Fluorine-containing cross-linked doped ion-exchange membrane of a kind of microporous film enhanced multilayer and preparation method thereof
The application is dividing an application of 200810138429.1 patent applications.
Technical field
The invention belongs to field of functional polymer composites, relate to fluorine-containing cross-linked doped ion-exchange membrane of a kind of microporous film enhanced multilayer 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.
Though the perfluorinated sulfonic acid PEM that uses is used for many years now, but still exists deficiency not reach the commercialization requirement,, poor dimensional stability low as the high temperature proton conductivity, 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 operating 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 DMFC, 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.
People have proposed certain methods and have solved these problems at present.Gore-Select series composite membrane liquid as the exploitation of W.L.Gore company adopts the porous teflon to fill the method (US5547551 of Nafion ionic conductivity liquid, US5635041, US5599614), this film has high proton conductive and bigger dimensional stability, but teflon creep at high temperature is very big, causes performance to descend.Japan Patent JP-B-7-68377 also proposed a kind of method, the porous media made from the proton exchange resins filled polyolefin, but its chemical durability deficiency, thereby long-time stability aspect existing problems.
In addition, Japan Patent JP-A-6-231779 has proposed another kind of Enhancement Method, is 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 of film is tending towards difficulty, and the film resistance increase takes place possibly.In the U.S. Pat 5834523, Ballard company is the α of sulfonation, β, β-trifluorostyrene sulfonic acid and m-trifluoromethyl-α, β, the methyl alcohol/propanol solution of β-trifluorostyrene copolymer is immersed in the hole of porous PTFE film of swelling, under 50 ℃ of conditions, dry then, obtain composite membrane.But need repeat polymer fully is filled in the hole of PTFE microporous barrier.
In WO98/51733, by hot pressing under 310 ℃ of vacuum states together the PTFE film of the film of the thick sulfuryl fluoride type of 25 μ m and Gore company.Then film hydrolysis in the KOH of dimethyl sulfoxide (DMSO) solution, make in the film-SO
2The F group changes into-SO
3 -At last be coated with three times 5% sulfonate resin solution, in 150 ℃ of vacuum drying ovens, make film become as a whole in the one side of porous PTFE film.This method is too time-consuming, and microporous barrier is difficult to be filled by sulfonate resin full.
The crosslinked heat endurance 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 PEM, 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 PEM 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 electrical conductivity of film that makes in surface sharply descends.
The disclosed respectively triazine ring cross-linked structure perfluoro sulfonic acid membrane that contains of US7259208 and CN101029144 (application number 200710013624.7) has good mechanical strength and dimensional stability equally.
For solving the high temperature proton conduction behavior of sulfonic fluoropolymer film, the inorganic additive that much has the high-temp water-preserving ability is added in the sulfonic fluoropolymer exchange membrane.Choosing these inorganic water conservation machines of inorganic water conservation particle requirement must have: (1) particle has the better water holding capacity that gets, and higher dehydration temperature is just arranged; (2) has intermiscibility preferably with proton exchange resins; (3) particle has certain proton conducting ability; (4) be easy to obtain nanometer particle; (5) particle structure good stability is not accompanied tangible structural change in suction, dehydration; (6) help keeping or improving the mechanical strength or the physical size stability of PEM.Usually the inorganic water conservation particle that adopts is SiO
2, TiO
2, Zr (HPO
4)
2Or ZrO
2Particle, heteropoly acid or solid acid particle, zeolite family mineral particle, stratotype clay mineral such as montmorillonite and intercalation clay mineral thereof etc.
For example Chinese patent CN1862857 discloses in the sulfonic fluoropolymer resin and has added SiO
2Can be etc. inorganic water-loss reducer to improve the high-temperature electric conduction performance of PEM.
J.Electrochem.Soc. (V154,2007, p.B288-B295) Nafion resin and basic zirconium phosphate composite membrane-forming have been described.This film still has very high electrical conductance in relative humidity less than 13%.
But above each patent and document have only improved the performance of an aspect of film, fail to improve the dimensional stability of film simultaneously and the electricity under the high temperature low humidity is led.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 industrial ten minutes needs.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of microporous film enhanced multilayer fluorine-containing crosslinked ion-doped film and preparation method.
