CN115991822A - Ionic polymer membrane containing perfluorobutyl ethyl ether and preparation method thereof - Google Patents
Ionic polymer membrane containing perfluorobutyl ethyl ether and preparation method thereof Download PDFInfo
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- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 73
- 239000012528 membrane Substances 0.000 title claims abstract description 71
- KSOCRXJMFBYSFA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,6,6,6-tridecafluoro-5-(1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluorohexan-2-yloxy)hexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(C(F)(F)F)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F KSOCRXJMFBYSFA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 62
- 229920005989 resin Polymers 0.000 claims abstract description 62
- -1 perfluorovinyl ether phosphonate Chemical compound 0.000 claims abstract description 48
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 29
- 239000011737 fluorine Substances 0.000 claims abstract description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 25
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 239000003381 stabilizer Substances 0.000 claims description 107
- 239000007788 liquid Substances 0.000 claims description 48
- 239000000835 fiber Substances 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000003446 ligand Substances 0.000 claims description 26
- 239000006185 dispersion Substances 0.000 claims description 24
- 238000005342 ion exchange Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 229920000554 ionomer Polymers 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 230000003014 reinforcing effect Effects 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- IOSNRMYCWFCSLE-UHFFFAOYSA-N ethenyl hypofluorite sulfuryl difluoride Chemical compound FOC=C.FS(F)(=O)=O IOSNRMYCWFCSLE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000667 (NH4)2Ce(NO3)6 Inorganic materials 0.000 claims description 2
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001774 Perfluoroether Polymers 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920006221 acetate fiber Polymers 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 150000004696 coordination complex Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000002557 mineral fiber Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000131 polyvinylidene Polymers 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 7
- HDMTWPVKWCLZNV-UHFFFAOYSA-N sulfuryl difluoride 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FS(F)(=O)=O.FC(F)=C(F)OC(F)=C(F)F HDMTWPVKWCLZNV-UHFFFAOYSA-N 0.000 abstract description 5
- 230000020477 pH reduction Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 229920001002 functional polymer Polymers 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000446 fuel Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000005266 casting Methods 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000003014 ion exchange membrane Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- PZHIWRCQKBBTOW-UHFFFAOYSA-N 1-ethoxybutane Chemical class CCCCOCC PZHIWRCQKBBTOW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical group CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention belongs to the technical field of functional polymer materials, and particularly relates to an ionic polymer membrane containing perfluorobutyl ethyl ether and a preparation method thereof. The fluorine-containing resin used for the ionic polymer film is prepared by quaternary copolymerization of perfluoroolefin/perfluoroolefin ether monomer, perfluorovinyl ether phosphonate monomer, perfluorovinyl ether sulfonyl fluoride monomer and perfluorobutyl ethyl ether sulfonyl fluoride monomer, and then hydrolysis and acidification. The ionic polymer membrane contains a phosphonic acid structural group, a perfluorovinyl ether sulfonic acid structural group and a perfluorobutyl ethyl ether sulfonic acid structural group, and can not only have high proton conductivity under a high-temperature (120-150 ℃) low-humidity environment, but also have better structural stability, good mechanical property and chemical property.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to an ionic polymer membrane containing perfluorobutyl ethyl ether and a preparation method thereof.
Background
The ionomer membrane serves as one of the key materials of the fuel cell, and its operating temperature determines the operating temperature of the fuel cell. Ionic polymer membranes are bottlenecks, in addition to catalysts, that limit the commercial application of proton exchange membrane fuel cells, determining the cost and life of the fuel cell.
Proton conductivity is used as a basic performance index of the ionic polymer membrane, and influences the synthesis and modification directions of the ionic polymer membrane material. The fuel cell is now widely used as a perfluorosulfonic acid ionomer membrane, most typically a Nafion membrane from DuPont, usa.
The Nafion membrane has a mixed phase structure, namely, a continuous and hydrophobic fluorocarbon high polymer main chain region contains hydrophilic sulfonic acid groups, the hydrophobic fluorocarbon main chain has excellent thermal stability and chemical stability, the service life of the polymer membrane is ensured, the hydrophilic sulfonic acid groups are media for adsorbing water, the water is used as a carrier for proton conduction in the membrane, protons can be promoted to be dissociated from the hydrophilic sulfonic acid groups, and flowing hydrated protons are provided, so that the proton conduction process is completed, and the higher the water content of the membrane is, the faster the proton conduction rate of the membrane is. Nafion membranes have the advantage of high chemical stability and proton conductivity, but the performance of the membrane is severely dependent on the water content in the membrane. Thus, the proton exchange membrane using perfluorosulfonic acid has good proton conductivity at lower temperature (less than or equal to 80 ℃) and higher humidity, but the proton conductivity is far lower than 10mS/cm at the high temperature of 120 ℃ when the working temperature is high, and the requirement of ion conductivity cannot be met.
Disclosure of Invention
The invention aims to provide an ionic polymer film containing perfluorobutyl ethyl ether and a preparation method thereof, wherein the ionic polymer film contains a phosphonic acid structural group, a perfluorovinyl ether sulfonic acid structural group and a perfluorobutyl ethyl ether sulfonic acid structural group, and can not only have high proton conductivity under a high-temperature (120-150 ℃) low-humidity environment, but also have better structural stability, mechanical property and chemical property. Especially, the existence of the perfluoro butyl ethyl ether sulfonic acid structural group is matched with other structural groups to provide more physical crosslinking points, so that the strength of the ionic polymer membrane is effectively improved. The ionic polymer membrane provided by the invention can be used for fuel cells, electrochemical hydrogen pumps, water electrolysis hydrogen production and electrolytic cell devices.
The technical scheme of the invention is as follows: the ionic polymer film containing perfluoro butyl ethyl ether is prepared with perfluoro olefin/perfluoro vinyl ether monomer, perfluoro vinyl ether phosphonate monomer, perfluoro vinyl ether sulfonyl fluoride monomer and perfluoro butyl ethyl ether sulfonyl fluoride monomer and through quaternary copolymerization, hydrolysis and acidification.
