CN114524912A - Side-chain piperidine cation grafted polybiphenyl alkaline membrane and preparation method thereof - Google Patents
Side-chain piperidine cation grafted polybiphenyl alkaline membrane and preparation method thereof Download PDFInfo
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- CN114524912A CN114524912A CN202210250840.8A CN202210250840A CN114524912A CN 114524912 A CN114524912 A CN 114524912A CN 202210250840 A CN202210250840 A CN 202210250840A CN 114524912 A CN114524912 A CN 114524912A
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- polybiphenyl
- piperidine
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- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000012528 membrane Substances 0.000 title claims abstract description 80
- -1 piperidine cation Chemical class 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims description 45
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical class CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 238000005266 casting Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 13
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical class CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000005956 quaternization reaction Methods 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 claims description 3
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 3
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 claims description 3
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical compound CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims description 2
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 claims description 2
- LVWSZGCVEZRFBT-UHFFFAOYSA-N 1,7-dibromoheptane Chemical compound BrCCCCCCCBr LVWSZGCVEZRFBT-UHFFFAOYSA-N 0.000 claims description 2
- WGAXVZXBFBHLMC-UHFFFAOYSA-N 1,9-dibromononane Chemical compound BrCCCCCCCCCBr WGAXVZXBFBHLMC-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- 238000007766 curtain coating Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- KVZQVTSNCUIGMU-UHFFFAOYSA-N 1,1'-biphenyl;piperidine Chemical compound C1CCNCC1.C1=CC=CC=C1C1=CC=CC=C1 KVZQVTSNCUIGMU-UHFFFAOYSA-N 0.000 claims 4
- 239000003011 anion exchange membrane Substances 0.000 abstract description 22
- 239000000446 fuel Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 125000002091 cationic group Chemical group 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 150000001768 cations Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 208000016261 weight loss Diseases 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- BTVVEKSXUOEVAY-UHFFFAOYSA-N 4,4-diphenylpiperidine Chemical compound C1CNCCC1(C=1C=CC=CC=1)C1=CC=CC=C1 BTVVEKSXUOEVAY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102100037709 Desmocollin-3 Human genes 0.000 description 1
- 101000968042 Homo sapiens Desmocollin-2 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical group C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000013421 nuclear magnetic resonance imaging Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G10/00—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
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- 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
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Abstract
The invention discloses a side chain piperidine cation grafted polybiphenyl alkaline membrane and a preparation method thereof, belonging to the technical field of preparation of fuel cell anion exchange membranes; the method comprises the following steps: (1) preparing a polybiphenyl skeleton; (2) preparing side chain piperidine cations; (3) preparing a side chain piperidine cation graft type polybiphenyl alkaline membrane. The side-chain piperidine cation grafted polybiphenyl alkaline membrane has high ionic conductivity and chemical stability, the hydroxyl ionic conductivity can reach 117.1mS/cm at 80 ℃, and the ionic conductivity is only reduced by less than 13.6 percent after the membrane is soaked in a 2M NaOH solution for 1500 hours at 80 ℃, so that good chemical stability is shown. In addition, the method has the characteristics of simple preparation process and low cost, and has wide application prospect in alkaline membrane fuel cells.
Description
Technical Field
The invention relates to an alkaline membrane and a preparation method thereof, in particular to a side chain piperidine cation grafted polybiphenyl alkaline membrane and a preparation method thereof, belonging to the technical field of preparation of fuel cell anion exchange membranes.
Technical Field
In recent years, Anion Exchange Membrane Fuel Cells (AEMFCs) have received much attention because they allow the use of non-noble metal catalysts and have a series of advantages such as rapid redox kinetics. As a key component of Anion Exchange Membrane Fuel Cells (AEMFCs) in transporting hydroxide ions and sequestering fuel and oxidant, Anion Exchange Membranes (AEMs) must maintain excellent durability, high ionic conductivity, and thermal stability in alkaline operating environments.