It is as follows that technology of the present invention is put case:
A kind of microporous film enhanced multilayer fluorine-containing crosslinked ion-doped film, with the EW value is that 600~1300 ion exchange fluoro resin is the 2-40 tunic of matrix, gross thickness 10~300 μ m, have at least 1 tunic to have cross-linked structure, have at least 1 tunic to add the inorganic doping thing with water retaining function or proton exchange function, having 1 tunic at least is with the porous enhancing film of microporous barrier as reinforce; Electrical conductivity 40~150mS/cm, hot strength 10~60Mpa;
The mass ratio of described inorganic doping thing and ion exchange fluoro resin is 0.1~100: 100, and 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;
Preferably, the number of plies of multilayer film is the 2-20 layer, and gross thickness is 10~100 μ m.
Described inorganic doping thing is selected from: oxide, orthophosphates or condensed phosphate, polyacid, multi-acid salt and hydrate thereof, silicate, sulfate, one of selenite and arsenide or combination; Wherein preferred oxides, orthophosphates or condensed phosphate, polyacid, multi-acid salt, further preferred oxides, orthophosphates or condensed phosphate.
Below above various inorganic doping things are further specified in detail:
(1) oxide is shown in general formula: QO
E/2E=1~8; Wherein Q can be second and third, four, five major elements and transition elements e=1~8 as: SiO
2, Al
2O
3, Sb
2O
5, SnO
2, ZrO
2, TiO
2, MoO
3, OsO
4
(2) phosphate, comprise first, second, third and fourth, the various forms of orthophosphates and the condensed phosphate of five major elements, transition elements.As: BPO
4, Zr
3(PO
4)
4, Zr (HPO
4)
2, HZr
2(PO
4)
3, Ce (HPO
4)
2, Ti (HPO
4)
2, KH
2PO
4, NaH
2PO
4, LiH
2PO
4, NH
4H
2PO
4, CsH
2PO
4, CaHPO
4, MgHPO
4, HSbP
2O
8, HSb
3P
2O
14, H
5Sb
5P
2O
20Zr
5(P
3O
10)
4, Zr
2H (P
3O
10)
2
(3) polyacid, multi-acid salt and hydrate thereof are shown in general formula: A
iB
jC
kO
lMH
2O.Wherein A can be first, second, third and fourth, five major elements, transition elements or, two, three, four, pentavalent group; B, C can be second and third, four, five, six, seven major elements, transition elements; I=1~10, j=0~50, k=0~50,1=2~100, m=0~50.As: H
3PW
12O
40α H
2O (α=21-29), H
3SiW
12O
40β H
2O (β=21-29), H
xWO
3, HSbWO
6, H
3PMo
12O
40, H
2Sb
4O
11, HTaWO
6, HNbO
3, HTiNbO
5, HTiTaO
5, HSbTeO
6, H
5Ti
4O
9, HSbO
3, H
2MoO
4
(4) silicate comprises zeolite, zeolite (NH
4 +), phyllosilicate, web-like silicon hydrochlorate, H-sodalite, H-modenite, NH
4-analcime, NH
4-sodalite, NH
4-gallate or H-montmorillonite;
(5) sulfate is shown in general formula: D
oH
pS
qO
rWherein D can be first, second, third and fourth, five major elements, transition elements or, two, three, four, pentavalent group; O=1~10, p=0~10, q=1~5, r=2~50.As: CsHSO
4, Fe (SO
4)
2, (NH
4)
3H (SO
4)
2, LiHSO
4, NaHSO
4, KHSO
4, RbSO
4, LiN
2H
5SO
4, NH
4HSO
4
(6) selenite and arsenide are shown in general formula: E
sH
tF
uO
vWherein A can be first, second, third and fourth, five major elements, transition elements or, two, three, four, pentavalent group; F can be As or Se; S=1~10, t=0~10, u=1~5, v=2~50.As: (NH
4)
3H (SeO
4)
2, (NH
4)
3H (SeO
4)
2, KH
2AsO
4, Cs
3H (SeO
4)
2, Rb
3H (SeO
4)
2
To sum up, concrete preferred inorganic doping thing is SiO among the present invention
2, ZrO
2, TiO
2, BPO
4, Zr
3(PO
4)
4, Zr (HPO
4)
2, HZr
2(PO
4)
3, Ti (HPO
4)
2Or Zr
2H (P
3O
10)
2In one or more.