Further, the molecular structural formula of the fluorine-containing resin used in the ionic polymer film is shown as the following formula:
wherein k is an integer of 0 to 3, and f is an integer of 1 to 4; preferably, k=1, f=2;
a. b and c are independent integers of 1 to 20, a ', b ' and c ' are independent integers of 1 to 3;
x/(x+y+z)＝0.1～0.8，y/(x+y+z)＝0.05～0.5，z/(x+y+z)＝0.1～0.6；
wherein R is- (OCF) 2 ) m (CF 2 ) n X, wherein X is Cl or F; m and n are integers from 0 to 3.
The structural formula of the perfluoroolefin/perfluorovinyl ether monomer in the scheme is as follows: CF (compact flash) 2 ＝CF-(OCF 2 ) m (CF 2 ) n X, X is Cl or F, m and n are independent integers of 0 to 3.
The structural formula of the perfluorobutyl ethyl ether sulfonyl fluoride monomer is as follows: CF (compact flash) 2 ＝CF-OCF 2 CF 2 CF 2 CF 2 SO 2 F；
The structural formula of the perfluorovinyl ether sulfonyl fluoride monomer is as follows: CF (compact flash) 2 ＝CF-OCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 F；
The structural formula of the perfluorovinyl ether phosphonate monomer is as follows:
wherein k is an integer of 0 to 3, f is an integer of 1 to 4, and p is an integer of 1 to 3.
Further, the number average molecular weight of the fluorine-containing resin used for the ionic polymer film is 20-80 ten thousand; preferably, the number average molecular weight is 30 to 50 ten thousand.
Further, the ionic polymer membrane also comprises a stabilizer A and/or a stabilizer B;
the stabilizer A is a metal complex formed by metal M and ligand L according to a molar ratio of 1:1-8;
preferably, the molar ratio of the metal M to the ligand L is 1:1-6;
wherein the metal M is selected from CeO 2 、CePO 4 、Ce(NO 3 ) 3 ·6H 2 O、Ce(SO 4 ) 2 、Ce(OH) 4 、Ce 2 (CO 3 ) 3 ·xH 2 O、(NH 4 ) 2 Ce(NO 3 ) 6 、Ce(CH 3 COO) 3 ·xH 2 One or more of O;
the structural formula of the ligand L is as follows:
r in the formula 1 、R 2 、R 3 、R 4 Independently selected from H, OH, CH 3 (CH 2 ) n O，CH 3 (CH 2 ) n ，NH 2 ，CH 2 OH，C 6 H 5 ，CF 3 (CF 2 ) n ，CF 3 (CF 2 ) n One of O, wherein n is an integer of 0 to 10;
the structural formula of the stabilizer B is as follows:
r in the formula 11 、R 22 、R 33 、R 44 Independently selected from H, OH, CH 3 (CH 2 ) n O，CH 3 (CH 2 ) n ，NH 2 ，CH 2 OH，C 6 H 5 ，CF 3 (CF 2 ) n ，CF 3 (CF 2 ) n O, wherein n is an integer of 0-10.
Further, the ionic polymer membrane also comprises a stabilizer A and a stabilizer B, wherein the content of the stabilizer A in the ionic exchange membrane is 0.01 to 3 weight percent, and the content of the stabilizer B in the ionic exchange membrane is 0.01 to 2 weight percent.
Further, the ion exchange capacity of the ionic polymer membrane is 1.0-2.4 mmol/g;
preferably, 0.9 to 1.5mmol/g;
more preferably 1.0 to 1.4mmol/g.
The preparation method of the ionic polymer film comprises the following steps:
(1) Dissolving the fluorine-containing resin into a solvent to prepare a dispersion liquid, and adding a stabilizer A and/or a stabilizer B into the dispersion liquid to uniformly disperse the stabilizer A and/or the stabilizer B, thereby obtaining uniform film-forming liquid;
(2) And (3) coating the obtained film-forming liquid into a film, and heating to volatilize the solvent to obtain the ionic polymer film.
In the step, the film forming liquid is coated and formed into a film by conventional operation, and the film can be formed on glass or fiber reinforced layer materials by adopting solution casting, wire rod coating, doctor blade coating, spraying or dipping and other modes.
In addition, the ionic polymer film can also be prepared by a melt extrusion film forming mode, and the ionic polymer film is specifically as follows:
1) Firstly, preparing a polymer precursor obtained by quaternary copolymerization of a perfluoroolefin/perfluorovinyl ether monomer, a perfluorovinyl ether phosphonate monomer, a perfluorovinyl ether sulfonyl fluoride monomer and a perfluorobutyl ethyl ether sulfonyl fluoride monomer;
2) Regulating the temperature of each section of the twin-screw extruder and the temperature of the die of the extruder to be 200-280 ℃, preparing a polymer precursor into a polymer base film by a melt extrusion mode, wherein the thickness of the film can be regulated by regulating the width of the die;
3) Placing a porous fiber reinforced material on the surface or inside of a base film by adopting a continuous vacuum compounding process to prepare a reinforced polymer base film;
4) And soaking the obtained enhanced polymer base film in an alkali metal hydroxide solution, hydrolyzing and transforming, soaking in an acid solution, and washing with deionized water to obtain the ionic polymer film.
Wherein the volume ratio of the porous fiber reinforced material in the step 3) in the ion exchange membrane is 5-70%; preferably, the volume ratio of the porous fiber reinforced material in the ion exchange membrane is 10% -60%; more preferably, the porous fibrous reinforcing material is present in the ion exchange membrane in a volume ratio of 20% to 50%.
The alkali metal hydroxide in the step 4) can be KOH or NaOH aqueous solution; the acid solution can be nitric acid, sulfuric acid, nitric acid and other common strong acids or mixed solution of strong acids.
