enhanced down at 120 ℃.
Carry out hot pressing with three of multilayer film 8# are stacked, make nine layers of perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 9#) of enhancing.
Embodiment 8:
With repetitive be
The EW=1250 polymer dissolution obtains 30% solution in the hempa acid amide, by the spraying coating process method, obtain the film that thickness is 40 μ m.Film is handled 100min down at 230 ℃, obtain crosslinked individual layer perfluoro sulfonic acid membrane (monofilm 9#).
Both sides at crosslinked perfluoro sulfonic acid membrane are passed through the spraying coating process method once more, make three layers of crosslinked perfluoro sulfonic acid membrane of 60 μ m.At its both sides hot pressing monofilm 9#, make crosslinked five layers of perfluoro sulfonic acid membrane (multilayer film 10#).
Embodiment 9:
With repetitive be
The polymer of EW=900 is extruded and is obtained the film that thickness is 30 μ m.Soak and NH
3DMF solution in 5 hours.Get the film that (II) plants cross-linked structure at 200 ℃.With this film alkali lye, the cross linking membrane (monofilm 10#) that acid solution is handled.
With repeat unit structure be
The polymer of EW=1200 and tetraphenyltin are extruded into the film of 50 μ m with double screw extruder, then film are heated to 230 ℃ and obtain the films (monofilm 11#) that (V) plants cross-linked structure in 10 hours.With monofilm 10, the hot pressing of 11# high temperature is compound, this film is placed 35% hydrazine hydrate kind 10 hours again, take out the back heating had simultaneously in 5 hours (V) plant cross-linked structure and layer by layer between (III) plant the film of cross-linked structure, this film alkali lye, the cross linking membrane (multilayer film 11#) that acid solution is handled.
The crosslinked eleventh floor film (multilayer film 12#) of multilayer film 11# and the overlapping hot pressing of multilayer film 7# film, thickness is 300 μ m
Embodiment 10:
With repetitive be
The polymer of EW=700 and repetitive are
20% the solution that the polymer of EW=1300 (the resin quality ratio is 1: 0.2) and AMBN mixed dissolution are made in DMF, 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 cross-linked structure, again this amberplex is put in the film (monofilm 12#) that obtains (IV) cross-linked structure in the chlorosulfonic acid again.
With monofilm 12# and multilayer film 2# hot pressing, make five layers of perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 13#).
Embodiment 11:
With repetitive be
The polymer of EW=1200 and triphenyl tin hydroxide are scattered among the DMF, and the method by casting is at 170 ℃, and 60min makes the film that the having of 20 μ m (V) planted cross-linked structure.Re-use perfluorinated sulfonic resin among the embodiment 4 and be dissolved in the N-methyl pyrrolidone and become the film of 30 μ m, prepare three layers of perfluorinated ion-exchange membrane in the spin coating of the both sides of above-mentioned film.Film is handled 2.4h down at 190 ℃.Obtain three layers cross-linked perfluorinated sulfonate film (multilayer film 14#).
Embodiment 12:
With repetitive be
The polymer of EW=1200 prepares monofilm with the method that melt extrudes, and this film is at high temperature handled obtaining the monofilm 13# that cross-linked structure is formula II in 3 hours then.On the two sides of monofilm 13# folded on multilayer film 12# and 120 ℃ of hot-pressing processing, hydrolysis acidification obtains 23 layers of cross-linked perfluorinated sulfonate film (multilayer film 15#) then.
Embodiment 13:
With repetitive be
Polymer and repetitive be:
Polymer be that mixed mixed melting in sieve bar extruder of 2: 3 extrudes that to obtain thickness be 50 microns film (monofilm 13#) with mass ratio.
With repetitive be
Polymer be dissolved in the hempa acid amide that to form solid content be 50% dispersion. the method by curtain coating is at the monofilm of 150 ℃ of systems. place the DMF solution of peroxidating perfluorocarboxylic acid to soak the cross-linked structure monofilm 14#. that heating obtains the formula that forms (I) this film
Monofilm 13# is placed between two monofilm 7# and two the compound hot pressing posthydrolysis of monofilm 14# acidifyings again, obtain multilayer film 16#.
Embodiment 14:
With repetitive be
Polymer dispersed to form solid content in the N-methyl pyrrolidone be 30% dispersion liquid. utilize method film forming on plate glass of spraying. (monofilm 15#).