Preferably, the mass ratio of described inorganic doping material and ion exchange fluoro resin is 0.5~50: 100, further preferred 1~25: 100; The particle diameter of described inorganic doping thing is 0.005~50 μ m.
Preferably, 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, also can be the mixture of above-mentioned copolymer, the EW value be 600~1300, preferred 700~1200.
Described Fluorine containing olefine is selected from: tetrafluoroethene, and CTFE, trifluoro-ethylene, hexafluoropropene, and/or in the vinylidene one or more, preferred, Fluorine containing olefine is selected from tetrafluoroethene or CTFE.
The described 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; N is 0 or 1; X is selected from F, Cl, Br or I;
D is 0~5 integer
R
F1, R
F2And R
F3Be selected from perfluoroalkyl or dichlorodifluoromethan base respectively;
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
2, 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.
The microporous barrier that strengthens usefulness among the present invention is organic micro film or inorganic microporous barrier, preferred polymers film wherein, ultra-thin ceramic film, ultra-thin molecular screen membrane.Special preferred fluorocarbon polymer film, ultra-thin Si O
2Film, TiO
2Film, ZrO
2Film, cellular glass film etc.Employed microporous barrier preferably carries out surperficial silicic acid, sulfonation, sulphation, phosphorylation, hydrophilic modification.Concrete method of modifying can be with reference to prior art.The invention provides following microporous barrier surface modifying method:
As to the fluorocarbon polymer film, silicic acid, sulfonation, sulphation, phosphorylation etc. are carried out in the surface.Existing surface modifying method for polytetrafluoroethylene (PTFE) all is suitable for the modification to the fluorocarbon polymer film, comprises reduction modification, laser emission modification, plasma modification and the silicic acid activation method of sodium naphthalene solution.Its mesosilicic acid activation method is first-selected method because it can be on fluorocarbon polymer film surface directly deposits the silica of water conservation.By fluorocarbon polymer film surface after the modification hydrophilic group has been arranged, but preferably on this basis more further modification as with the fiber of modification at ethyl orthosilicate, ZrOCl
2-H
3PO
4Or further modification in the titanate esters etc.
This can directly be positioned over ethyl orthosilicate, ZrOCl with these inorganic microporous barriers for the surface modification of inorganic microporous barrier
2-H
3PO
4Or titanate esters, H
3PO
4, H
2SO
4Deng in carry out modification, also can when the synthesizing inorganic microporous barrier, add modifier directly to generate the modified inorganic microporous barrier, as phosphate and ethyl orthosilicate are mixed, become Modified Membrane with the alkali gel.The concrete grammar of for example silica modified voided polytetrafluoroethylene film is placed on SiCl with voided polytetrafluoroethylene film exactly
4Be warmed up to 110 ℃ in the atmosphere after 1 hour and kept 1 hour, be cooled to 60 ℃ again after, water spray is handled and is obtained silica modified voided polytetrafluoroethylene film.
Titania modified cellular glass film method is for to place Ti (OEt) with the cellular glass film
4Stir in the water mixed system and add the static cellular glass film that obtains the titanium dioxide modification of concentrated ammonia liquor hydrolysis down.
Also can be with inorganic ultrathin membrane such as TiO
2Film, ZrO
2Film is directly at H
3PO
4And H
2SO
4Deng soaking surface modification in the inorganic acid.
Also have a kind of method of modified inorganic ultrathin membrane of separating out jointly such as triethyl phosphate to mix to add entry and the static gel of concentrated ammonia liquor 12 hours with ethyl orthosilicate (1: 100 mass ratio), utilize surfactant such as hexadecyltrimethylammonium chloride to make lamina membranacea then, the ultra-thin silicon dioxide film of gel phosphoric acid modification.
