CN101757861B - Multi-layer perfluor cross-linking ion membrane and preparation method thereof - Google Patents
Multi-layer perfluor cross-linking ion membrane and preparation method thereof Download PDFInfo
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- CN101757861B CN101757861B CN2009102311269A CN200910231126A CN101757861B CN 101757861 B CN101757861 B CN 101757861B CN 2009102311269 A CN2009102311269 A CN 2009102311269A CN 200910231126 A CN200910231126 A CN 200910231126A CN 101757861 B CN101757861 B CN 101757861B
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Abstract
The invention relates to a multi-layer cross-linking ion membrane generated from perfluor ion-exchange resin, belonging to the field of functional polymer composite materials. At least one layer of the multi-layer cross-linking ion membrane has a cross-linking reticular structure, and at least one layer of the multi-layer cross-linking ion membrane contains high-valence metallic compounds; moreover, high-valence metallic compounds are added to the multi-layer cross-linking ion membrane, so that the high-valence metallic compounds and the acidic exchanging groups in the resin can physically bonded. Accordingly, the invention further improves the stability and mechanical properties of the multi-layer cross-linking ion membrane and particularly improves the performance in gas permeation prevention.
Description
Technical field
The invention belongs to field of functional polymer composites, relate to a kind of cross-linked structure that has, and added perfluorinated ion-exchange membrane of high-valency metal compound and preparation method thereof.
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.
Present employed perfluorinated sulfonic acid PEM has good proton-conducting and chemical stability under (as 80 ℃) and the higher humidity at a lower temperature.But they also have a lot of defectives,, poor stability not high as poor dimensional stability, mechanical strength etc.Film is the water absorption rate difference under different humidity, expands also different with the size that causes because of suction.When film during at different operating mode down conversions, therefore the size of film also will change.Conversion so repeatedly finally causes PEM generation mechanical damage.In addition, under the special working environment of fuel cell, usually can produce the material such as the free radical of a lot of strong oxidizing properties, the 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, 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.
Therefore the crosslinked mechanical strengths that can improve the heat endurance of polymer, the swelling that reduces solvent, raising polymer etc. have 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, crosslinking technological is explored and studied.
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 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, thereby 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 and sulfuryl fluoride react in the process of infiltration, the sulfuryl fluoride of reaction will stop ammonia to the inner further diffusion of film, 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.
The degree of cross linking that crosslinked in the past Modified Membrane obtains is often not high, and the mechanical strength of the film after crosslinked is not significantly improved.Chinese patent 200810138705.4 provides a kind of crosslinked sandwich construction exchange membrane containing fluorine and preparation method, this method is crosslinked and sandwich construction dual mode with chemical bond, solve the infiltrative problem of the gentle body of Mechanics of Machinery character of film to a certain extent, but still had problems such as the degree of cross linking is not high.
Though all above documents have carried out certain improvement in performance to such amberplex, but these documents have only improved the performance of an aspect of film, do not improve the dimensional stability of film and the electric conductivity under the high temperature low humidity simultaneously, especially prevent from not improve significantly and improve aspect the working media permeability at film.
And the perfluorinated sulfonic acid ionic membrane that is used for fuel cell need satisfy following specification requirement: 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.And the also rising thereupon of the medium osmosis of film, this has produced very fuel cell performance and has seriously influenced.Therefore; preparation has the macroion exchange capacity; have favorable mechanical mechanical strength and air-tightness simultaneously, and the film with good stable becomes and make fuel cell, especially the fuel cell that uses on delivery vehicles such as automobile is able to the key point of scale practicality.
Summary of the invention
For solving above-mentioned many defectives, inventor's process is furtherd investigate, and has paid a large amount of creative works, thereby has finished the present invention.