The chemical stability of Anion Exchange Membranes (AEMs) is largely dependent on the nature of the membrane material itself, especially dominated by the polymer backbone and grafted functional cationic groups. Currently, commonly used as polymer backbones are: polyphenylene Oxide (PPO), polyether sulfone (PES), polyether ether ketone (PEEK), and the like. However, the aryl ether bonds contained in the main chain of these polymer backbones have an electron withdrawing effect, and promote the nucleophilic attack of hydroxide ions, so that the main chain is broken, and the degradation of the membrane is accelerated.
In recent years, a series of ether-free frameworks have been used to develop highly stable Anion Exchange Membranes (AEMs).
Cationic groups are another key factor limiting the chemical stability of Anion Exchange Membranes (AEMs), and Anion Exchange Membranes (AEMs) based on cyclic quaternary ammonium groups exhibit superior chemical stability under the same alkaline conditions compared to Anion Exchange Membranes (AEMs) based on cationic groups such as trimethylamine, imidazolium, etc., because the lower ring strain of cyclic aminium and the conformational constraints imposed by the ring structure increase the transition state energy of substitution and elimination reactions during degradation and thus have higher chemical stability.
Although much progress has been made in the research on polymer backbones and cationic groups, the development of practically useful Anion Exchange Membranes (AEMs) remains a significant challenge. To achieve better Anion Exchange Membrane (AEM) performance, more and more research has focused on optimizing the manner in which the framework is attached to the cation. Through the long and flexible alkyl spacer chain, cations are far away from the framework, the electron-withdrawing capability of the framework to the cations can be weakened, the degradation of cationic groups is reduced, and the method is one of effective means for improving chemical stability. In addition, the flexible alkyl spacer chain can improve the local mobility of the cationic group, is beneficial to the self-aggregation of the cationic group, can manufacture a high-efficiency ion transmission channel, and can promote the formation of a hydrophilic hydrophobic microphase separation form, thereby improving the ion conductivity.
Therefore, the side-chain piperidine cation grafted polybiphenyl alkaline membrane and the preparation method thereof are provided, the polybiphenyl piperidine skeleton is synthesized through super acid catalysis, then strong alkali-resistant piperidine cations are grafted to the skeleton through flexible alkyl side chains, the side-chain piperidine cation grafted polybiphenyl alkaline membrane is prepared, the ionic conductivity and the chemical stability of an Anion Exchange Membrane (AEM) are effectively improved, the preparation method is simple and direct, and the side-chain piperidine cation grafted polybiphenyl alkaline membrane has a wide application prospect in an alkaline membrane fuel cell.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the side-chain piperidine cation grafted polybiphenyl alkaline membrane which has the advantages of high thermal stability, high chemical stability, high ionic conductivity, simple manufacturing process and the like.
The above object of the present invention is achieved by the following technical solutions:
the side chain piperidine cation grafted polybiphenyl alkaline membrane is characterized in that the side chain piperidine cation grafted polybiphenyl contains a polybiphenyl piperidine polymer skeleton and side chain piperidine cations.
Preferably, the side-chain piperidine cation-grafted polybiphenyl is 1- (3-bromopropyl) -1-methylpiperidine cation-grafted polybiphenyl (PBP-3-Pip), 1- (6-bromohexyl) -1-methylpiperidine cation-grafted polybiphenyl (PBP-6-Pip) or 1- (8-bromooctyl) -1-methylpiperidine cation-grafted polybiphenyl (PBP-8-Pip).
Preferably, the molecular weight of the side-chain piperidine cation-grafted polybiphenyl is between 1 and 50 ten thousand.
Preferably, the polybiphenyl is polydiphenylpiperidine or polyparaterphenylpiperidine or poly-m-terphenylpiperidine.
Preferably, the side-chain piperidine cation is any one or more of 1- (2-bromoethyl) -1-methylpiperidine, 1- (3-bromopropyl) -1-methylpiperidine, 1- (4-bromobutyl) -1-methylpiperidine, 1- (5-bromopentyl) -1-methylpiperidine, 1- (6-bromohexyl) -1-methylpiperidine, 1- (7-bromoethylheptyl) -1-methylpiperidine, 1- (8-bromooctyl) -1-methylpiperidine and 1- (9-bromononyl) -1-methylpiperidine.