The aperture of microporous barrier is 0.1~1 μ m, and thickness is 5~100 μ m, porosity 30~99%, preferred 70~97%.
Ion exchange fluoro resin in the fluorine-containing cross-linked doped ion-exchange membrane of microporous film enhanced multilayer of the present invention can be at microporous barrier surface-crosslinked, also can be crosslinked in the space of microporous barrier.
The preparation method of the fluorine-containing cross-linked doped ion-exchange membrane of microporous film enhanced multilayer of the present invention comprises the steps:
(1) solution of available ion exchange fluoro resin of each layer in the fluorine-containing cross-linking ion membrane of microporous film enhanced multilayer and inorganic doping thing or fused mass by cast, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology make, also can be simultaneously and the microporous barrier composite membrane-forming;
(2) preparation of multilayer film can be by compound the making of monofilm of preparation in (1), the basis of also can be or having made multilayer film at monofilm utilize the solution described in (1) or fused mass by cast, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology make, equally can by multilayer film and monofilm or multilayer film and multilayer film is compound make;
(3) when needs added crosslinking agent and/or initator, crosslinking agent and/or initator can add when carrying out step (1) and/or (2), also crosslinking agent and/or initator can be scattered in the solvent to enter in the film by film mode of swelling in solvent;
(4) film that (2), (3) are handled is handled by the method that following cross-linked structure forms, form described formula (I), (II), (III), (IV) and/or (V) shown in cross-linked structure;
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 or azo-initiator; Preferably, initator is an organic peroxide evocating agent; Preferred, initator is the perfluor organic peroxide;
The method that forms (II), (III) cross-linked structure is: utilize sulfuryl fluoride, sulfonic acid chloride or 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 include but not limited to ammonia through the material that chemical treatment discharges ammonia, hydrazine, organic diamine, organic or inorganic acid hydrochlorate, urea or the guanidine of hydrazine or 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 Bronsted acid or lewis acid; Wherein Bronsted 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;
(5) step (4) products therefrom is more successively through alkali lye, and acid solution is handled and obtained the crosslinked exchange membrane containing fluorine that microporous barrier strengthens.
The described acid of step (5) is hydrochloric acid, sulfuric acid or nitric acid; Described alkali is LiOH, NaOH or KOH; Described alkali lye and acid solution are the aqueous solution.
In above preparation method, when using casting, spin coating, curtain coating, silk-screen printing technique, spraying or impregnating technology, solvent can be but be not limited only to a kind of of following solvent or combination: 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.Solid content in the prepared resin solution is 1~80%, weight ratio.Will be under 30~300 ℃ temperature during film forming heat treatment 10~100 minutes, preferred, will be under 80~250 ℃ temperature during film forming heat treatment 20~60 minutes.
Use microporous barrier and crosslinked two kinds of means to act on the mechanical strength that has improved ionic membrane simultaneously at the fluorine-containing cross-linked doped ion-exchange membrane of microporous film enhanced multilayer of the present invention.Using when we also find two kinds of means has not only increased the dimensional stability of film in the length and width direction greatly, but also film is increased greatly in the stability of thickness direction.This point in the past never find; show according to our repeated test; though single enhancements can increase the stability of film in the length and width direction to a certain extent; when this stability increases, make very big that the thickness of film increases, even again the film dehydration all can't be returned to original thickness through regular meeting.Our invention has improved this situation.The amberplex that general microporous barrier strengthens has very high fuel permeability, this is because always have some micropores not filled up by resin, the result of various technology descends greatly but we can also find to compare in the past by the fuel permeability of film, this makes the infiltration of fuel be subjected to the resistance at interface because of this ascribes 1 multi-layer film structure to, multilayer film has also been eliminated the micropore that does not fill up in addition, and 2 cross-linked structures make the ion cluster of conduction fuel be limited in the resistance that very little space has increased fuel infiltration.In addition, the moisture in the film that the existence of interfacial structure also makes is difficult for running off because of interfacial resistance becomes, and the high temperature or the electric conductivity under the low humidity of adding the feasible film that is obtained of existence of water retaining function inorganic doping thing are higher than general amberplex far away.
