CN101733011B - Fiber reinforced perfluoro dual crosslinked ion membrane and preparation method thereof - Google Patents
Fiber reinforced perfluoro dual crosslinked ion membrane and preparation method thereof Download PDFInfo
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- CN101733011B CN101733011B CN2009102311362A CN200910231136A CN101733011B CN 101733011 B CN101733011 B CN 101733011B CN 2009102311362 A CN2009102311362 A CN 2009102311362A CN 200910231136 A CN200910231136 A CN 200910231136A CN 101733011 B CN101733011 B CN 101733011B
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Abstract
The invention relates to a fiber reinforced perfluoro dual crosslinked ion membrane and a preparation method thereof, belonging to the field of functional polymer composites. The exchange membrane takes fluorine-containing ion exchange resins as membrane-forming resins and reinforcing fibers are added. Chemical crosslinking structures are formed among the fluorine-containing ion exchange resins or between the fluorine-containing ion exchange resins and crosslinking agents, and the acidic groups on the chemical crosslinking structures are physically bonded and crosslinked with high-valence metal compounds, thereby forming a dual network structure. The fluorine-containing ion exchange membrane prepared by the invention has higher proton conductivity and mechanical property.
Description
Technical field
The invention belongs to field of functional polymer composites, relate to fluorine-containing cross-linking ion membrane of a kind of fiber reinforcement 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 (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.Conversion so repeatedly finally causes PEM generation mechanical damage.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 because 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.
People have proposed certain methods and have solved these problems at present.Propose a kind of Enhancement Method as Japan Patent JP-A-6-231779, be to use fluororesin fiber.The amberplex that it adopts the fluorocarbon polymer reinforcing material of fibrillation form to strengthen.But this method must add a large amount of relatively reinforcing materials, and in this case, the processing characteristics of film is tending towards difficulty, and the film resistance increase takes place possibly.
European patent EP 0875524B1 discloses the technology that the glass fibre membrane that utilizes the preparation of glass fibre non-woven technology strengthens the nafion film, mentions oxides such as can using silica in this patent simultaneously.But non-woven glass fibre cloth is the base material that must use in this patent, and this will limit the scope of application of this enhancing film greatly.
U.S. Pat 6692858 discloses the technology of polytetrafluoroethylene fibre enhancing perfluorinated sulfonic resin.In this technology, with perfluor sulfonyl fluororesin and polytetrafluoroethylene fibre mix, extrude, making the transition makes fibre-reinforced perfluorinated sulfonic resin.This method can not be produced continuously because transformation process is consuming time.
But often there is phase-splitting in fiber reinforcement between enhancing body and film-forming resin, also just have very big gap, thereby the film that causes making has 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, thereby forms the PEM of sulfimide cross-linked structure, and the perfluoro sulfonic acid membrane of Chu Liing has excellent mechanical intensity 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 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.
CN200710013624.7 and US7259208 disclose and have contained triazine ring cross-linked structure perfluoro sulfonic acid membrane, have excellent mechanical intensity and dimensional stability equally.
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 fiber of a kind of chemical bonding.Chemical bonding is crosslinked to carry out modification with two kinds of means of tunica fibrosa 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, the film that preparation has the macroion exchange capacity, have good Mechanics of Machinery intensity and air-tightness, have good stability 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, a kind of fiber reinforcement perfluoro dual crosslinked ion membrane and preparation method thereof is provided.
Fiber reinforcement perfluor chain cross-linked perfluorinated ion-exchange membrane provided by the invention, it is characterized in that: with ion exchange fluoro resin as film-forming resin, described ion exchange fluoro resin forms the chemical crosslinking structure each other or with crosslinking agent, and adds the fiber as reinforce; It is crosslinked that structural acidic-group of described chemical crosslinking and high-valency metal compound form physical bond, thereby form dual cross-linked network structure; Wherein, described chemical crosslinking structure has the cross-bridge shown in the formula (I):
Wherein, G
1=CF
2Or O, G
2=CF
2Or O, R
fBe C
2-C
10The perfluor carbochain.
The cross-linked network structure that high-valency metal compound [is example with the Ce ion] that forms and acidic exchange group physical bond form is shown in (II)
Described ion exchange fluoro 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.