The purpose of this invention is to provide a kind of cross-linked perfluorinated multilayer ionic membrane.Form at the exchanger resin that employing has a crosslinked group on the basis of crosslinking net network structure of chemical bonding, carry out physical bond by the acidic exchange group that adds in high-valency metal compound and the film, thereby further consolidate cross-linked structure.Simultaneously,, thereby greatly reduce the permeability of gas and working media, improved the Mechanics of Machinery character and the stability of film because this film has adopted sandwich construction.
The invention provides the crosslinked synergistic ionic membrane of physical bond of crosslinked and high-valency metal compound of a kind of chemical bond and acidic exchange group, again film is made sandwich construction.By on the crosslinked basis of chemical bond, add the high-valency metal compound can between metallic element and the acidic exchange group, metallic element and some crosslinked group form further physical bond or complex bound as between amino, the imide.This bonding action makes the Mechanics of Machinery intensity of film be greatly improved, and the inventor finds that also this Modified Membrane has the good air-tightness of non-height (performance than the multilayer cross-linked structure film that does not add high-valency metal improves a lot) simultaneously.In addition, the inventor also is surprised to find, and so the film of modification has obtained further raising to the stability of free radical, traces it to its cause, thereby should be that the film fine and close oxidant such as free radical that makes that becomes can't diffuse in the film easily.
Multi-layer perfluor cross-linking ion membrane of the present invention, this film is the multilayer film of the 2-40 layer that formed by perfluorinated ion exchange resin, and being preferably is 2～5 layers, wherein has at least 1 layer to have cross-linked structure, and have at least one deck to have the high-valency metal compound, gross thickness can be 10-100 μ m; Wherein the EW value of perfluorinated ion exchange resin is not special limits, and for example can be 700～1200mmol/g, comprises that any subrange in this scope is as 600～1300mmol/g.
Wherein, described cross-linked structure is selected from as shown in the formula (I), (II), (III), (IV) or one or more in the structure (V):
Wherein, G
1=CF
2Or O, G
2=CF
2Or O, R
fBe C
2-C
10The perfluor carbochain.
Wherein, R is methylene or perfluor methylene, and n is 0～5 integer;
Following formula (I), (II), (III), (IV) or (V) in the sweep representative contain fluorocarbon chain.
Wherein, described perfluorinated ion exchange resin is to be formed by tetrafluoroethene, one or more perfluor alkene monomer, one or more fluorine-containing alkene monomer copolymerization that contain crosslink sites that contain the acidic exchange group, perhaps the mixture of one or more above-mentioned copolymers.
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
Wherein, the described perfluor alkene monomer that contains the acidic exchange group is selected from (A) with following formula structure or (B):
CF
2＝CFO[CF
2CF(CF
3)]
fO(CF
2)
gSO
2R
F=0 or 1; The integer of g=2～4; R is OH, F, Cl or Br (A)
CF
2＝CFO(CF
2)
3PO
3HR’(B)
R ' is H or Me.
Wherein, the described fluorine-containing alkene monomer that contains crosslink sites is selected from (IX) with following formula structure or (X):
F
2C＝CFR
f4Y
4
(IX)
Wherein, Y
4, Y
5Be Br, I or CN independently;
A ',, b ', c ' they are 0 or 1 independently, but a '+b '+c ' ≠ 0;
X
1Be selected from F, Br or I;
N ' is 0 or 1;
R
F4, R
F5, R
F6Be perfluoroalkyl independently.
Wherein, the metallic element of described high-valency metal compound is selected from down one of column element or combination: W, Zr, Ir, Y, Mn, Ru, Ce, V, Zn, Ti or La.The amount of these metallic compounds is not special to be limited, and for example can account for 0.001～5% of perfluorinated ion exchange resin quality.
Described high-valency metal compound can be selected from a kind of or combination double salt in the nitrate, sulfate, carbonate, phosphate, acetate of the highest price attitude of these metallic elements and middle valence state.
Described high-valency metal compound can be selected from the complex compound of cyclodextrin, crown ether, acetylacetone,2,4-pentanedione, nitogen-contained crown ether and nitrogen heterocyclic ring, EDTA (ethylenediamine tetra-acetic acid), DMF (N, dinethylformamide) or the DMSO (dimethyl sulfoxide (DMSO)) 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 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.