The specific 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 and granularity are the Zr (HPO of 0.005 μ m
4)
2(Zr (HPO
4)
2With the mass ratio of resin be 3: 100) make the aqueous propanol solution of 5wt%, be disposed at concentration then and be 5% peroxidating perfluor malonyl DMF solution, the eptfe film that 30 μ m are thick (porosity 70%) places above-mentioned solution to soak about 1 hour, the film that will soak carries out drying on heating plate then, with rubber roll film is carried out roll extrusion therebetween.Above-mentioned solution-cast being arrived in the polytetrafluoroethylene (PTFE) mold of horizontal positioned again,, after 12 hours film is peeled off through 80 ℃ of vacuum drying, is the H of 0.5M in molar concentration
2SO
4Boil 1 hour in the solution, and spend deionised water.Obtaining each individual layer perfluorinated sulfonic acid crosslinked with NaOH solution, sulfuric acid solution processing film successively after the heat treated is (I) species complexity ionic membrane (monofilm 1#).Carry out hot pressing with above-mentioned two individual layer perfluorinated cross-linked doped ion-exchange membrane is stacked, make double-deck microporous barrier and strengthen perfluor cross-linking ion membrane (multilayer film 101#).
Embodiment 2: with repetitive be
The polymer of EW=800 and granularity are 0.03 μ mSiO
2(SiO
2With the mass ratio of perfluorinated sulfonic resin be 5: 100), extrude obtain thickness be 30 μ m film again with the silica modified porous hexafluoropropene of 12 μ m film (porosity 90%) by hot pressing under 310 ℃ of vacuum states together, in 150 ℃ of vacuum drying ovens, be soaked in NH then in 1 hour
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 (monofilm 2#) of (II) with the cross-linked structure that KOH solution, hydrochloric acid solution are handled successively.
With repetitive be
The polymer of EW=1200 and tetraphenyltin are extruded into the film of 50 μ m with 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 monofilm 2#, overlapping, the hot pressing of 3#, and the crosslinked two-layer doped micropore film that obtains strengthens amberplex (multilayer film 102#), and thickness is 80 μ m.
Embodiment 3: with repetitive be
The polymer of EW=1100 and H
3PW
12O
40Make 3% polymer solution in 100: 1 ratio, with porous Al
2O
3Film (porosity 50%) immerses in the above-mentioned solution, after 30 minutes film is taken out drying, and then this film being obtained 20 μ m cross-linked structures through the 50KGy crosslinking with radiation is the ionic membrane that (I) plants.(monofilm 4#)
With repetitive be
The polymer of EW=940 and H
3PW
12O
40Press polymer and H
3PW
12O
40100: 20 ratio of mass ratio is made 30% DMSO solution, by the casting method at 170 ℃, 60min makes the film (monofilm 5#) of 10 μ m.
With monofilm 2#, 4,5# perfluorinated sulfonic acid ionic membrane is stacked to carry out hot pressing, then with multilayer film 102# hot pressing, obtains 60 μ m microporous barriers and strengthens three layers of cross-linked doped ion-exchange membrane (multilayer film 103#).
Embodiment 4: with repetitive be
The polymer of EW=700 and CsHSO
4Mix by 100: 40 mass ratios, be dissolved in the solution of 20% (weight) made among the DMF then, porous tetrafluoroethene-perfluoroalkyl ethylene oxy copolymer film (porosity 95%) that 50 μ m are thick places above-mentioned solution to soak about 1 hour 120 ℃ of processing 10min and gets the individual layer perfluorinated sulfonic acid ionic membrane that 50 μ m microporous barriers strengthen.It must cross-linked structure be the film (monofilm 6#) of formula (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 layers of doping (multilayer film 104#).
Embodiment 5: with repetitive be
The polymer of EW=1300 and 0.8 μ mZrO
2(with the mass ratio of resin be 2: 100), AMBN, 1,4-diiodo-octafluorobutane is dissolved among the DMF, phosphoric acid modification gets ZrO2 microporous barrier (porosity 80%, 20 μ m) and soaks 30min at 170 ℃, 60min makes the film of 20 μ m.Re-use perfluorinated sulfonic resin and 5 μ m H-modenite powder (mass ratio of H-modenite and resin is 1: 1) among the embodiment 4, be mixed in the N-methyl pyrrolidone and become the film of 30 μ m, prepare three layers of perfluorinated ion-exchange membrane (multilayer film 105#) 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 (I).