Further, the solid content of the film-making liquid in the step (1) of the preparation method of the ionic polymer film is 20-35 wt%; the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetone, butanone, aqueous solution of C1-C5 alcohol/alcohol, formic acid or acetic acid.
In the step (2) of the preparation method of the ionic polymer film, the obtained film-forming liquid is coated on the porous fiber reinforced net layer for film formation.
The total thickness of the porous fiber reinforced net layer is 2-50 mu m; preferably, the total thickness of the porous fibrous reinforcing web is from 5 to 20 μm.
The number of the porous fiber reinforced net layers is 2-30; preferably, the number of the porous fiber reinforced net layers is 2-10; more preferably, the number of fiber reinforced mesh layers is 2 to 5.
The porosity of the porous fiber reinforced net layer is 70% -95%; preferably, the porous fiber reinforced web layer has a porosity of 75% to 95%; more preferably, the porous fibrous reinforcing web layer has a porosity of 80% to 95%.
The gram weight of the porous fiber reinforced net layer is 3-6 g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the porous fiber-reinforced web layer has a grammage of 3 to 5g/m 2 。
The porous fiber reinforced net is made of one or more materials selected from polytetrafluoroethylene, polyethylene, polyvinylidene fluoride-Co-hexafluoropropylene polypropylene, polyethylene-Co-propylene, polyimide, polyvinyl chloride, poly (perfluoroethylene-propylene) fiber, poly (perfluoropropyl vinyl ether) fiber, perfluoroalkoxy vinyl ether copolymer fiber, acetate fiber, ceramic fiber, mineral fiber and oxide fiber.
Further, the thickness of the prepared ionic polymer film is 10-250 μm.
Preferably, the ionomer film has a thickness of 10 to 150 μm.
More preferably, the thickness of the ionomer membrane is 10 to 50 μm.
The beneficial effects of the invention are as follows: the ionic polymer membrane has the following advantages:
1. the fluorine-containing resin adopted by the ionic polymer membrane simultaneously has a phosphonic acid structure group, a perfluorovinyl ether sulfonic acid structure group and a perfluorobutyl ethyl ether sulfonic acid structure group, and the groups are mutually cooperated, so that the problem that the proton conductivity of the proton exchange membrane in the prior art is poor at a high temperature (120-150 ℃) is solved, and the structure is more stable. In addition, the existence of the perfluoro butyl ethyl ether sulfonic acid structural group and other structural groups are matched to provide more physical crosslinking points, so that the strength of the ionic polymer membrane is effectively improved. Therefore, the phosphonic acid structural group and the long-short branched sulfonic acid structural group in the ionic polymer membrane are matched together, so that the proton conductivity under the high-temperature condition is greatly improved, and meanwhile, the ionic exchange membrane is ensured to have high ionic exchange capacity and good mechanical property, stability and chemical property.
The ionic polymer membrane provided by the invention can be used for fuel cells, electrochemical hydrogen pumps, water electrolysis hydrogen production and electrolytic cell devices. The conductivity of the ionic polymer membrane measured at 150 ℃ is still higher than 60mS/cm, so that the ionic polymer membrane can completely meet the application requirements of the proton membrane of the fuel cell under the high-temperature working condition, and is more suitable for the high-temperature fuel cell.
2. The stabilizer A and/or the stabilizer B are/is added into the ionic polymer membrane, so that the service life of the ionic exchange membrane at high temperature is effectively prolonged, and the performance of the ionic polymer membrane is not damaged.
Detailed Description
The following describes the technical scheme of the invention in detail.
The following examples are further illustrative of the invention, which is not limited thereto. The reaction kettles used in the embodiments are stainless steel high-pressure reaction kettles, and are provided with temperature sensors, pressure sensors, a heating circulation system, a cooling circulation system, a stirring motor, an internal cooling water pipe, a liquid metering pump, a gas feeding valve, a liquid feeding valve and a material discharging valve in the reaction kettles.
The ion exchange capacity is determined from the conversion of sulfonyl fluoride to sulfonic acid and the conversion of phosphonate to phosphinic acid unless otherwise specified in the examples below.
The potassium persulfate adopted in the synthesis process is purchased through a national drug group; the fluorine-containing surfactant, tetrafluoroethylene monomer and perfluoro vinyl ether sulfonyl fluoride monomer can be purchased from Shandong Dongyue polymer material Co.
Tetrafluoroethylene monomer adopted in the synthesis process is purchased from Shandong Dongyue polymer material limited company; the perfluorobutyl ethyl ether sulfonyl fluoride monomer was prepared as described in chinese patents CN200910229444.1, CN200910229446.0, CN 200910230218.5. Perfluoro vinyl ether phosphonate monomers can be prepared using the methods disclosed in literature Facile Synthesis of Fluorinated Phosphonates Via Photochemical and Thermal Reactions [ J ], haridasan K.Nair and Donald J.Burton, J.Am.Chem.Soc.1997,119,9137-9143.
The preparation method of the resin adopted in the technical scheme comprises the following specific steps:
1) Adding deionized water and a fluorine-containing surfactant CF into a reaction kettle 3 CF 2 (CF 2 OCF(CF 3 )) 2 COONH 4 Stirring; filling nitrogen to ensure that the oxygen content in the reaction kettle is less than 5ppm, and vacuumizing;
2) Adding all the required perfluorovinyl ether sulfonyl fluoride monomers and all the perfluorovinyl ether phosphonate monomers into a reaction kettle at one time; and adding an initial amount of perfluorobutyl ethyl ether sulfonyl fluoride monomer, wherein the initial amount is 50% -80% of the total required addition amount of the perfluorobutyl ethyl ether sulfonyl fluoride monomer;
then, tetrafluoroethylene monomer is filled into the reaction kettle until the pressure in the kettle is 0.1-8 MPa, and after the temperature is raised to 30-100 ℃, an initiator potassium persulfate is added to initiate dispersion polymerization;
continuously introducing tetrafluoroethylene monomer in the reaction process, keeping the pressure at 0.1-8 MPa, and adding the residual added amount of perfluorobutyl ethyl ether sulfonyl fluoride monomer into the reaction system every 45-60 min; simultaneously adding an initiator into the system every 20-25 min;
finally, after the reaction is finished, filtering, separating and drying to obtain a polymer precursor containing the perfluorobutyl ethyl ether;
3) Carrying out transformation reaction on a polymer precursor containing perfluorobutyl ethyl ether and a sodium hydroxide aqueous solution with the mass percentage of 3-10% for 8-24 hours at the temperature of 40-100 ℃ under the protection atmosphere of nitrogen;
4) After the reaction is finished, filtering, washing with water to be neutral, then carrying out acid washing by adopting hydrochloric acid with the concentration of 3-8wt%, and drying to obtain the fluorine-containing resin.