Described oxide with perovskite structure for example can be Compound C e
xTi
(1-x)O
2(x=0.25～0.4), Ca0.6
La0.27TiO
3, La
(1-y)Ce
yMnO
3(y=0.1～0.4) or La
0.7Ce
0.15Ca
0.15MnO
3
Each layer in the described multi-layer perfluor cross-linking ion membrane can all form cross-linked structure, also allows part layer not form cross-linked network structure, perhaps forms cross-linked structure between layer and the layer.Can make that the active force between the layer-layer is greatly strengthened because form crosslinking net between layer and the layer, thus more difficult the disengaging increased the mechanical strength of this film, so preferably the top and nethermost two skins have cross-linked structure.
The present invention also provides the preparation method of described multi-layer perfluor cross-linking ion membrane: each monofilm is the cast that utilizes solution or fused mass, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology are prepared; And the preparation of multilayer film is by compound preparation the between compound between compound between the monofilm, multilayer film and the monofilm or multilayer film and the multilayer film, also can be 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 be prepared.
Wherein, the step of solution casting, solution casting, silk-screen printing technique, spin coating, spraying or dipping is as follows:
(1) perfluorinated ion exchange resin, crosslinking agent (when existing), acid, radical initiator and high-valency metal compound are distributed to solvent and form mixture; The mass content of perfluorinated ion exchange resin is 1～80% in the mixture; Used solvent is one or more in 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 the glycerine; Described crosslinking agent is selected from following formula (XI), ammonia, hydrazine, organic diamine or can discharges the material of ammonia, hydrazine, organic diamine through chemical treatment;
(2) with the mixture of preparation in the step (1) on flat board, or on the single or multiple lift film that has prepared, form film by solution casting, solution casting, silk-screen printing technique, spin coating, spraying or impregnation technology; Needed under 30～300 ℃ temperature heat treatment during film forming 10～100 minutes;
(3) between film forming stage, or carry out after the film forming crosslinked, form formula (I), (II), (III), (IV) or (V) shown in cross-linked structure.
Preferably, the temperature in the step (2) is 80～250 ℃, more preferably 100～200 ℃; Heat treatment time is 20～60 minutes, more preferably 30～50 minutes.
The method that forms the cross-linked structure shown in the formula (I) is included in heat, light, electron radiation, plasma, X ray or radical initiator and exists down, forms cross-linked network structure by heat, light, electron radiation, plasma, X ray or action of free radical initiator shape in the time of perhaps in the presence of one or more crosslinking agents.The structure of wherein said crosslinking agent is as shown in the formula shown in (XI):
X
2R
f7X
3
(XI)
X
2, X
3Be independently 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 described peroxide initiator can be (XII) or (XIII):
R
1OOR
2
(XII)
Non-limiting ground, R
1,, R
2Can be following group: H, C independently
1～C
20The C that alkyl or aryl replaces
1～C
20Alkyl, C
1～C
20Acyl group, C
1～C
20Aroyl, C
1～C
20Contain fluoroalkyl or perfluor C
1～C
20The C that alkyl or aryl replaces
1～C
20Base, C
1～C
20Perfluoro acidyl or C
1～C
20Fluorine-containing acyl group, C
1～C
20Fluorine-containing aroyl or C
1～C
20The perfluor aroyl; But R
1R
2Can not be H simultaneously.
R
3,, R
4Can be following group independently:
C
1～C
20The C that alkyl or aryl replaces
1～C
20Alkyl, C
1～C
20Contain perfluoroalkyl or C
1～C
20The C that perfluoroalkyl or aryl replace
1～C
20Alkyl.
Described azo-initiator is optional from as follows: Celogen Az, azodiisobutyronitrile, AMBN, ABVN, 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 or 4,4 '-azo two (4-cyanopentanoic acid).