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 is independently selected from Br or I;
A ', b ', c ' are respectively 0 or 1, but a '+b '+c ' ≠ 0;
X
1Be selected from F, Br or I;
N ' is 0 or 1;
R
F4, R
F5, R
F6Be independently selected from perfluoroalkyl, preferred C
1-C
5Perfluoroalkyl
Include but not limited to one or more mixing of following substances as the fiber of reinforce: polymer fiber, simple substance fiber, oxide fibre, oxysalt fibrid, carbide fibre, nitride fiber, boride fiber, sulphide fibres, silicide fiber or phosphide fiber.
Preferably, be selected from glass fibre, fluorocarbon polymer fiber, ceramic fibre, mineral fibres or the oxide fibre one or more as the fiber of reinforce.Described glass fibre is selected from alkali-resistant glass fibre or alkali-free glass fibre; Described fluorocarbon polymer fiber is selected from fiber with ion exchanging function or the poly-perfluoro propyl vinyl ether fiber that makes as polytetrafluoroethylene fibre, perfluoroethylene-propylene fiber, according to prior art CN101003588A; Described ceramic fibre is selected from natural coal jewel fiber or alumina silicate fibre; Described mineral fibres is selected from quartz fibre, silicon carbide fibre or basalt fibre.
Preferably have ion-exchange capacity or surperficial fiber with water conservation group.As the fiber that makes according to prior art CN101003588A with ion exchanging function, the hydrophilic modifying fluorocarbon polymer fiber of surface silicon acidifying, sulfonation, sulphation, phosphorylation, the surface silicifies, oxide of sulfonation, sulphation, phosphorylation modification, carbide, oxysalt class etc.Existing surface modifying method for polytetrafluoroethylene (PTFE) all is suitable for the modification to the fluorine carbon fiber, comprises reduction modification method, laser emission modification method, 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 fluorine carbon fiber surface.Other method of modifying by modification after the fluorine carbon fiber surface hydrophilic group has been arranged, but preferably further carry 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, these fibers directly can be positioned over ethyl orthosilicate, ZrOCl for the surface modification of inorfil
2-H
3PO
4Or carry out modification in the titanate esters etc., and also can when synthetic fibers, add modifier directly to generate modified fibre, as phosphate and ethyl orthosilicate are mixed, reeling off raw silk from cocoons with the alkali gel obtains modified fibre again.
The concrete grammar of for example silica modified polytetrafluoroethylene (PTFE) is placed on SiCl with polytetrafluoroethylene fibre exactly
4Be warmed up to 110 ℃ in the atmosphere after 1 hour also, kept 1 hour, be cooled to 60 ℃ again after, water spray is handled and to be obtained silica modified polytetrafluoroethylene fibre.
The method of titania modified alkali-free glass is that alkali-free glass fibre is placed Ti (OEt)
4Stir adding concentrated ammonia liquor down in the/water mixed system, hydrolysis is left standstill and is obtained the alkali-free glass fibre that titanium dioxide is modified.
The method that also has a kind of modified fibre of separating out jointly, for example triethyl phosphate is mixed with ethyl orthosilicate (1: 100 mass ratio) and add entry and concentrated ammonia liquor, leave standstill gel 12 hours, and utilized this gel to use electrostatic spinning or the technology of reeling off raw silk from cocoons to obtain the phosphoric acid modification silicon dioxide fibre then.
Because the surface active modification of fortifying fibre, make it have acidity or functional group and make and to form strong crosslinked action by the physical bond of high-valency metal compound between fortifying fibre and the film-forming resin.
The diameter of fiber is 0.005 μ m～5 μ m, is preferably 0.01～4 μ m, and more preferably 0.1～3 μ m most preferably is 1～2 μ m; Length is 0.05 μ m～3mm, is preferably 0.1 μ m～2mm, 1 μ m～1000 μ m more preferably, and more preferably 5 μ m～100 μ m most preferably are 10 μ m～50 μ m; The mass ratio of described fiber and ion exchange fluoro resin is 0.5～50: 100, is preferably 1～40: 100, more preferably 3～30: 100, most preferably be 5～20: 100.
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 element.
This metallic compound account for ion exchange fluoro resin quality 0.001～5%, be preferably 0.01～4%, more preferably 0.1～3%, most preferably be 1～2%.