The invention also aims to provide a preparation method of the side-chain piperidine cation-grafted polybiphenyl basic membrane.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of a side-chain piperidine cation grafted polybiphenyl alkaline membrane comprises the following steps:
(1) preparation of polybiphenylpiperidines
Dissolving a certain amount of biphenyl in dichloromethane, adding excessive N-methylpiperidinone, uniformly mixing, and dropwise adding a sufficient amount of mixed solution of trifluoromethanesulfonic acid and trifluoroacetic acid to perform polycondensation; after the reaction is finished, the polymer solution is placed in K2CO3Precipitating in an aqueous solution, soaking for 12-36h at room temperature, filtering to obtain a white solid sample, fully washing with deionized water, and drying to obtain a polybiphenyl piperidine polymer;
(2) preparation of side-chain piperidine cations
Adding halogenated alkane, N-methylpiperidine and ethyl acetate into a round-bottom flask according to a certain proportion, introducing nitrogen, fully reacting to obtain white solid precipitate, performing suction filtration, purifying with ethyl acetate, removing excessive reactant, and performing vacuum drying to obtain side-chain piperidine cation;
(3) preparation of side chain piperidine cation graft type polybiphenyl
Dissolving the polybiphenyl piperidine polymer prepared in the step (1) in a first organic solvent, and after the polymer is completely dissolved, adding the side chain piperidine cation obtained in the step (2) for quaternization; after full reaction, spin-drying the solution to obtain a crude product side chain piperidine cation grafted polybiphenyl solid; washing the crude product by deionized water, washing off redundant side chain piperidine cations, performing suction filtration and drying to obtain a pure side chain piperidine cation grafted polybiphenyl polymer;
(4) preparation of side-chain piperidine cation grafted polybiphenyl alkaline membrane
Dissolving the side chain piperidine cation graft polybiphenyl polymer prepared in the step (3) in a second organic solvent to prepare a casting solution with a certain concentration, and then casting or curtain coating the casting solution on a substrate, curing and stripping; and finally, soaking the obtained alkaline membrane in alkaline liquor to obtain the final side-chain piperidine cation grafted polybiphenyl alkaline membrane.
Preferably, the weight ratio of the trifluoromethanesulfonic acid to the trifluoroacetic acid in the mixed solution in step (1) is 10: 1.
Preferably, the reaction temperature in the step (1) is 0 ℃, the reaction time is 5-12h, and the K is2CO3The aqueous solution had a concentration of 2M.
Preferably, the polybiphenylpiperidine polymer in step (1) is polydibiphenylpiperidine or polyparaterphenylpiperidine or poly-m-terphenylpiperidine;
preferably, the halogenated alkane in the step (2) is any one of 1, 2-dibromoethane, 1, 3-dibromopropane, 1, 4-dibromobutane, 1, 5-dibromopentane, 1, 6-dibromohexane, 1, 7-dibromoheptane, 1, 8-dibromooctane or 1, 9-dibromononane.
Preferably, the first organic solvent in step (3) is any one of or a mixture of at least two of dimethyl sulfoxide, N dimethylformamide, N-methylpyrrolidone, acetonitrile, acetone or trichloromethane in any proportion.
Preferably, the reaction time of the quaternization reaction in the step (3) is 72h, and the reaction temperature is 90 ℃.
Preferably, the second organic solvent in step (4) is any one of or a mixture of at least two of dimethyl sulfoxide, N dimethylformamide, N-methylpyrrolidone, dimethylacetamide, methanol, ethanol or isopropanol in any ratio.
Preferably, the side chain piperidine cation graft type polybiphenyl basic membrane in the step (4) is a side chain piperidine cation graft type polydibiphenyl basic membrane or a side chain piperidine cation graft type polyparaterphenyl basic membrane or a side chain piperidine cation graft type poly-m-terphenyl basic membrane.
Preferably, the concentration of the casting solution in the step (4) is 0.1 g/mL.
Preferably, the substrate in step (4) includes, but is not limited to, a heat-resistant glass plate, a steel plate, or a polytetrafluoroethylene plate.
Preferably, the thickness of the alkaline film in step (4) is 10 to 100. mu.m.
Preferably, in the step (4), the alkaline membrane is soaked in an alkaline solution, the alkaline solution is an aqueous solution of NaOH, the concentration of the alkaline solution is 2M, and the soaking time is 48 hours.