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 react through the material that chemical treatment discharges ammonia, hydrazine, organic diamine and obtain.
Described organic diamine is C
1～C
10Alkyl or perfluoroalkyl diamines, described organic or inorganic acid hydrochlorate, urea or the guanidine that can include but not limited to ammonia, hydrazine, organic diamine through the material that chemical treatment discharges ammonia, hydrazine, organic diamine.
The method that forms (IV) cross-linked structure is to utilize chlorosulfonic acid to handle and obtain perfluorinated sulfonic resin.
The method that forms (V) cross-linked structure is that the perfluor sulfonyl fluororesin in the perfluorinated sulfonic resin in cyano-containing site, cyano-containing site, the sulfonic acid bromide resin that contains that contains sulfonic acid chloride resin or cyano-containing site in cyano-containing site form under hot or sour effect.
Described acid is strong protonic acid or lewis acid; Wherein said strong protonic acid is selected from H
2SO
4, CF
3SO
3H or H
3PO
4Deng; Lewis acid is selected from ZnCl
2, FeCl
3, AlCl
3, organotin, antimony organic or organic tellurium etc.
Melt extrude with the step of pressure sintering as follows:
(1) according to the needs of each layer formula in the multi-layer perfluor cross-linking ion membrane, the mixture of perfluorinated ion exchange resin, crosslinking agent, acid, radical initiator and high-valency metal compound that preparation is fit to utilizes double screw extruder, banbury or mill to mix at 200～280 ℃; Described perfluorinated ion exchange 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) between film forming stage, or carry out crosslinkedly after the film forming, obtain monofilm;
(4) monofilm of step (3) is carried out compound, obtain described multilayer film.
Wherein, the film of gained can be converted in advance behind the acid type again with other film carry out compound, also can be earlier and the compound acid type that transfers to again of other film.
Utilize extrusion by melting form layer with layer between cross-linked structure method can also for: two kinds of resins that can form cross-linked structure are at high temperature extruded, and increase pressure carries out compound, make the surface of two kinds of resins merge mutually, utilize cross-linking method to make its generation crosslinked then; Be dipped into perhaps with a kind of prior film forming of resin that contains crosslink sites, and with this film and carry out swelling in the resin solution that contains identical crosslink sites, do crosslinking Treatment, thereby obtain film crosslinked between the layer-layer.
Preferably, can be after preparing film (can be multilayer film, also can be monofilm), it is immersed in the solution of required high-valency metal compound reaches the purpose that makes up metal corsslinking.
Owing to introduced the high-valency metal compound in film, it is crosslinked to form electrostatic bonding effectively in film and between sulfonic acid group or the phosphate group, also can realize easily simultaneously the multilayer film middle level with layer between crosslinked (in the accompanying drawing 1 be example with the sulfonate radical).So not only further use mechanical strength and the dimensional stability that has improved ionic membrane, and inventor's fuel permeability of also finding film is than the little several times of multilayer cross linking membrane of original no high-valency metal compound even tens times.Studying carefully its possible reason, should be that metallic compound has carried out physical bond with the ion-exchange group in the film, has further reduced the distance between these groups, thereby has dwindled the volume of ion cluster, has increased the resistance of fuel infiltration.
The specific embodiment:
By the following examples the present invention is further specified, but it will be understood by those skilled in the art that these embodiments only are used to exemplify, but not spirit of the present invention and claimed scope are carried out any type of restriction.
Embodiment 1:
With repetitive be
, EW=1000 fluoropolymer resin make the aqueous propanol solution that mass concentration is 5wt%, add MnCO to above-mentioned solution again
3(account for resin quality 0.01%) is mixed with mass concentration then and is peroxidating perfluor malonyl-DMF solution of 5%, and be cast in the polytetrafluoroethylene (PTFE) mold of horizontal positioned,, after 12 hours film is peeled off through 80 ℃ of vacuum drying, and in molar concentration the H of 0.5M
2SO
4Boil 1 hour in the solution, and spend deionised water.Obtain the having structural formula individual layer perfluorinated sulfonic acid cross-linking ion membrane (monofilm 1#) of (I).Carry out hot pressing with above-mentioned two individual layer perfluor cross-linking ion membranes are stacked, make the double-deck perfluor cross-linking ion membrane (multilayer film 1#) that contains the high price manganese ion.