Described high-valency metal compound can load on the fortifying fibre.
Described high-valency metal compound can be selected from a kind of or combination double salt in nitrate, sulfate, carbonate, phosphate 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.Described oxide with perovskite structure comprises but is not only following Compound C e
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 described fibre-reinforced dual cross-linked perfluorinated ionic membrane.It is characterized in that: utilize solution-cast, curtain coating, silk-screen printing technique, spin coating, spraying or impregnation technology to make, cross-linked structure can form in film forming procedure, also can form after film forming.
For example, the step of the casting of solution or fused mass, curtain coating, silk-screen printing technique, spin coating, spraying or dipping is as follows:
(1) perfluorinated ion exchange resin, the fiber as reinforce, crosslinking agent (existing under the situation of crosslinking agent), radical initiator, high-valency metal compound are distributed to solvent and form mixture; The mass content of ion exchange fluoro resin is 1～80% in the mixture, is preferably 5～60%, more preferably 10～50%, most preferably be 20～40%;
(2) utilize the solution of preparation in the step (1) on flat board, to pass through solution casting, solution casting, silk-screen printing technique, spin coating, spraying or impregnation technology film forming; Needed under 30～300 ℃ temperature heat treatment during film forming 10～100 minutes;
(3) form the cross-bridge structure shown in the formula (I),
The solvent that step (1) is used can be but be not limited only to a kind of of following solvent or combination: 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, will be under 80～250 ℃ temperature during film forming heat treatment 20～60 minutes.
Form one or more combinations that the cross-linked structure method shown in the formula (I) is included in heat, light, electron radiation, plasma, X ray, radical initiator etc. down, also can form cross-linked structure under the effect with means such as heat, light, electron radiation, plasma, X ray, radical initiators in the presence of one or more crosslinking agents.Wherein said crosslinking agent is shown in general formula (VII):
X
2R
f7X
3
(VII)
X
2, X
3Be selected from Cl, Br or I; R
F7Be selected from alkyl or perfluoroalkyl;
Described radical initiator is organic peroxide, azo-initiator etc., can only also can select for use several radical initiators to work in coordination with use with a kind of.Wherein said peroxide initiator is as general formula (VIII) or (IX):
R
1OOR
2
(VIII)
(IX)
R
1, R
2Can independently be selected from following groups: H, C
1～C
20The C that alkyl or aryl replaces
1～C
20Alkyl, C
1～C
20Acyl group, C
1～C
20Aroyl, C
1～C
20The C that fluorine-containing or perfluoroalkyl or aryl replace
1～C
20Alkyl, C
1～C
20Fluorine-containing or perfluoro acidyl, C
1～C
20Fluorine-containing or perfluor aroyl; But R
1, R
2Can not select H simultaneously.
R
3, R
4Be independently selected from following groups: C
1～C
20The C that alkyl or aryl replaces
1～C
20Alkyl, C
1～C
20The C that fluorine-containing or perfluoroalkyl or aryl replace
1～C
20Alkyl.
Azo-initiator is but is not limited only to following several: 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) etc.
In the dual cross-linking ion membrane of the fibre-reinforced perfluor of the present invention, by use fortifying fibre,, multiple means such as crosslinked, the high-valency metal compound of chemical bonding and acidic exchange group physical bond be crosslinked, act on the mechanical strength that has improved ionic membrane simultaneously.So the film of modification adds fiber reinforcement than general chemistry bonding cross-linking has had large increase aspect the dimensional stability, also solved a fibre-reinforced perfluoro sulfonic acid membrane gas permeability difficult problem, trace it to its cause, be because employed chemical bonding network structure and metal-cation exchange groups physical bond network structure acting in conjunction, especially metal-cation exchange groups physical bond network structure acting in conjunction have improved the degree of cross linking of film greatly.Simultaneously, the inventor also is surprised to find, and those gas permeabilities by the formed composite membrane of fiber of surface modification are very low.This may be because following reason: 1, surface-functionalized fiber and film-forming resin adhesion are improved; 2. because the functional group that the surface of fiber has can form bonding structure with metallic compound, thereby further reduced resin and interfibrous space.