With above-mentioned polymer be with repetitive
Polymer be to be scattered among the DMSO after 1: 5 the mixed by mass ratio, again to above-mentioned mixed liquor, form triazine crosslinked rings by the The tape casting film forming and with film at 230 ℃ after adding a spot of antimony organic catalyst again. (monofilm 16#).
It is 300 microns 15 tunics (multilayer film 17#) that monofilm 16# and monofilm 15# are stacked alternately the compound thickness that obtains of hot pressing.
Embodiment 15:
With repetitive be
The EW=1250 polymer obtains 19% solution in the hempa acid amide, by the silk-screen printing technique method, at multilayer film 14# upper layer film.Film is handled 300min under the irradiation of ultraviolet light, obtaining cross-linked structure is the multi-layer perfluor sulfonate film (multilayer film 18#) of I.
Embodiment 16:
With repetitive be
Polymer, tertbutanol peroxide, 1,4-diiodo-octafluoro fourth is dissolved among the DMF, obtains the film that thickness is 25 μ m by the silk-screen printing technique method.Film is handled 3min down at 160 ℃.Obtain crosslinked perfluoro sulfonic acid membrane.(monofilm 17#)
Above-mentioned ionic membrane is placed same polymer, benzoyl peroxide, 1 once more, soaked 0.5 hour in the dimethyl sulphoxide solution of 14-diiodo-20 fluorine ten alkane, then film is taken out drying, repeat above-mentioned steps, film is handled 300min down at 120 ℃, obtain three layers of perfluorinated sulfonic acid cross-linking ion membrane.
Carry out hot pressing with above-mentioned three individual layer perfluorinated sulfonic acid cross-linking ion membranes are stacked, make nine layers of perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 19#).。
Embodiment 17:
With repetitive be
Polymer and repetitive be:
Polymer be to be scattered in after 1: 4 the mixed to form 22% solution among the NMP with mass ratio, going out to obtain thickness through curtain coating is 50 microns film (monofilm 18#).
With monofilm 18# place between two monofilm 7# again with two compound hot pressing of monofilm 14# after sodium type multilayer amberplex (multilayer film 20#).
Embodiment 18:
With repetitive be
The polymer of EW=700 and repetitive are
The polymer of EW=1300 (the resin quality ratio is 1: 0.5) is dissolved in 22% the solution of making among the DMF, 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 cross-linked structure, this amberplex are put in the film (monofilm 19#) that obtains (IV) cross-linked structure in the chlorosulfonic acid more again.
With monofilm 19# and multilayer film 2# hot pressing, make five layers of perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 21#).
Embodiment 19:
With repetitive be
Polymer melt extrude. (monofilm 20#).
Monofilm 16# and monofilm 20# are stacked alternately hot pressing, and compound to obtain thickness be 100 microns 5 tunics and the hydrolysis in acid of this film is got multilayer film (multilayer film 22#).
Embodiment 20:
With repetitive be
Polymer and repetitive be:
Polymer be that 0.5: 5 mixed is scattered in and forms 24% solution among the NMP with mass ratio, going out to obtain thickness through curtain coating is 50 microns film (monofilm 21#).
With monofilm 21# place between two monofilm 7# again with two compound hot pressing of monofilm 14# after acidifying get multilayer amberplex (multilayer film 23#).
Embodiment 21: with repetitive be
EW=900 polymer-extruded obtains the film that thickness is 30 μ m.Soak and 1 in the DMF solution of 2-ethylenediamine 5 hours.Get the film that (III) plants cross-linked structure at 200 ℃.With this film alkali lye, the cross linking membrane (monofilm 22#) that acid solution is handled.
With monofilm 22#, crosslinked 16 tunics (multilayer film 24#) of monofilm 11# and multilayer film 11# and the overlapping hot pressing of multilayer film 7# film, thickness is 300 μ m
Comparative example 22:
The method of utilizing 10%nafion DMF soln using to pour into a mould obtains the amberplex of 60 micron thickness 170 ℃ of processing.
Embodiment 23
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 multilayer fluorine-containing cross-linking ion film ℃ of conductivity, hot strength, hydrogen permeate electric current all is better than common exchange membrane containing fluorine.