Example 1
The molecular structural formula of the fluorine-containing resin used in the perfluorinated butyl ethyl ether-containing ionomer membrane is shown as the following formula:
wherein k=1, f=2; a. b and c are independent integers of 1 to 20, a ', b ' and c ' are independent integers of 1 to 3;
x＝3,y＝2,z＝4；
wherein R is F.
The ion exchange capacity of the resin was 1.4mmol/g and the number average molecular weight was 42 ten thousand.
The molar ratio of the phosphonic acid structural unit in the resin is 20.5 percent, the molar ratio of the perfluorobutyl ethyl ether sulfonic acid structural unit is 10.2 percent, and the molar ratio of the perfluorovinyl ether sulfonic acid structural unit is 19.3 percent.
The preparation method of the ionic polymer film comprises the following steps:
(1) Dissolving the fluorine-containing resin in N, N-dimethylformamide to prepare a dispersion liquid, adding a stabilizer A and a stabilizer B into the dispersion liquid, and stirring and dispersing uniformly to obtain a film-forming liquid with the solid content of 22%; wherein stabilizer A: the mass ratio of the stabilizer B is 2:1, and the addition amount of the stabilizer A is 1.1% of the mass of the resin;
the ligand L in the stabilizer A is
Wherein R is 1 And R is 4 Are all C 6 H 5 ，R 3 Is H, R 2 OH;
the metal M in the stabilizer A is Ce 2 (CO 3 ) 3 ·xH 2 O; ligand L: ce (Ce) 3+ The molar ratio of (2) is 3:1.
Stabilizer B is
Wherein R is 11 And R is 22 Are all OCH 3 ；R 33 And R is 44 All are H.
(2) The obtained film-forming liquid was coated by a wire rod to form a film, and the solvent was evaporated after heating to obtain a perfluorobutyl ethyl ether-containing ionomer film having a thickness of 12. Mu.m.
Example 2
The molecular structural formula of the resin used in the perfluorinated butyl ethyl ether-containing ionomer membrane is shown as the following formula:
wherein k=1, f=2; a. b and c are independent integers of 1 to 20, a ', b ' and c ' are independent integers of 1 to 3;
x＝3,y＝2,z＝3；
wherein R is F.
The ion exchange capacity of the resin was 1.4mmol/g and the number average molecular weight was 42 ten thousand.
The molar ratio of the phosphonic acid structural unit in the resin is 20.3 percent, the molar ratio of the perfluorobutyl ethyl ether sulfonic acid structural unit is 10.5 percent, and the molar ratio of the perfluorovinyl ether sulfonic acid structural unit is 19.5 percent.
The preparation method of the ionic polymer film comprises the following steps:
(1) Dissolving the fluorine-containing resin in N, N-dimethylformamide to prepare a dispersion liquid, adding a stabilizer A and a stabilizer B into the dispersion liquid, and stirring and dispersing uniformly to obtain a film-forming liquid with the solid content of 22%; wherein stabilizer A: the mass ratio of the stabilizer B is 2:1, and the addition amount of the stabilizer A is 1.2% of the mass of the resin;
the ligand L in the stabilizer A is
Wherein R is 1 And R is 4 Are all C 6 H 5 ，R 3 Is H, R 2 OH;
the metal M in the stabilizer A is Ce 2 (CO 3 ) 3 ·xH 2 O; ligand L: ce (Ce) 3+ The molar ratio of (2) is 3:1.
Stabilizer B is
Wherein R is 11 And R is 22 Are all OCH 3 ；R 33 And R is 44 All are H.
Coating on polytetrafluoroethylene reinforced net by using wire rod, heating and volatilizing solvent to obtain the ionic polymer film with thickness of 12 micrometers. Wherein the polytetrafluoroethylene isEthylene reinforcing net 2 layers, porosity of 80%, gram weight of 3.2g/m 2 。
Example 3
The molecular structural formula of the fluorine-containing resin used in the ionic polymer film is shown as the following formula:
wherein k=1, f=2; a. b and c are independent integers of 1 to 20, a ', b ' and c ' are independent integers of 1 to 3;
x＝3,y＝2,z＝3；
wherein R is F.
The ion exchange capacity of the resin was 1.4mmol/g and the number average molecular weight was 45 ten thousand.
The molar ratio of the phosphonic acid structural unit in the resin is 20.3 percent, the molar ratio of the perfluorobutyl ethyl ether sulfonic acid structural unit is 20.4 percent, and the molar ratio of the perfluorovinyl ether sulfonic acid structural unit is 20.2 percent.
The preparation method of the ionic polymer film comprises the following steps:
(1) Dissolving the fluorine-containing resin in N, N-dimethylformamide to prepare a dispersion liquid, adding a stabilizer A and a stabilizer B into the dispersion liquid, and stirring and dispersing uniformly to obtain a film-forming liquid with the solid content of 20%; wherein stabilizer A: the mass ratio of the stabilizer B is 2:1, and the addition amount of the stabilizer A is 1% of the mass of the resin;
the ligand L in the stabilizer A is
Wherein R is 1 And R is 4 Are all C 6 H 5 ，R 3 Is H, R 2 OH;
the metal M in the stabilizer A is (NH) 4 ) 2 Ce(NO 3 ) 6 The method comprises the steps of carrying out a first treatment on the surface of the Ligand L: ce (Ce) 3+ The molar ratio of (2) was 4:1.