Embodiment 2:
With repetitive be
, EW=800 fluoropolymer resin and have the Ce of perovskite structure
xTi
(1-x)O
2(x=0.4) (account for resin quality 2%) mixes, and extrudes at 250 ℃ and to obtain the film that thickness is 10 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 was placed triethylamine 2 hours at 200 ℃, obtain having the film of crosslinking net.This film is handled with KOH solution, hydrochloric acid solution successively, obtained the amberplex (duplicature 2#) of layer-layer cross-linked structure for (II).
Above-mentioned ionic membrane put with repetitive be
, EW=1200 fluoropolymer resin and tetraphenyltin mix, extrude under 200 ℃ with double screw extruder then, make the film that thickness is 20 μ m, then with film 230 ℃ of down heating 10 hours, obtain having the film of cross-linked structure for (V).This film is used LiOH successively, and salpeter solution is handled and is obtained individual layer cross-linking ion membrane (monofilm 3#); As if duplicature 2# and 3# are carried out hot pressing, obtain crosslinked trilamellar membrane, and this trilamellar membrane is immersed in the aqueous solution of cerous nitrate (should be cerous nitrate), obtain the multilayer cross linking membrane (multilayer film 2#) of Ce and Ce-Ti modified oxide, thickness is 40 μ m.
Embodiment 3:
With repetitive be
, EW=1100 fluoropolymer resin and La
0.7Ce
0.15Ca
0.15MnO
3(account for resin quality 1%) and urea is by being hot pressed into the film that thickness is 50 μ m, and 170 ℃ of heating 5 hours down, obtaining having cross-linked structure with alkali and acid treatment successively is (the ionic membrane of II (monofilm 4#) then.
With repetitive be
, to make mass concentration be 30% DMSO solution for the fluoropolymer resin of EW=940 and La-DMSO complex compound (account for resin quality 0.007%), the method by casting made the film that thickness is 10 μ m (monofilm 5#) in following 60 minutes at 170 ℃.
Carry out hot pressing with the perfluorinated sulfonic acid ionic membrane of monofilm 4# and 5# is stacked, carry out hot pressing with monofilm 1# then, obtain containing three layers of cross-linking ion membrane (multilayer film 3#) of three kinds of different metals high price things.
Embodiment 4:
With repetitive be
, the fluoropolymer resin of EW=700 and zinc carbonate (account for resin quality 0.02%) be dissolved in that to make mass concentration among the DMF be 20% solution, the method for utilizing curtain coating then made the individual layer perfluorinated sulfonic acid cross-linking ion membrane that thickness is 30 μ m through 20 minutes under 230 ℃.This amberplex be impregnated in obtain having the film that cross-linked structure is formula (IV) (monofilm 6#) in the chlorosulfonic acid.
Above-mentioned ionic membrane is placed once more fluoropolymer resin and peroxidating perfluor bay two acyls, 1 of embodiment 1, in DMF-acetylacetone,2,4-pentanedione-V (III) complex (3wt%) solution of 4-diiodo-octafluorobutane, soaked 0.5 hour, then film is taken out, drying obtains the crosslinked trilamellar membrane (multilayer film 4#) that contains vanadium and zinc.