Compared with the prior art, the invention has the following beneficial effects:
(1) the side-chain piperidine cation grafted polybiphenyl alkaline membrane has super-strong alkali resistance, and is degraded by no more than 15% after being soaked in an alkaline solution for 1600 hours;
(2) the side-chain piperidine cation grafted polybiphenyl alkaline membrane has higher ionic conductivity, can reach 117.1mS/cm at 80 ℃, and meets the requirement of the alkaline membrane of the fuel cell at the present stage;
(3) the side-chain piperidine cation grafted polybiphenyl alkaline membrane has excellent thermal stability and completely meets the requirement of the working temperature of a fuel cell.
The invention is further illustrated by the following figures and specific examples, which are not meant to limit the scope of the invention.
Drawings
FIG. 1 is a flow chart showing the preparation of a 1- (3-bromopropyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-3-Pip) basic membrane in example 1 of the present invention.
FIG. 2 is a flow chart showing the preparation of a 1- (6-bromohexyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-6-Pip) basic membrane in example 2 of the present invention.
FIG. 3 is a flow chart showing the preparation of a 1- (8-bromooctyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-8-Pip) basic membrane in example 3 of the present invention.
FIG. 4-1 shows the general structure of 1- (3-bromopropyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-3-Pip) polymer prepared in example 1 of the present invention.
FIG. 4-2 shows the general structure of 1- (6-bromohexyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-6-Pip) polymer prepared in example 2 of the present invention.
FIG. 4-3 shows the general structure of 1- (8-bromooctyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-8-Pip) polymer prepared in example 3 of the present invention.
FIG. 5 is a nuclear magnetic structural diagram of polydiphenyls and respective side-chain piperidine cation-grafted polybiphenyl polymers prepared in examples 1-3 of the present invention.
FIG. 6 is a graph comparing thermal stability of side-chain piperidine cation-grafted polybiphenyl basic films prepared in examples 1-3 of the present invention.
FIG. 7 is a graph showing the relationship between the conductivity and the temperature of the side-chain piperidine cation-grafted polybiphenyl basic film prepared in examples 1-3 of the present invention.
FIG. 8 is a graph showing the change in ionic conductivity with soaking time of the side-chain piperidine cation-grafted polybiphenyl basic film prepared in examples 1-3 of the present invention in a 2M NaOH solution and at 80 ℃.
Detailed Description
Unless otherwise specified, the raw materials used in the examples of the present invention are commercially available, the equipment used is conventional in the art, and the methods used are conventional in the art.
Example 1
Preparation of 1- (3-bromopropyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-3-Pip) alkaline membrane, as shown in fig. 1, is a preparation flow of 1- (3-bromopropyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-3-Pip) alkaline membrane in example 1 of the present invention, and the specific steps are as follows:
(1) preparation of polydibiphenyl (PBP)
Biphenyl (1g) and N-methylpiperidinone (0.83mL) were dissolved in dichloromethane (5 mL); subsequently, a mixed liquid of trifluoromethanesulfonic acid (5mL) and trifluoroacetic acid (0.5mL) was dropwise added thereto, reacted at 0 ℃ for 6 hours to obtain a wine-red viscous liquid, and the above mixture was dissolved in 2M K2CO3Precipitating in water solution, soaking at room temperature for 24 hr, filteringObtaining a white solid sample, fully washing with deionized water, and drying to obtain a poly (diphenyl-piperidine) (PBP) polymer;
(2) preparation of 1- (3-bromopropyl) -1-methylpiperidine (Br-3-Pip)
Adding 1, 3-dibromopropane (1.25mL), N-methylpiperidine (1mL) and ethyl acetate (20mL) into a round-bottom flask, introducing nitrogen, fully reacting to obtain a white solid precipitate, performing suction filtration, purifying with ethyl acetate, removing excessive reactants, and drying to obtain side-chain piperidine cation 1- (3-bromopropyl) -1-methylpiperidine (Br-3-Pip);