Stabilizer B is
Wherein R is 11 And R is 22 Are all OCH 3 ；R 33 And R is 44 All are H.
(2) The obtained film-forming liquid was coated on a polyethylene reinforcing net by a wire bar, and the solvent was volatilized after heating to obtain an ionomer film having a thickness of 15. Mu.m. Wherein the polytetrafluoroethylene reinforced net has 3 layers, the porosity is 82 percent, and the gram weight is 3.0g/m 2 。
Example 4
The molecular structural formula of the fluorine-containing resin used in the ionic polymer film is shown as the following formula:
wherein k=1, f=2; a. b and c are independent integers of 1 to 20, a ', b ' and c ' are independent integers of 1 to 3;
x＝3,y＝2,z＝3；
wherein R is F.
The ion exchange capacity of the resin was 1.4mmol/g and the number average molecular weight was 40 ten thousand.
The molar ratio of the phosphonic acid structural unit in the resin is 20.4 percent, the molar ratio of the perfluorobutyl ethyl ether sulfonic acid structural unit is 10.3 percent, and the molar ratio of the perfluorovinyl ether sulfonic acid structural unit is 20.5 percent.
The preparation method of the ionic polymer film comprises the following steps:
(1) Dissolving the fluorine-containing resin in N, N-dimethylformamide to prepare a dispersion liquid, adding a stabilizer A and a stabilizer B into the dispersion liquid, and stirring and dispersing uniformly to obtain a film-forming liquid with the solid content of 20%; wherein stabilizer A: the mass ratio of the stabilizer B is 1:1, and the addition amount of the stabilizer A is 1% of the mass of the resin;
the ligand L in the stabilizer A is
Wherein R is 1 And R is 4 Are all C 6 H 5 ，R 3 Is H, R 2 OH;
the metal M in the stabilizer A is Ce 2 (CO 3 ) 3 ·xH 2 O; ligand L: ce (Ce) 3+ The molar ratio of (2) is 3:1.
Stabilizer B is
Wherein R is 11 And R is 22 Are all OCH 3 ；R 33 And R is 44 All are H. />
(2) Coating on a polytetrafluoroethylene reinforced net by adopting a solution casting method, heating and volatilizing a solvent to obtain the ionic polymer film with the thickness of 15 mu m. Wherein the polyethylene reinforcing net has 3 layers, the porosity is 82 percent, and the gram weight is 3.0g/m 2 。
Example 5
The molecular structural formula of the fluorine-containing resin used in the ionic polymer film is shown as the following formula:
wherein k=0, f=2; a. b and c are independent integers of 1 to 20, a ', b ' and c ' are independent integers of 1 to 3;
x＝3,y＝2,z＝3；
wherein R is F.
The ion exchange capacity of the resin was 1.6mmol/g and the number average molecular weight was 40 ten thousand.
The molar ratio of the phosphonic acid structural unit in the resin is 20.3 percent, the molar ratio of the perfluorobutyl ethyl ether sulfonic acid structural unit is 10.6 percent, and the molar ratio of the perfluorovinyl ether sulfonic acid structural unit is 20.2 percent.
The preparation method of the ionic polymer film comprises the following steps:
(1) Dissolving the fluorine-containing resin in N, N-dimethylformamide to prepare a dispersion liquid, adding a stabilizer A and a stabilizer B into the dispersion liquid, and stirring and dispersing uniformly to obtain a film-forming liquid with the solid content of 20%; wherein stabilizer A: the mass ratio of the stabilizer B is 1:1, and the addition amount of the stabilizer A is 1% of the mass of the resin;
the ligand L in the stabilizer A is
Wherein R is 1 And R is 4 Are all C 6 H 5 ，R 3 Is H, R 2 OH;
the metal M in the stabilizer A is Ce 2 (CO 3 ) 3 ·xH 2 O; ligand L: ce (Ce) 3+ The molar ratio of (2) was 4:1.
Stabilizer B is
Wherein R is 11 And R is 22 Are all OCH 3 ；R 33 And R is 44 All are H.
(2) And (3) scraping the obtained film-making solution on a polytetrafluoroethylene reinforced net by adopting a solution casting method, and volatilizing the solvent after heating to obtain the multi-element copolymer ion exchange film with the thickness of 15 mu m. Wherein the polytetrafluoroethylene reinforced net has 3 layers, the porosity is 85 percent, and the gram weight is 3.1g/m 2 。
Example 6
The molecular structural formula of the fluorine-containing resin used in the ionic polymer film is shown as the following formula:
wherein k=1, f=2; a. b and c are independent integers of 1 to 20, a ', b ' and c ' are independent integers of 1 to 3;
x＝3,y＝2,z＝3；
wherein R is F.
The ion exchange capacity of the resin was 1.6mmol/g and the number average molecular weight was 50 ten thousand.
The molar ratio of the phosphonic acid structural unit in the resin is 25.2%, the molar ratio of the perfluorobutyl ethyl ether sulfonic acid structural unit is 10.2%, and the molar ratio of the perfluorovinyl ether sulfonic acid structural unit is 20.3%.
The preparation method of the ionic polymer film comprises the following steps:
(1) Dissolving the fluorine-containing resin in N, N-dimethylformamide to prepare a dispersion liquid, adding a stabilizer A and a stabilizer B into the dispersion liquid, and stirring and dispersing uniformly to obtain a film-forming liquid with the solid content of 25%; wherein stabilizer A: the mass ratio of the stabilizer B is 1:1, and the addition amount of the stabilizer A is 1.3% of the mass of the resin;
the ligand L in the stabilizer A is
Wherein R is 1 And R is 4 Are all C 6 H 5 ，R 3 Is H, R 2 OH;
the metal M in the stabilizer A is Ce 2 (CO 3 ) 3 ·xH 2 O; ligand L: ce (Ce) 3+ The molar ratio of (2) was 4:1.