Embodiment 5:
With repetitive be
, EW=1300 fluoropolymer resin, AMBN, EDTA-yttrium (III) complex compound (account for resin quality 0.03%) and 1,4-diiodo-octafluorobutane is dissolved among the DMF, and the method by casting made the film that thickness is 20 μ m through 10 minutes under 270 ℃.Again the perfluorinated sulfonic resin among the embodiment 4 is dissolved in the N-methyl pyrrolidone, and to become thickness in the spin coating of the both sides of above-mentioned film be the film of 30 μ m, prepare the three layers of perfluorinated ion-exchange membrane (multilayer film 5#) that contain yttrium.This film was handled 2.4 hours down at 69 ℃, obtained having three layers of perfluoro sulfonic acid membrane that cross-linked structure is a formula (II).
Above-mentioned ionic membrane and monofilm 1# are carried out hot pressing, obtain four layers of perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 6#).
Embodiment 6:
With repetitive be
, EW=1300 fluoropolymer resin, bipyridyl-Ru complex compound (account for resin quality 0.03%) and and Ca0.6
La0.27TiO
3(account for resin quality 0.3%) is scattered in the hempa acid amide (solid masses content is 5%), by the spraying coating process method, obtains the film that thickness is 10 μ m through 30 minutes under 200 ℃.This film was handled 100 minutes down at 230 ℃, obtained having the individual layer perfluoro sulfonic acid membrane that cross-linked structure is a formula (II) (monofilm 7#).
Use is scattered in the above-mentioned solution in the hempa acid amide, sprays by the spraying coating process method once more in the both sides of this monofilm 7#, and making thickness is crosslinked four layers of perfluoro sulfonic acid membrane (multilayer film 7#) of 40 μ m.
Embodiment 7:
With repetitive be
The fluoropolymer resin of EW=1300, benzoyl peroxide, 1,14-diiodo-20 fluorine, ten alkane and zirconium nitrate (account for resin quality 0.2%) are scattered in and make solution in the dimethyl sulfoxide (DMSO), obtain the film that thickness is 25 μ m by the silk-screen printing technique method then.Film was handled 3 minutes down at 160 ℃, obtained crosslinked individual layer perfluoro sulfonic acid membrane (monofilm 8#).
Above-mentioned ionic membrane is placed above-mentioned fluoropolymer resin, benzoyl peroxide, 1 once more, 14-diiodo-20 fluorine ten alkane, DMF-cerium (III) complex compound (account for resin quality 0.04%) are scattered in the solution that makes in the dimethyl sulfoxide (DMSO), soaked 0.5 hour, then film is taken out and carry out drying, repeat repeatedly above-mentioned soaking step, thereby in the two sides film forming.Then film was handled 300 minutes 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 multilayer film 8# and monofilm 8# are stacked, make four layers of perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 9#) of enhancing.
Embodiment 8:
With repetitive be
, EW=1250 fluoropolymer resin and nitogen-contained crown ether (N
5O
3-24-hat-8)-W complex compound (account for resin quality 0.15%) is dissolved in the hempa acid amide, obtains mass concentration and be 30% solution, by the spraying coating process method, obtains the film that thickness is 40 μ m.Film was handled 100 minutes down at 230 ℃, obtained crosslinked individual layer perfluoro sulfonic acid membrane (monofilm 9#).
Use is scattered in the above-mentioned solution in the hempa acid amide, sprays by the spraying coating process method once more in the both sides of this monofilm 9#, and making thickness is 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
, EW=900 fluoropolymer resin and Zr (OH)
4(account for resin quality 3%) extruded, obtained the film that thickness is 30 μ m.This film is immersed in NH
3DMF solution in 5 hours.Under 200 ℃, handle and obtain having the film of structure for the cross-linked structure of (II).This film is obtained individual layer cross linking membrane (monofilm 10#) with alkali lye, acid solution processing.