With above-mentioned ionic membrane place once more above-mentioned polymer, 10 μ mH-montmorillonites (with the mass ratio of resin be 0.5: 100), AMBN, 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 down at 120 ℃, and five layers of microporous barrier that obtain strengthen perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 106#).
With multilayer film 105,106# carries out hot pressing, makes ten layers of microporous barrier and strengthens perfluorinated sulfonic acid cross-linking ion doping (multilayer film 107#).
Embodiment 6: with repetitive be
The polymer dissolution of EW=1300 is in the hempa acid amide, add then after 0.7 μ m H-montmorillonite (the H-montmorillonite is 10: 100 with the mass ratio of resin) mixes, by spraying coating process method in a vacuum in sulfuric acid modified ZrO2 microporous barrier (porosity 80%, 20 μ m), obtain the film that thickness is 20 μ m.Film is handled 100min down at 230 ℃.Obtaining cross-linked structure is the individual layer perfluoro sulfonic acid membrane (monofilm 7#) of formula (I).
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 108#).
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), again with 3 μ mTiO
2(is 15: 100 with the mass ratio of resin) mixes, and the improved silica microporous barrier with phosphate and the cogelled thick porosity 60% of 30 μ m that obtains of esters of silicon acis soaks above-mentioned again solution again, and film is handled 3min down at 160 ℃.Obtain 30 crosslinked μ m inorganic doping microporous barriers and strengthen 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 down at 120 ℃, obtain three layers of perfluorinated sulfonic acid cross-linked doped ion-exchange membrane (multilayer film 109#).
Carry out hot pressing with three of multilayer film 9# are stacked, nine layers of microporous barrier that make enhancing strengthen perfluorinated sulfonic acid cross-linked doped ion-exchange membranes (multilayer film 110#).
Embodiment 8: with repetitive be
EW=1250 polymer and CsH
2PO
4Mix by 100: 20 (weight ratio), be dissolved in then and obtain 30% solution in the hempa acid amide, with the thick porosity of 10 μ m is that porous tetrafluoroethene-perfluoroalkyl ethylene oxy copolymer film of 89% places above-mentioned solution to soak about 1 hour, obtains the film that thickness is 10 μ m.Film is handled 100min down at 230 ℃, obtain crosslinked individual layer micropore and strengthen adulterated full fluorin sulfonate film (monofilm 9#).
Both sides at crosslinked adulterated full fluorin sulfonate film are passed through the spraying coating process method once more, make three layers of crosslinked adulterated full fluorin sulfonate film of 60 μ m.At its both sides hot pressing monofilm 9#, make crosslinked five layers of micropore and strengthen adulterated full fluorin sulfonate film (multilayer film 111#).
Embodiment 9: with repetitive be
The polymer of EW=900 and 0.03 μ mSiO
2(with the mass ratio of perfluorinated sulfonic resin be 5: 100) with thickness be that the porosity of 30 μ m is 50% expander polytetrafluoroethylene (PTFE) hot pressing film forming.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 mix membrane porosity 80%TiO with 50 μ m with double screw extruder again
2Microporous barrier hot pressing is compound, then film is heated to 230 ℃ of films that obtained (V) kind cross-linked structure in 10 hours.This film was placed 35% hydrazine hydrate kind 10 hours, taking out the back heating was had (V) to plant the film that cross-linked structure and (III) plant cross-linked structure, this film alkali lye, the cross linking membrane (monofilm 11#) of acid solution processing in 5 hours simultaneously again.