Stabilizer B is
Wherein R is 11 And R is 22 Are all OCH 3 ；R 33 And R is 44 All are H.
(2) And (3) scraping the obtained film-making solution on a polyethylene reinforced net by adopting a solution casting method, and volatilizing the solvent after heating to obtain the multi-element copolymer ion exchange film with the thickness of 25 mu m. Wherein the polyethylene reinforcing net has 3 layers, the porosity is 86 percent, and the gram weight is 3.0g/m 2 。
Example 7
The molecular structural formula of the fluorine-containing resin used in the ionic polymer film is shown as the following formula:
wherein k=1, f=2; a. b and c are independent integers of 1 to 20, a ', b ' and c ' are independent integers of 1 to 3;
x＝3.5,y＝2.5,z＝3；
wherein R is F.
The ion exchange capacity of the resin was 1.6mmol/g and the number average molecular weight was 45 ten thousand.
The molar ratio of the phosphonic acid structural unit in the resin is 25.4%, the molar ratio of the perfluorobutyl ethyl ether sulfonic acid structural unit is 15.2%, and the molar ratio of the perfluorovinyl ether sulfonic acid structural unit is 20.2%.
The preparation method of the ionic polymer film comprises the following steps:
(1) Dissolving the fluorine-containing resin in N, N-dimethylformamide to prepare a dispersion liquid, adding a stabilizer A and a stabilizer B into the dispersion liquid, and stirring and dispersing uniformly to obtain a film-forming liquid with the solid content of 30%; wherein stabilizer A: the mass ratio of the stabilizer B is 1:1, and the addition amount of the stabilizer A is 1.2% of the mass of the resin;
the ligand L in the stabilizer A is
Wherein R is 1 And R is 4 Are all C 6 H 5 ，R 3 Is H, R 2 OH;
the metal M in the stabilizer A is Ce 2 (CO 3 ) 3 ·xH 2 O; ligand L: ce (Ce) 3+ The molar ratio of (2) was 4:1.
Stabilizer B is
Wherein R is 11 And R is 22 Are all OCH 3 ；R 33 And R is 44 All are H.
(2) And (3) blade-coating the obtained film-making solution on a polytetrafluoroethylene reinforced net by adopting a solution casting method, and volatilizing the solvent after heating to obtain the ionic polymer film with the thickness of 50 mu m. Wherein the polyethylene reinforced net has 3 layers, the porosity is 83 percent, and the gram weight is 3.0g/m 2 。
Example 8
The molecular structural formula of the resin used in the ionic polymer film is shown as the following formula:
wherein k=1, f=2; a. b and c are independent integers of 1 to 20, a ', b ' and c ' are independent integers of 1 to 3;
x＝3,y＝2,z＝3.5；
wherein R is F.
The ion exchange capacity of the resin was 1.6mmol/g and the number average molecular weight was 45 ten thousand.
The molar ratio of the phosphonic acid structural unit in the resin is 20.4%, the molar ratio of the perfluorobutyl ethyl ether sulfonic acid structural unit is 15.2%, and the molar ratio of the perfluorovinyl ether sulfonic acid structural unit is 25.0%.
The preparation method of the ionic polymer film comprises the following steps:
(1) Dissolving the resin in N, N-dimethylacetamide to prepare a dispersion liquid, adding a stabilizer A and a stabilizer B into the dispersion liquid, and stirring and dispersing uniformly to obtain a film forming liquid with the solid content of 25%; wherein stabilizer A: the mass ratio of the stabilizer B is 1:1, and the addition amount of the stabilizer A is 1% of the mass of the resin;
the ligand L in the stabilizer A is
Wherein R is 1 And R is 4 Are all C 6 H 5 ，R 3 Is H, R 2 OH;
the metal M in the stabilizer A is Ce 2 (CO 3 ) 3 ·xH 2 O; ligand L: ce (Ce) 3+ The molar ratio of (2) was 4:1.
Stabilizer B is
Wherein R is 11 And R is 22 Are all OCH 3 ；R 33 And R is 44 All are H.
(2) The obtained film-making solution is coated on a polyethylene reinforced net by adopting a solution casting method, and the solvent is volatilized after heating, so that the multipolymer ion exchange film with the thickness of 50 mu m is obtained. Wherein the polyethylene reinforcing net has 3 layers, the porosity is 82 percent, and the gram weight is 3.0g/m 2 。
Example 9
The molecular structural formula of the resin used in the ionic polymer film is shown as the following formula:
wherein k=1, f=2; a. b and c are independent integers of 1 to 20, a ', b ' and c ' are independent integers of 1 to 3;
x＝3.5,y＝2.5,z＝3；
wherein R is F.
The ion exchange capacity of the resin was 1.2mmol/g and the number average molecular weight was 43 ten thousand.
The molar ratio of the phosphonic acid structural unit in the resin is 24.2%, the molar ratio of the perfluorobutyl ethyl ether sulfonic acid structural unit is 15.0%, and the molar ratio of the perfluorovinyl ether sulfonic acid structural unit is 20.2%.
The preparation method of the ionic polymer film comprises the following steps:
(1) Dissolving the resin in N, N-dimethylformamide to prepare a dispersion liquid, adding a stabilizer A and a stabilizer B into the dispersion liquid, and stirring and dispersing uniformly to obtain a film forming liquid with 30% of solid content; wherein stabilizer A: the mass ratio of the stabilizer B is 1:1, and the addition amount of the stabilizer A is 1% of the mass of the resin;
the ligand L in the stabilizer A is
Wherein R is 1 And R is 4 Are all C 6 H 5 ，R 3 Is H, R 2 OH;
the metal M in the stabilizer A is Ce 2 (CO 3 ) 3 ·xH 2 O; ligand L: ce (Ce) 3+ The molar ratio of (2) was 4:1.
Stabilizer B is
Wherein R is 11 And R is 22 Are all OCH 3 ；R 33 And R is 44 All are H.