With repeat unit structure be
, EW=1200 fluoropolymer resin, and Ti (OH)
2(account for resin quality 0.32%), Ca0.6
La0.27TiO
3(account for resin quality 1.3%) and tetraphenyltin are extruded into the film that thickness is 20 μ m with double screw extruder, then film are added 10 hours down at 230 ℃, obtain having the cross-linked structure film (monofilm 11#) of structure for (V).Compress into monofilm 10# and 11# elevated temperature heat capable compound, the gained film being placed mass concentration is that 35% hydrazine hydrate reaches 10 hours again, take out back heating 5 hours, the film that has (III) cross-linked structure between (V) cross-linked structure and the layer-layer is arranged simultaneously, this film is handled obtaining crosslinked multilayer film (multilayer film 11#) with alkali lye, acid solution.。
Two multilayer film 11#, a monofilm 8# film are carried out overlapping hot pressing, obtain five crosslinked tunics (multilayer film 12#).
Embodiment 11:
With repetitive be
, EW=1200 fluoropolymer resin, triphenyl tin hydroxide and ruthenium sulfate (account for resin quality 0.067%) be scattered among the DMF, the method by casting under 170 ℃, made through 60 minutes thickness be 20 μ m have the film of structure for the cross-linked structure of (V).The perfluorinated sulfonic resin among the embodiment 4 is dissolved in the N-methyl pyrrolidone, using gained solution to become thickness in the spin coating of the both sides of above-mentioned film is the film of 30 μ m, prepares three layers of perfluorinated ion-exchange membrane again.This trilamellar membrane was handled 2.4 hours down at 190 ℃, and carried out hot pressing, obtain five layers cross-linked perfluorinated sulfonate film (multilayer film 13#) with monofilm 6#, monofilm 9#.
Embodiment 14:
With repetitive be
Fluoropolymer resin and lanthanum nitrate (account for resin quality 0.13%) be scattered in the N-methyl pyrrolidone, form solid masses content and be 30% dispersion liquid, utilize method film forming (monofilm 12#) on plate glass of spraying.
With above-mentioned fluoropolymer resin be with repetitive
Fluoropolymer resin be after 1: 5 ratio is mixed in mass ratio, be scattered in and form solution among the DMSO, in this solution, add a spot of antimony organic catalyst again, then by the The tape casting film forming, and film is carried out crosslinked at 230 ℃, have the triazine crosslinked ring film (monofilm 13#) of structure thereby form for (V).
Monofilm 13# and monofilm 12# be stacked alternately to carry out hot pressing compound, obtaining thickness is five tunics (multilayer film 14#) of 100 μ m.
Comparative example 15:
With repetitive be
, EW=800 fluoropolymer resin under 250 ℃, extrude, obtain the film that thickness is 10 μ m.With two film high-temp. hot pressing of gained together, and be soaked in NH
4In the DMF solution of Cl 5 hours.Then the film that soaks is placed triethylamine 2 hours under 200 ℃, obtain cross linking membrane.This film is handled with KOH solution, hydrochloric acid solution successively, obtained having the amberplex (duplicature 15#) of layer-interlayer cross-linked structure for (II).
With above-mentioned ionic membrane and repetitive be
The fluoropolymer resin of EW=1200 and tetraphenyltin are extruded under 200 ℃ with double screw extruder, make the film that thickness is 20 μ m, then film are heated 10 hours down at 230 ℃, obtain having the film of cross-linked structure for (V).This film is obtained cross-linking ion membrane (monofilm 14#) with LiOH, salpeter solution processing successively.Duplicature 15# and monofilm 14# are carried out hot pressing, obtain cross-linked three-layer film (multilayer film 15#), thickness is 40 μ m.
Comparative example 16:
Utilizing mass concentration is 10% nafion DMF solution, handles down at 170 ℃ with the method for cast, obtains the amberplex that thickness is 60 μ m.
Embodiment 17
Performance to various films characterizes, and the results are shown in Table 1.As can be seen from Table 1, performance such as the electrical conductivity of the multi-layer perfluor cross-linking ion membrane that has added the high-valency metal compound under 95 ℃, hot strength, hydrogen permeate electric current all is better than common perfluorinated ion-exchange membrane.Especially electrical conductivity and hydrogen permeate electric current are better than not adding the cross-linking ion membrane of high-valency metal compound significantly,, thus favorable conductive ability and anti-medium osmosis performance had.