The specific embodiment:
By the following examples the present invention is further specified, but 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:
Polytetrafluoroethylene fibre is placed on SiCl
4Be warmed up to 110 ℃ in the atmosphere after 1 hour, and kept 1 hour, be cooled to 60 ℃ again after, water spray is handled and to be obtained silica modified polytetrafluoroethylene fibre.
Embodiment 2:
Alkali-free glass fibre is placed Ti (OEt)
4In/the water mixed system, stir adding concentrated ammonia liquor down, hydrolysis is left standstill and is obtained the alkali-free glass fibre that titanium dioxide is modified.
Embodiment 3:
Triethyl phosphate mixes with ethyl orthosilicate (1: 100 mass ratio), adds entry and concentrated ammonia liquor and leaves standstill gel 12 hours, utilizes this gel to use electrostatic spinning or the technology of reeling off raw silk from cocoons to obtain the phosphoric acid modification silicon dioxide fibre then
Embodiment 4:
To gather the tetrafluoro fiber and place cerous nitrate, citric acid to utilize the document sol-gel process to prepare nano ceric oxide (" technology and market " the 4th phase in 2008) method, obtain the poly-tetrafluoro fiber that ceria is modified.
Embodiment 5: the mass concentration that will be immersed in cerous nitrate (III) or manganese nitrate (II) or lanthanum nitrate (III) according to the fiber with ion exchanging function that prior art CN101003588A makes is in 10% the solution 24 hours, obtains the fiber that cerium, manganese or lanthanum ion are modified
Embodiment 6:
With repetitive be
, EW=1000 fluoropolymer resin and manganese carbonate (accounting for resin quality 0.01%) be distributed in propyl alcohol-water, make total mass concentration and be propyl alcohol-aqueous solution of 5%, join mass concentration then and be in 5% the peroxidating perfluor malonyl DMF solution, to the polytetrafluoroethylene fibre that wherein adds the silicic acid modification (diameter 1 μ m, length 50 μ m, with polymer quality than 7: 100), be cast to after the dispersion in the polytetrafluoroethylene (PTFE) mold of horizontal positioned, through 80 ℃ of vacuum drying after 12 hours, film is peeled off, obtained fibre-reinforced individual layer perfluorinated sulfonic acid cross-linking ion membrane.
Embodiment 7:
With repetitive be
The fluoropolymer resin of the fluoropolymer resin of EW=700 and embodiment 1 is pressed mass ratio and is mixed at 2: 3, add oxidation perfluor bay two acyls then, 1,4-diiodo-octafluorobutane, lanthanum acetate (lanthanum acetate account for total resin quality 0.001%) fully mixes, being dissolved at last and making total mass concentration among the DMF is 20% solution, (diameter is 5 μ m to the fiber with ion exchanging function that the cerium of embodiment 5 is modified, length is 100 μ m, fiber is 1: 5 with the mass ratio of total resin) mix with it, utilize the method for curtain coating to make the individual layer perfluorinated sulfonic acid cross-linking ion membrane that thickness is 30 μ m then.
Embodiment 8:
With repetitive be
, EW=1300 fluoropolymer resin, perovskite structure oxide La
0.7Ce
0.15Ca
0.15MnO
3, AMBN, 1,4-diiodo-octafluorobutane is dissolved among the DMF, adds ZrO again
2-H
3The silicon carbide fibre of PO4 modification (diameter 5 μ m, length is 100 μ m, the mass ratio of fiber and resin is 1: 100), and be mixed in the N-methyl pyrrolidone, handled 60 minutes down at 170 ℃ with spraying method, making thickness is the cross-linked perfluorinated sulfonate film of 30 μ m.
Embodiment 9:
With repetitive be
, EW=1300 fluoropolymer resin be dissolved in the hempa acid amide, (diameter is 15 μ m to add quartz fibre then, length is 100 μ m, fiber is 3: 100 with the mass ratio of resin), after H-montmorillonite (is 10: 100 with the mass ratio of resin), 18-hat-6-Y complex compound (account for resin quality 0.3%) fully mix, by the spraying coating process method, obtain the film that thickness is 40 μ m, film was handled 100 minutes down at 230 ℃, obtain cross-linked perfluorinated sulfonate film.