With monofilm 10,11# and multilayer film 11# and the crosslinked microporous barrier of the overlapping hot pressing of multilayer film 7# film strengthen 16 tunics (multilayer film 112#), and thickness is 300 μ m
Embodiment 10: with repetitive be
The polymer of EW=700 and repetitive are
The polymer of EW=1300 (the resin quality ratio is 1: 0.2) and 10nmZrO
220% the solution that (is 2: 100 with the mass ratio of polymer) and AMBN mixed dissolution are made in DMF mixes, be that 50 μ m porositys are that 75% micropore glass film film places above-mentioned solution to soak about 3 hours with thickness then, heat to such an extent that thickness is that the individual layer perfluorinated sulfonic acid of 50 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 102# hot pressing, make five layers of perfluorinated sulfonic acid micropore and strengthen cross-linking ion membrane (multilayer film 113#).
Embodiment 11: with repetitive be
The polymer of EW=1200 and triphenyl tin hydroxide and 8 μ mZrO
2(with the mass ratio of resin be 2: 100), be scattered among the DMF, place above-mentioned solution to soak half an hour approximately the thick porous polyimide film of 20 μ m, at 170 ℃, 60min makes the film that (V) plants cross-linked structure that has of 20 μ m.Re-use perfluorinated sulfonic resin and 5 μ m H-modenite powder (mass ratio of H-modenite and resin is 1: 1) among the embodiment 4 and be mixed in the N-methyl pyrrolidone and become the film of 30 μ m, prepare three layers of micropore and strengthen perfluorinated ion-exchange membranes in the spin coating of the both sides of above-mentioned film.Film is handled 2.4h down at 190 ℃.The crosslinked micropore that obtains three layers strengthens perfluoro sulfonic acid membrane (multilayer film 114#).
Embodiment 12: with repetitive be
The TiO of the polymer of EW=1200 and 0.02 micron
2Mix (mass ratio is: 100: 3) and prepare monofilm, this film is at high temperature handled obtaining the monofilm 13# that cross-linked structure is formula II in 3 hours then with the method that melt extrudes.On the two sides of monofilm 13# folded on multilayer film 112# and 120 ℃ of hot-pressing processing, hydrolysis acidification obtains 33 layers of cross-linked perfluorinated sulfonic acid micropore and strengthens films (multilayer film 115#) then.
Embodiment 13: with repetitive be
Polymer and repetitive be:
Polymer be that 2: 3 ratio is mixed the back and added Ti (HPO with mass ratio
4)
2(particle diameter is 0.05 micron, account for gross weight 12%) mixed melting extrudes that to obtain thickness be 50 microns film (monofilm 14#) in sieve bar extruder.
With repetitive be
Polymer and Ce (HPO
4)
2(granularity is 0.5 micron), HTaWO
6(polymer: Ce (HPO
4)
2: HTaWO
6=100: 4: 8, weight ratio), being scattered 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. and place the DMF solution of peroxidating perfluorocarboxylic acid to soak the cross-linked structure monofilm 15#. that heating obtains the formula that forms (I) this film
Monofilm 14# is placed between two monofilm 7# and two the compound hot pressing posthydrolysis of monofilm 15# acidifyings again, obtain multilayer film 116#.
Embodiment 14: with repetitive be
Polymer and ZrO
2(0.01 micron of particle diameter) is to be scattered in that to form solid content in the N-methyl pyrrolidone be 30% dispersion liquid after mixing at 100: 9 by mass ratio. the porosity 65% expanded ptfe film that 80 μ m are thick places above-mentioned solution to soak half an hour approximately, 190 ℃ of film forming. (monofilm 16#).
With above-mentioned polymer be with repetitive
Polymer be to be scattered among the DMSO after 1: 5 ratio is mixed in mass ratio, in above-mentioned mixed liquor, add particle diameter again and be 0.05 micron Zr
3(PO
4)
4Portions of resin Zr wherein
3(PO
4)
4Add a spot of antimony organic catalyst after again by The tape casting film forming and with film at 230 ℃ form triazine crosslinked rings at=100: 12.. and (monofilm 17#).
It is 300 microns 15 tunics (multilayer film 117#) that monofilm 16# and monofilm 17# are stacked alternately the compound thickness that obtains of hot pressing.