(2) And (3) scraping the obtained film-making solution on a polytetrafluoroethylene reinforced net by adopting a solution casting method, and volatilizing the solvent after heating to obtain the multipolymer ion exchange film with the thickness of 50 mu m. Wherein the polyethylene reinforced net has 3 layers, the porosity is 83 percent, and the gram weight is 3.0g/m 2 。
Example 10
The molecular structural formula of the resin used in the ionic polymer film is shown as the following formula:
wherein k=1, f=2; a. b and c are independent integers of 1 to 20, a ', b ' and c ' are independent integers of 1 to 3;
x＝3,y＝2.5,z＝3；
wherein R is F.
The ion exchange capacity of the resin was 1.1mmol/g and the number average molecular weight was 45 ten thousand.
The molar ratio of the phosphonic acid structural unit in the resin is 25.1%, the molar ratio of the perfluorobutyl ethyl ether sulfonic acid unit is 15.0%, and the molar ratio of the perfluorovinyl ether sulfonic acid structural unit is 20.2%.
The preparation method of the ionic polymer film comprises the following steps:
(1) Preparing a polymer precursor obtained by quaternary copolymerization of a perfluoroolefin/perfluorovinyl ether monomer, a perfluorovinyl ether phosphonate monomer, a perfluorovinyl ether sulfonyl fluoride monomer and a perfluorobutyl ethyl ether sulfonyl fluoride monomer;
(2) Melt extrusion film forming is carried out through a double screw extruder at 270 ℃ to obtain a polymer base film;
(3) Placing 3 layers of polyethylene reinforced mesh cloth into the interior by adopting a continuous vacuum compounding process to obtain a reinforced film with the thickness of 150 mu m;
(4) By passing through a 30% strength by mass sodium hydroxide solution at 80℃and a 30% strength by mass sulfuric acid solution (H) 2 SO 4 ) A flowing deionized water washing tank. The film stays in the sodium hydroxide solution for 30min,The residence time in sulfuric acid solution is 30min, the precursor film is rinsed with deionized water for 10min, and the precursor film is then rinsed with sulfonyl fluoride (-SO) 2 F) The side groups being converted to sulphonate ions (-SO) 3 H) Form (-PO (OR) in phosphonate ester 2 ) The side group is converted into phosphorous acid (-PO) 3 H 2 ) In the form, the reinforced ionic polymer membrane is obtained after hydrolytic acidification.
Comparative example 1
Selecting perfluorinated sulfonic acid resin with exchange capacity of 1.1mmol/g and number average molecular weight of 30 ten thousand, dissolving the perfluorinated sulfonic acid resin into dispersion liquid, adding stabilizer A and stabilizer B into the dispersion liquid, and stirring and dispersing uniformly to obtain film-forming liquid with solid content of 20%; wherein stabilizer A: the mass ratio of the stabilizer B is 1.7:1, and the addition amount of the stabilizer A is 1.75% of the mass of the resin;
the ligand L in the stabilizer A is
Wherein R is 1 And R is 4 Are all C 6 H 5 ，R 3 Is H, R 2 OH;
the metal M in the stabilizer A is Ce 2 (CO 3 ) 3 ·xH 2 O; ligand L: ce (Ce) 3+ The molar ratio of (2) was 4:1.
Stabilizer B is
Wherein R is 11 And R is 22 Are all OCH 3 ；R 33 And R is 44 All are H.
Stirring and dispersing uniformly to obtain film-forming liquid with the solid content of 20%, knife coating to form a film, heating and volatilizing the solvent to obtain the perfluorosulfonic acid proton film with the solid content of 15 mu m.
Comparative example 2
The perfluorosulfonic acid proton membrane of comparative example 1 was immersed in a phosphoric acid solution to obtain a phosphoric acid doped perfluorosulfonic acid proton membrane, the mass ratio of the doped phosphoric acid was 40%, and the exchange capacity was 1.2mmol/g.
Comparative example 3
A sulphonic acid film of model NRE211 from dupont.
The ion exchange membranes obtained in the above examples and comparative examples were tested for mechanical properties, conductivity, and dimensional change rate as follows:
1. and (3) testing mechanical properties of the film: the method is GB/T1040-92.
2. Measurement of conductivity: the temperature of the test conditions was 120℃and 150℃as measured by an electrochemical impedance tester.
3. Measurement of dimensional Change Rate: the adopted method is GB/T20042.3-2009.
4. The stability of the proton membrane is characterized by adopting the fluoride ion release rate, and the testing method comprises the following steps: 80ppm of Fe was added to 100mL of 30wt% hydrogen peroxide solution 2+ The ions were carefully weighed out and a mass (0.06-0.3 g) of the proton exchange membrane of the fuel cell was placed in the ion exchange membrane, and after holding at 80 ℃ for 8 hours, the sample was taken out of the solution. Washed with deionized water, dried at 80 ℃ for 2h, and weighed. Determination of F in solution - Is contained in the composition.
5. Ion exchange capacity test method: the test was performed using GB/T30296-2013.
The results of the sample testing are summarized in table 1.
TABLE 1 proton conductivity data for examples 1-10 and comparative examples 1-3
As shown by the test results in the table 1, compared with the sulfonic acid proton exchange membrane and the phosphoric acid doped perfluorosulfonic acid proton membrane, the ionic polymer membrane containing the perfluorobutyl ethyl ether unit prepared by the invention has high chemical stability, high dimensional stability, high ion exchange capacity and good high-temperature proton conductivity; the addition of the stabilizer can effectively reduce the release rate of fluorine ions and improve the chemical stability of the proton membrane.
Claims (10)
1. The ionic polymer film containing perfluoro butyl ethyl ether is characterized in that fluorine-containing resin used by the ionic polymer film is obtained by quaternary copolymerization of perfluoro olefin/perfluoro vinyl ether monomer, perfluoro vinyl ether phosphonate monomer, perfluoro vinyl ether sulfonyl fluoride monomer and perfluoro butyl ethyl ether sulfonyl fluoride monomer and then is hydrolyzed and acidified.