(3) preparation of 1- (3-bromopropyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-3-Pip) polymer
Dissolving PBP (1g) prepared in the step (1) in dimethyl sulfoxide (DMSO) (50mL), adding excessive side chain piperidine cation 1- (3-bromopropyl) -1-methylpiperidine (Br-3-Pip) obtained in the step (2) after a polymer is completely dissolved, and carrying out quaternization reaction; after reacting for 72 hours at 90 ℃, spin-drying the solution to obtain crude side chain piperidine cation grafted polybiphenyl solid; washing the crude product by ethyl acetate and deionized water, removing the residual Br-3-Pip, carrying out suction filtration and drying to obtain a pure 1- (3-bromopropyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-3-Pip) polymer; as shown in fig. 4-1, it is a general structure of 1- (3-bromopropyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-3-Pip) polymer prepared in example 1 of the present invention;
(4) preparation of 1- (3-bromopropyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-3-Pip) alkaline membrane
Dissolving 1- (3-bromopropyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-3-Pip) polymer (1g) prepared in the step (3) in dimethyl sulfoxide (DMSO) (10mL) to prepare casting solution with a certain concentration, and then casting or curtain-casting the casting solution on a heat-resistant glass plate, curing and stripping; and finally, soaking the obtained alkaline membrane in 2M NaOH aqueous solution for 48 hours to obtain the final 1- (3-bromopropyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-3-Pip) alkaline membrane in the form of hydroxide radical.
Example 2
Preparation of 1- (6-bromohexyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-6-Pip) basic membrane, as shown in fig. 4-2, is a flow chart for preparing 1- (6-bromohexyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-6-Pip) basic membrane in example 2 of the present invention; the preparation process comprises the following steps:
(1) preparation of polydibiphenyl (PBP)
The same as example 1;
(2) preparation of 1- (6-bromohexyl) -1-methylpiperidine (Br-6-Pip)
Adding 1, 6-dibromohexane (1.5mL), N-methylpiperidine (1mL) and ethyl acetate (20mL) into a round-bottom flask, introducing nitrogen, fully reacting to obtain a white solid precipitate, performing suction filtration, purifying with ethyl acetate, removing excessive reactants, and drying to obtain side-chain piperidine cation 1- (6-bromohexyl) -1-methylpiperidine (Br-6-Pip);
(3) preparation of 1- (6-bromohexyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-6-Pip) polymer
Dissolving PBP (1g) prepared in the step (1) in DMSO (50mL), and after the polymer is completely dissolved, adding excessive side chain piperidine cation Br-6-Pip obtained in the step (2) for quaternization; after reacting for 72 hours at 90 ℃, spin-drying the solution to obtain crude side chain piperidine cation grafted polybiphenyl solid; washing the crude product by ethyl acetate and deionized water, removing the residual Br-6-Pip, carrying out suction filtration and drying to obtain a pure 1- (6-bromohexyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-6-Pip) polymer; as shown in fig. 4-2, it is a general structure of 1- (6-bromohexyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-6-Pip) polymer prepared in example 2 of the present invention;
(4) preparation of 1- (6-bromohexyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-6-Pip) alkaline membrane
Dissolving 1- (6-bromohexyl) -1-methylpiperidine cation graft polybiphenyl (PBP-6-Pip) polymer (1g) prepared in the step (3) in DMSO (10mL) to prepare a casting solution with a certain concentration, then casting or curtain-casting the casting solution on a heat-resistant glass plate, curing and stripping, and finally soaking the obtained alkaline membrane in 2M NaOH aqueous solution for 48h to obtain the final 1- (6-bromohexyl) -1-methylpiperidine cation graft polybiphenyl (PBP-6-Pip) alkaline membrane in the form of hydroxyl.