Embodiment 10:
With repetitive be
, EW=1300 fluoropolymer resin, benzoyl peroxide, 1,14-dibromo 20 fluorine ten alkane are dissolved in the dimethyl sulfoxide (DMSO), then with ZrO
2Modified carbonize silica fibre (diameter is 2 μ m, and length is 100 μ m, and the mass ratio of fiber and resin is 1: 50), granularity are the TiO of 4 μ m
2(is 23: 100 with the mass ratio of fluoropolymer resin), cyclodextrin-zinc complex (account for resin quality 2%) fully mix, obtain the film that thickness is 35 μ m by the silk-screen printing technique method then, this film was handled 3 minutes down at 160 ℃, obtained cross filament and strengthen perfluoro sulfonic acid membrane.
Embodiment 11:
With repetitive be
, the EW=1250 fluoropolymer resin is dissolved in that to obtain mass concentration in the hempa acid amide be 30% solution, (diameter is 30 μ m to add basalt fibre, length is 3mm, the mass ratio of fiber and resin is 0.01: 100), nitogen-contained crown ether-lanthanum (III) complex compound (accounting for resin quality 1%), by the pouring technology method, obtain the film that thickness is 40 μ m.This film was handled 100 minutes down at 230 ℃, obtained fibre-reinforced individual layer perfluoro sulfonic acid membrane.
Embodiment 12:
With repetitive be
, EW=700 fluoropolymer resin, repetitive is
, EW=1300 fluoropolymer resin (two kinds of resin quality ratios are 1: 0.2), AMBN, yttrium nitrate (account for total resin quality 0.067%) mixed dissolution is in DMF, make total mass concentration and be 20% solution, the fiber with ion exchanging function (diameter is 15 μ m, and length is 20mm, and fiber is 0.5: 5 with the mass ratio of two kinds of resins) that makes according to CN101003588A of ruthenium surface modification is mixed with it, through curtain coating, heat to such an extent that thickness is the individual layer cross linking membrane of 45 μ m then.
Embodiment 13:
With repetitive be
, EW=700 fluoropolymer resin, benzoyl peroxide, 1,14-diiodo-20 fluorine ten alkane, zirconium nitrate (account for resin quality 0.2%) and with TiO
2(diameter is 0.01 μ m to the BN fiber of modification, length is 120 μ m, account for the solution gross mass 5%) be scattered in the dimethyl sulfoxide (DMSO), obtain the film that thickness is 25 μ m by the silk-screen printing technique method, this film was handled 60 minutes down at 170 ℃, made cross-linked perfluorinated sulfonic acid BN fiber reinforced film.
Embodiment 14:
With repetitive be
Fluoropolymer resin with repetitive be
Fluoropolymer resin be after 1: 5 ratio is mixed, to be scattered among the DMSO in mass ratio, in above-mentioned mixed liquor, add Zr again
3(PO
4)
4, phosphoric acid modification SiO
2Fiber (diameter is 0.05 μ m, and length is 10 μ m) and SiN fiber (diameter is 0.5 μ m, and length is 50 μ m), wherein total portions of resin Zr
3(PO
4)
4: SiO
2: SiN=100: 12.4: 5: 3.Then to wherein adding nitogen-contained crown ether (N
5O
3-24-hat-8)-and W complex compound (account for total resin quality 0.15%), benzoyl peroxide, 1,14-dibromo 20 fluorine ten alkane form cross-linked doped film by the The tape casting film forming and with film 230 ℃ of following heat treated.
Comparative example 15:
With repetitive
Polymer (EW=1200) be distributed in propyl alcohol-water, make mass concentration and be propyl alcohol-aqueous solution of 5%, join mass concentration then and be in 5% the peroxidating perfluor malonyl DMF solution, (diameter is 1 μ m by silica modified polytetrafluoroethylene fibre to wherein adding then, length is 50 μ m, with fluoropolymer resin mass ratio 7: 100), be cast to after the dispersion in the polytetrafluoroethylene (PTFE) mold of horizontal positioned, through 80 ℃ of vacuum drying after 12 hours, film is peeled off, and obtaining thickness is the fiber reinforcement sulfonic fluoropolymer cross-linking ion membrane of 50 μ m.
Comparative example 16:
To mass concentration 10% nafion
Add polytetrafluoroethylene fibre (diameter is 1 μ m, and length is 50 μ m, with fluoropolymer resin mass ratio 7: 100) in the solution, utilize the method for cast to obtain the thick exchange membrane containing fluorine of 60 μ m 170 ℃ of processing.