2. The ionic polymer membrane of claim 1, wherein the molecular structural formula of the fluorine-containing resin used in the ionic polymer membrane is as follows:
wherein k is an integer of 0 to 3, and f is an integer of 1 to 4; preferably, k=1, f=2;
a. b and c are independent integers of 1 to 20, a ', b ' and c ' are independent integers of 1 to 3;
x/(x+y+z)＝0.1～0.8，y/(x+y+z)＝0.05～0.5，z/(x+y+z)＝0.1～0.6；
wherein R is- (OCF) 2 ) m (CF 2 ) n X, wherein X is Cl or F; m and n are integers from 0 to 3.
3. The ionic polymer membrane according to claim 1, wherein the number average molecular weight of the fluorine-containing resin used in the ionic polymer membrane is 20 to 80 ten thousand;
preferably, the number average molecular weight is 30 to 50 ten thousand.
4. The ionic polymer membrane of claim 1, further comprising a stabilizer a and/or a stabilizer B;
the stabilizer A is a metal complex formed by metal M and ligand L according to a molar ratio of 1:1-8;
preferably, the molar ratio of the metal M to the ligand L is 1:1-6;
wherein the metal M is selected from CeO 2 、CePO 4 、Ce(NO 3 ) 3 ·6H 2 O、Ce(SO 4 ) 2 、Ce(OH) 4 、Ce 2 (CO 3 ) 3 ·xH 2 O、(NH 4 ) 2 Ce(NO 3 ) 6 、Ce(CH 3 COO) 3 ·xH 2 One or more of O;
the structural formula of the ligand L is as follows:
r in the formula 1 、R 2 、R 3 、R 4 Independently selected from H, OH, CH 3 (CH 2 ) n O，CH 3 (CH 2 ) n ，NH 2 ，CH 2 OH，C 6 H 5 ，CF 3 (CF 2 ) n ，CF 3 (CF 2 ) n One of O, wherein n is an integer of 0 to 10;
the structural formula of the stabilizer B is as follows:
r in the formula 11 、R 22 、R 33 、R 44 Independently selected from H, OH, CH 3 (CH 2 ) n O，CH 3 (CH 2 ) n ，NH 2 ，CH 2 OH，C 6 H 5 ，CF 3 (CF 2 ) n ，CF 3 (CF 2 ) n O, wherein n is an integer of 0-10.
5. The ionic polymer membrane of claim 4, further comprising a stabilizer a and a stabilizer B, wherein the stabilizer a is present in the ionic polymer membrane in an amount of 0.01wt% to 3wt% and the stabilizer B is present in the ionic polymer membrane in an amount of 0.01wt% to 3wt%.
6. The ionic polymer membrane of any one of claims 1-5, wherein the ionic polymer membrane has an ion exchange capacity of 0.9 to 2.4mmol/g;
preferably, 1.0 to 1.5mmol/g;
more preferably 1.0 to 1.4mmol/g.
7. A method of preparing the ionic polymer membrane of any one of claims 1-6, comprising the steps of:
(1) Dissolving the fluorine-containing resin into a solvent to prepare a dispersion liquid, and adding a stabilizer A and/or a stabilizer B into the dispersion liquid to uniformly disperse the stabilizer A and/or the stabilizer B, thereby obtaining uniform film-forming liquid;
(2) And (3) coating the obtained film-forming liquid into a film, and heating to volatilize the solvent to obtain the ionic polymer film.
8. The method for producing an ionomer membrane according to claim 7, wherein the solid content of the membrane-producing liquid in the step (1) is 20wt% to 35wt%; the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetone, butanone, aqueous solution of C1-C5 alcohol/alcohol, formic acid or acetic acid.
9. The method for producing an ionomer membrane according to claim 7, wherein the membrane-forming liquid obtained in the step (2) is coated on a porous fiber-reinforced net layer to form a membrane;
the total thickness of the porous fiber reinforced net layer is 2-50 mu m; preferably, the total thickness of the porous fiber reinforced web is 5 to 20 μm;
the number of the porous fiber reinforced net layers is 2-30; preferably, the number of the porous fiber reinforced net layers is 2-10; more preferably, the number of the fiber reinforced net layers is 2-5;
the porosity of the porous fiber reinforced net layer is 70% -95%; preferably, the porous fiber reinforced web layer has a porosity of 75% to 95%; more preferably, the porous fibrous reinforcing mesh layer has a porosity of 80% to 95%;
the gram weight of the porous fiber reinforced net layer is 3-6 g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Excellent (excellent)Optionally, the porous fiber reinforced web layer has a grammage of 3-5 g/m 2 ；
The porous fiber reinforced net is made of one or more materials selected from polytetrafluoroethylene, polyethylene, polyvinylidene fluoride-Co-hexafluoropropylene polypropylene, polyethylene-Co-propylene, polyimide, polyvinyl chloride, poly (perfluoroethylene-propylene) fiber, poly (perfluoropropyl vinyl ether) fiber, perfluoroalkoxy vinyl ether copolymer fiber, acetate fiber, ceramic fiber, mineral fiber and oxide fiber.
10. The method for producing an ionomer membrane according to claim 7, wherein the thickness of the produced ionomer membrane is 10 to 250 μm;
preferably, the thickness of the ionomer membrane is 10 to 150 μm;
more preferably, the thickness of the ionomer membrane is 10 to 50 μm.
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| CN202211270056.XA Active CN115991825B (en) | 2021-10-18 | 2022-10-17 | Fluorine-containing ionic membrane and preparation method thereof |
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| CN202211272342.XA Active CN115991832B (en) | 2021-10-18 | 2022-10-18 | Mixed fluorine-containing ion resin |
| CN202211276230.1A Active CN115991835B (en) | 2021-10-18 | 2022-10-18 | Wide-temperature-zone polymerized phosphonic acid resin and preparation method thereof |
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