The various films of table 1 characterize
Claims (9)
1. multilayer fluorine-containing cross-linking ion film is to be the multilayer film of the 2-40 layer that forms of the ion exchange fluoro resin of 600～1300mmol/g with the EW value, wherein has at least 1 layer to have cross-linked structure, conductivity 40～150mS/cm, hot strength 10～60Mpa; Gross thickness 10～300 μ m;
Described cross-linked structure is selected from one or more as shown in the formula (I), (II), (III), (IV) and/or in the structure (V):
Wherein, G
1=CF
2Or O, G
2=CF
2Or O, R
fBe C2-C10 perfluor carbochain or chloride perfluor carbochain;
Wherein, R is methylene or perfluor methylene, and n is 0～10 integer;
2. a kind of multilayer fluorine-containing cross-linking ion film as claimed in claim 1, it is characterized in that: 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 copolymer;
Fluorine containing olefine is selected from: tetrafluoroethene, and chlorotrifluoroethylene, trifluoro-ethylene, hexafluoropropylene, and/or in the vinylidene one or more, preferred, Fluorine containing olefine is selected from tetrafluoroethene or chlorotrifluoroethylene;
The fluorine-containing alkene monomer that contains functional group is selected from one or more as shown in the formula (VI), (VII) and/or in the structure (VIII):
R
f3CF＝CF(CF
2)
dY
2
(VII)
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 dichlorodifluoromethan base respectively;
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 Br, F, Cl, OR or NR
1R
2Described R is selected from methyl, ethyl or 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 one or more as shown in the formula (IX) and/or in the structure (X):
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
3. a kind of multilayer fluorine-containing cross-linking ion film as claimed in claim 1 or 2 is characterized in that: the EW value of described ion exchange fluoro resin is 700-1200mmol/g; The number of plies of multilayer film is the 2-10 layer, gross thickness 10-50 μ m
4. the preparation method of a kind of multilayer fluorine-containing cross-linking ion film as claimed in claim 1 is characterized in that, each monofilm utilize solution or fused mass casting, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology make; The preparation of multilayer film is by compound between monofilm, compound between compound or multilayer film and multilayer film between multilayer film and monofilm, also can directly on monofilm that has made or multilayer film, utilize solution or fused mass casting, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology preparation.
5. the preparation method of a multilayer fluorine-containing cross-linking ion film as claimed in claim 4 is characterized in that, the step of solution casting, solution casting, silk-screen printing technique, spin coating, spraying or dipping is as follows:
(1) with ion exchange fluoro resin, crosslinking agent, additives such as acid and/or radical initiator are distributed to solvent and form mixture; Ion exchange fluoro resin content is 1～80% in the mixture, weight ratio;
(2) utilize the middle preparation of step (1) solution passing through solution casting, solution casting, silk-screen printing technique, spin coating, spraying or impregnation technology film forming on the flat board or on the single or multiple lift film that has prepared; Will be under 30～300 ℃ temperature during film forming heat 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 cross-linked structure.
6. the preparation method of a multilayer fluorine-containing cross-linking ion film as claimed in claim 5, it is characterized in that the used solvent of step (1) is one or more in dimethyl formamide, dimethylacetylamide, methylformamide, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, hempa acid amide, acetone, water, ethanol, methyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol or the glycerol; Described crosslinking agent is selected from the described material of formula (XI), ammonia, hydrazine, organic diamine or can discharge ammonia through chemical treatment, the material of hydrazine, organic diamine; Will be under 80～250 ℃ temperature during film forming in the step (2) heat treatment 20～60 minutes.
7. the preparation method of a multilayer fluorine-containing cross-linking ion film as claimed in claim 4 is characterized in that, melt extrudes with the step of pressure sintering as follows:
(1). according to the suitable ion exchange fluoro resin of needs preparation of each layer formula in the multilayer fluorine-containing cross-linking ion film, crosslinking agent, acid and/or radical initiator mixture utilize double screw extruder, banbury or mill 200～280 ℃ of mixing; Described ion exchange fluoro resin is selected from sulfuryl fluoride, sulfonic acid chloride or sulfonic acid bromide resin;
(2) resin that step (1) is mixed utilizes screw extruder or vulcanizing press film forming;
(3) crosslinked in the film forming, or after the film forming; Formation be (I), (II), (III), (IV) and/or (V) shown in cross-linked structure, monofilm;
(4) monofilm is compound, obtains described multilayer fluorine-containing cross-linking ion film.