Embodiment 17
Performance to various films characterizes, and the results are shown in Table 1.As can be seen from Table 1, performances such as 95 ℃ of electrical conductivity of the compound-modified fiber reinforcement cross-linked perfluorinated ion-exchange membrane of high-valency metal, hot strength, hydrogen permeate electric current all are better than common fiber reinforcement amberplex, and the raising and the improvement of highly significant have especially been arranged aspect gas barrier.
The various films of table 1 characterize
Claims (9)
1. dual cross-linking ion membrane of fiber reinforcement perfluor is characterized in that: as film-forming resin, described perfluorinated ion exchange resin and crosslinking agent form the chemical crosslinking structure with perfluorinated ion exchange resin, and add the fiber as reinforce; It is crosslinked that structural acidic-group of described chemical crosslinking and high-valency metal compound form physical bond, thereby form dual cross-linked network structure; Described chemical crosslinking structure has the cross-bridge shown in the formula (I):
Wherein, G
1=CF
2Or O, G
2=CF
2Or O, R
fBe C
2-C
10The perfluor carbochain;
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;
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 perfluor alkene monomer that contains crosslink sites has the structure of formula (X):
Wherein, Y
5Be independently selected from Br or I;
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
F5, R
F6Be independently selected from perfluoroalkyl
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 element; And
Described high-valency metal compound is selected from a kind of or combination double salt in nitrate, sulfate, carbonate, phosphate or the acetate 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 cyclodextrin, crown ether, acetylacetone,2,4-pentanedione, nitogen-contained crown ether and EDTA, DMF or the DMSO complex compound of 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; 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.
2. ionic membrane as claimed in claim 1 is characterized in that: R
F5, R
F6Be independently selected from C
1-C
5Perfluoroalkyl.
3. ionic membrane as claimed in claim 1 is characterized in that: be selected from alkali-resistant glass fibre, alkali-free glass fibre, fluorocarbon polymer fiber, ceramic fibre, mineral fibres or the oxide fibre one or more as the fiber of reinforce.
4. ionic membrane as claimed in claim 3 is characterized in that: the fluorocarbon polymer fiber is selected from polytetrafluoroethylene fibre, perfluoroethylene-propylene fiber or poly-perfluoro propyl vinyl ether fiber.
5. as each described ionic membrane of claim 1-3, it is characterized in that: described high-valency metal is compound loaded on described fortifying fibre.
6. as each described ionic membrane of claim 1-3, it is characterized in that: described high-valency metal compound is selected from a kind of or combination double salt in nitrate, sulfate, carbonate, phosphate or the acetate of the highest price attitude of these metallic elements and middle valence state.
7. as each described ionic membrane of claim 1-3, it is characterized in that: described high-valency metal compound is selected from the highest price attitude of these metallic elements and cyclodextrin, crown ether, acetylacetone,2,4-pentanedione, EDTA, DMF or the DMSO complex compound of middle valence state.
8. ionic membrane as claimed in claim 7 is characterized in that: described crown ether is a nitogen-contained crown ether.
9. as each described ionic membrane of claim 1-3, 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.
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| CN2009102311362A CN101733011B (en) | 2009-12-10 | 2009-12-10 | Fiber reinforced perfluoro dual crosslinked ion membrane and preparation method thereof |
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|---|---|---|---|
| CN2009102311362A CN101733011B (en) | 2009-12-10 | 2009-12-10 | Fiber reinforced perfluoro dual crosslinked ion membrane and preparation method thereof |
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| CN101733011B true CN101733011B (en) | 2011-04-06 |
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| CN102013498B (en) * | 2010-06-18 | 2013-12-11 | 山东华夏神舟新材料有限公司 | Fluorine-containing ionomer composite material with ion exchange function as well as preparation method and application thereof |
| CA2802973C (en) * | 2010-06-18 | 2017-09-12 | Shandong Huaxia Shenzhou New Material Co., Ltd | Fluorine containing ionomer composite with ion exchange function, preparation method and use thereof |
| CN102013499B (en) * | 2010-06-18 | 2013-06-12 | 山东华夏神舟新材料有限公司 | Fluorine-containing ionomer composite material with function of ion exchange and preparation method and application thereof |
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