Embodiment 15: with repetitive be
EW=1250 polymer and particle diameter are 10 microns BPO
4Mix by 100: 12 (weight ratio), be scattered in then and obtain 19% solution in the hempa acid amide, porosity 45% molecular sieve film that 40 μ m are thick places above-mentioned solution to soak about 10min, and 100 ℃ of film forming are compound with multilayer film 114# hot pressing again.Composite membrane is handled 300min under the irradiation of ultraviolet light, obtaining cross-linked structure is the multilayer microporous film enhancing adulterated full fluorin sulfonate film (multilayer film 118#) of I.
Embodiment 16: with repetitive be
Polymer, tertbutanol peroxide, 1,4-diiodo-octafluoro fourth is dissolved in the glycerine and 0.03 μ mSiO
2(is 11: 100 with the polymer quality ratio) mixes, and the porosity 85% expansion tetrafluoroethene film that 25 μ m are thick places above-mentioned solution to soak about 80min, 210 ℃ of film forming, and obtaining thickness is the crosslinked microporous barrier enhancing inorganic doping perfluoro sulfonic acid membrane of 25 μ m.(monofilm 18#)
Above-mentioned ionic membrane is placed same polymer 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, three layers of perfluorinated sulfonic acid cross-linked doped ion-exchange membrane that are enhanced down at 120 ℃.
Carry out hot pressing with above-mentioned three fibre-reinforced individual layer perfluorinated sulfonic acid cross-linking ion membranes are stacked, make nine layers of perfluorinated sulfonic acid cross-linked doped ion-exchange membrane (multilayer film 119#) that microporous barrier strengthens.。
Embodiment 17: with repetitive be
Polymer and repetitive be:
Polymer be that 1: 4 ratio is mixed the back and added CsH with mass ratio
2PO
4Be scattered in after (account for gross weight 7%) and form 22% solution among the NMP, going out to obtain thickness through curtain coating is 50 microns film (monofilm 19#).
With monofilm 19# place between two monofilm 7# again with two compound hot pressing of monofilm 14# after sodium type multilayer amberplex (multilayer film 120#).
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) and 50 μ mTiO
2(TiO
2: 2: 100 mass ratioes of polymer) be scattered 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 20#) that obtains (IV) cross-linked structure in the chlorosulfonic acid more again.
With monofilm 20# and multilayer film 2# hot pressing, make five layers of perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 121#).
Embodiment 19: with repetitive be
Polymer and ZrO
2(0.01 micron of particle diameter) is that 100: 6.7 mixed meltings are extruded by mass ratio. (monofilm 21#). and monofilm 18# and monofilm 21# 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 122#).
Embodiment 20: with repetitive be
Polymer and repetitive be:
Polymer be that 0.5: 5 ratio is mixed the back and added to be scattered in behind the H-modenite (5 microns of particle diameters) (account for gross weight 5.7%) and form 24% solution among the NMP with mass ratio, going out to obtain thickness through curtain coating is 50 microns film (monofilm 22#).
With monofilm 22# place between two monofilm 7# again with two compound hot pressing of monofilm 14# after acidifying get multilayer amberplex (multilayer film 123#).
Embodiment 21: with repetitive be
The polymer of EW=900 and 3 μ mSiO
2(with the mass ratio of perfluorinated sulfonic resin be 5: 100), extrude and obtain the film that thickness is 50 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 23#) that acid solution is handled.
With monofilm 23, crosslinked 16 tunics (multilayer film 124#) of 11# and multilayer film 111# and the overlapping hot pressing of multilayer film 7# film, thickness is 300 μ m
Comparative example 22: utilize 10%nafion
The eptfe film that solution is thick with 30 μ m (porosity 70%) places above-mentioned solution to soak about 1 hour, and the film that will soak carries out the polytetrafluoroethylene film enhancing amberplex that dry 170 ℃ of processing obtain 30 micron thickness on heating plate then.
Experimental example 23
Performance to various films characterizes, and the results are shown in Table 1.As can be seen from Table 1,100 ℃ of electrical conductivity of the fluorine-containing cross-linked doped ion-exchange membrane of microporous film enhanced multilayer, hot strength, hydrogen permeate electric current, performances such as size changing rate all are better than common polytetrafluoroethylene film and strengthen amberplex.
The various films of table 1 characterize