The various films of table 1 characterize
Claims (9)
1. multi-layer perfluor cross-linking ion membrane is characterized in that: this film is the multilayer film of the 2-40 layer that formed by perfluorinated ion exchange resin, and wherein at least 1 layer has cross-linked structure, and one deck has the high-valency metal compound at least; Described cross-linked structure have formula (I), (II), (III), (IV) or (V) shown in the structure one or more:
Wherein, G
1=CF
2Or O, G
2=CF
2Or O, R
fBe C
2-C
10The perfluor carbochain;
Wherein, R is methylene or perfluor methylene, and n is 0～5 integer;
Metallic element in the wherein said high-valency metal compound is selected from one of following or combination: W, Zr, Ir, Y, Mn, Ru, Ce, V, Zn, Ti or La; And
Described high-valency metal compound is selected from the complex compound of cyclodextrin, acetylacetone,2,4-pentanedione, nitrogen heterocyclic ring, EDTA, DMF and the DMSO of the highest price attitude of these metallic elements and middle valence state; Or be selected from the highest price attitude of these metallic elements and the hydroxide 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.
2. multi-layer perfluor cross-linking ion membrane as claimed in claim 1, it is characterized in that: described perfluorinated ion exchange resin be by tetrafluoroethene, one or more contain acidic exchange group perfluor alkene monomer and one or more fluorine-containing alkene monomer copolymerization that contains crosslink sites form, and perhaps are the mixture of multiple above-mentioned copolymer;
The described perfluor alkene monomer that contains the acidic exchange group is selected from as shown in the formula in the structure shown in (A), (B) one or more:
CF
2＝CFO[CF
2CF(CF
3)]
fO(CF
2)
gSO
3R
F=0 or 1; The integer of g=2～4; R is H, F, Cl or bromine; (A)
CF
2＝CFO(CF
2)
3PO
3HR (B)
R is H, F, Cl or bromine;
The described fluorine-containing alkene monomer that contains crosslink sites is selected from as shown in the formula (IX)/or (X):
F
2C＝＝CFRf
4Y
4
(IX)
Wherein, Y
4, Y
5Can be selected from Br, I or CN respectively;
A ', b ', c ' they are 0 or 1 independently, but a '+b '+c ' ≠ 0;
X
1Be selected from F, Br or I;
N ' is 0 or 1;
R
F4, R
F5, R
F6Independently for being selected from perfluoroalkyl.
3. multi-layer perfluor cross-linking ion membrane as claimed in claim 1 or 2 is characterized in that: this film is 2～5 layers the multilayer film that is formed by perfluorinated ion exchange resin.
4. as each described multi-layer perfluor cross-linking ion membrane of claim 1-2, it is characterized in that: described high-valency metal compound is selected from the complex compound of cyclodextrin, acetylacetone,2,4-pentanedione, nitrogen heterocyclic ring, EDTA, DMF and the DMSO of the highest price attitude of these metallic elements and middle valence state.
5. multi-layer perfluor cross-linking ion membrane as claimed in claim 4 is characterized in that: described high-valency metal compound is selected from the highest price attitude of these metallic elements and the nitrogenous heterocyclic complex compound of middle valence state.
6. multi-layer perfluor cross-linking ion membrane as claimed in claim 5 is characterized in that: described nitrogen heterocyclic ring is a nitogen-contained crown ether.
7. as each described multi-layer perfluor cross-linking ion membrane of claim 1-2, it is characterized in that: described high-valency metal compound is selected from the highest price attitude of these metallic elements and the hydroxide of middle valence state.
8. as each described multi-layer perfluor cross-linking ion membrane of claim 1-2, it is characterized in that: described high-valency metal compound is selected from the highest price attitude of these metallic elements and the oxide with perovskite structure of middle valence state.
9. multi-layer perfluor cross-linking ion membrane as claimed in claim 8 is characterized in that: described oxide with perovskite structure is selected from: Ce
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.
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