8. preparation method as claim 5 or 7 described multilayer fluorine-containing cross-linking ion films, it is characterized in that, the method that forms the cross-linked structure shown in the formula (I) comprises heat, light, electron radiation, plasma, X ray or radical initiator, also can pass through heat, light, electron radiation, plasma, X ray or action of free radical initiator and form cross-linked structure when one or more crosslinking agents exist; Wherein the structure of employed crosslinking 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 dichlorodifluoromethan base;
Described radical initiator is organic peroxide, azo-initiator etc., and wherein the general formula of peroxide initiator can be expressed as (XII) and (XIII):
R
1OOR
2
(XII)
R
1, R
2Respectively from following groups but be not limited only to choose arbitrarily these groups:
R
1, R
2Respectively from following groups but be not limited only to choose these groups: the alkyl that the aroyl of the alkyl that the alkyl or aryl of H, C1～C20 replaces, the acyl group of C1～C20, C1～C20, the fluorine-containing or perfluoroalkyl of C1～C20 or aryl replace, the fluorine-containing or perfluoro acidyl of C1～C20, the fluorine-containing or perfluor aroyl of C1～C20; But R
1, R
2Can not select H simultaneously;
R
3, R
4Respectively from following groups but be not limited only to choose arbitrarily these groups:
The alkyl that the alkyl that the alkyl or aryl of C1～C20 replaces, the fluorine-containing or perfluoroalkyl of C1～C20 or aryl replace;
Azo-initiator is but is not limited only to following several:
Azo-initiator is but is not limited only to following several: Celogen Az, azodiisobutyronitrile, AMBN, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, 1-((cyano group-1-Methylethyl) azo) formamide, 1,1 '-azo (cyclohexyl-1-cyano group), 2,2 '-azo (2-methyl-propyl amidine) dihydrochloride, 4,4 '-azo two (4-cyanopentanoic acid) or 3-hydroxyl-4-nitrobenzoic acids.
The method that forms (II), (III) cross-linked structure is: utilize sulfuryl fluoride, sulfonic acid chloride, sulfonic acid 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) cross-linked structure is that the sulfonic fluoropolymer resin utilizes the chlorosulfonic acid processing to obtain;
The method that forms (V) cross-linked structure is that the fluorine-containing sulfuryl fluoride resin in the sulfonic fluoropolymer resin in nitrile group-containing site, nitrile group-containing site, the sulfonic acid bromide resin that contains that contains sulfonic acid chloride resin or nitrile group-containing site in nitrile group-containing site form under hot or sour effect;
Described acid is strong protonic acid or lewis acid; Wherein strong 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.
9. the preparation method of multilayer fluorine-containing cross-linking ion film as claimed in claim 8 is characterized in that, described radical initiator is the perfluor organic peroxide.
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| CN2009101759992A Division CN101685865B (en) | 2008-07-29 | 2008-07-29 | Multilayer fluorine-containing cross-linked ion-exchange membrane and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102458618A (en) * | 2009-04-13 | 2012-05-16 | 国立大学法人山口大学 | Ion-exchange membrane and method for producing same |
| US20130190456A1 (en) * | 2010-12-07 | 2013-07-25 | Daikin Industries, Ltd. | Curable composition, molded article and method for producing molded article |
| CN111755702A (en) * | 2020-06-17 | 2020-10-09 | 鄂尔多斯市国科能源有限公司 | Method for preparing fuel cell catalyst layer containing self-crosslinking ionic polymer |
-
2008
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102458618A (en) * | 2009-04-13 | 2012-05-16 | 国立大学法人山口大学 | Ion-exchange membrane and method for producing same |
| US9266069B2 (en) | 2009-04-13 | 2016-02-23 | Yamaguchi University | Ion-exchange membrane and method for producing same |
| CN102458618B (en) * | 2009-04-13 | 2016-07-13 | 国立大学法人山口大学 | Ion exchange membrane and manufacture method thereof |
| US20130190456A1 (en) * | 2010-12-07 | 2013-07-25 | Daikin Industries, Ltd. | Curable composition, molded article and method for producing molded article |
| US9169339B2 (en) * | 2010-12-07 | 2015-10-27 | Daikin Industries, Ltd. | Curable composition, molded product and method for producing molded product |
| CN111755702A (en) * | 2020-06-17 | 2020-10-09 | 鄂尔多斯市国科能源有限公司 | Method for preparing fuel cell catalyst layer containing self-crosslinking ionic polymer |
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