Example 3
Preparation of 1- (8-bromooctyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-8-Pip) basic membrane, as shown in FIG. 4-3, is a flow chart for preparing 1- (8-bromooctyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-8-Pip) basic membrane in example 3 of the present invention; the preparation process comprises the following steps:
(1) preparation of polydibiphenylene (PBP)
The same as example 1;
(2) preparation of 1- (8-bromooctyl) -1-methylpiperidine (Br-8-Pip)
Adding 1, 8-dibromooctane (1.75mL), N-methylpiperidine (1mL) and ethyl acetate (20mL) into a round-bottom flask, introducing nitrogen, fully reacting to obtain a white solid precipitate, performing suction filtration, purifying with ethyl acetate, removing excessive reactants, and drying to obtain side-chain piperidine cation 1- (6-bromohexyl) -1-methylpiperidine (Br-8-Pip);
(3) preparation of 1- (8-bromooctyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-8-Pip) polymer
Dissolving PBP (1g) prepared in the step (1) in DMSO (50mL), and after the polymer is completely dissolved, adding excessive side chain piperidine cation Br-8-Pip obtained in the step (2) for quaternization; after reacting for 72 hours at 90 ℃, spin-drying the solution to obtain crude side chain piperidine cation grafted polybiphenyl solid; washing the crude product by ethyl acetate and deionized water, removing the residual Br-8-Pip, carrying out suction filtration and drying to obtain a pure 1- (8-bromooctyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-8-Pip) polymer; as shown in fig. 4-3, it is a general structure of 1- (8-bromooctyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-8-Pip) polymer prepared in example 3 of the present invention;
(4) preparation of 1- (8-bromooctyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-8-Pip) alkaline membrane
Dissolving the PBP-8-Pip polymer (1g) prepared in the step (3) in DMSO (10mL) to prepare casting solution with a certain concentration, and then casting or curtain-casting the casting solution on a heat-resistant glass plate, curing and stripping; finally, the obtained alkaline membrane is soaked in 2M NaOH aqueous solution for 48h to obtain the final PBP-8-Pip alkaline membrane in the form of hydroxide radical.
The products prepared in examples 1 to 3 of the present invention were characterized by using a nuclear magnetic resonance spectrometer (Bruker AV 400,400MHz), which has a resonance frequency of 400MHz, as shown in FIG. 5, which is a nuclear magnetic structural diagram of polydibiphenyls prepared in examples 1 to 3 of the present invention and of respective side chain piperidine cation graft polybiphenyls polymers; wherein a is a nuclear magnetic structural diagram of polydibiphenyl (PBP) prepared in step (1) of examples 1-3 of the present invention; b is a nuclear magnetic structure diagram of the 1- (3-bromopropyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-3-Pip) polymer prepared in the step (3) in example 1 of the present invention; c is a nuclear magnetic structure diagram of the 1- (6-bromohexyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-6-Pip) polymer prepared in the step (3) in example 2 of the present invention; d is a nuclear magnetic structure diagram of the 1- (8-bromooctyl) -1-methylpiperidine cation graft type polybiphenyl (PBP-8-Pip) polymer prepared in the step (3) in example 3 of the present invention; the individual polymers can be confirmed by nuclear magnetic resonance imaging.
The products of examples 1-3 of the present invention were analyzed for thermal stability using a TGA Q500 analyzer (METTLER, TGA/DSC3+), the samples were dried at 80 ℃ for 48 hours before the test, the temperature rise rate during the test was set to 10 ℃/min, the temperature range was 30-800 ℃, and as a result, as shown in fig. 6, the alkaline membranes prepared in examples 1-3 had similar degradation curves, which can be roughly divided into three stages: the first weight loss stage below 155 ℃ is due to evaporation of the residual water and solvent inside the membrane; the second stage is caused by the decomposition of piperidine cation at about 200-370 ℃; the third weight loss phase detected above 400 ℃ corresponds to the decomposition of the framework PBP. The results show that the PBP-n-Pip series membranes prepared in the embodiments 1 to 3 of the invention have good thermal stability and can completely meet the temperature requirement of daily work of the fuel cell.
The hydroxide conductivity of the membranes prepared in examples 1 to 3 of the present invention was measured by a four-electrode ac impedance method of an electrochemical workstation (Zahner Ennium) in a frequency range of 1MHz to 100Hz, and an ion conductivity-temperature change graph thereof was obtained as shown in fig. 7. Tests show that the conductivity of the alkaline membranes prepared in the embodiments 1-3 at 80 ℃ can reach 74.5mS/cm, 117.1mS/cm and 92.6mS/cm respectively, and the alkaline membranes meet the conductivity requirement of the alkaline membranes of the fuel cells at the present stage, wherein the embodiment 2(PBP-6-Pip) shows extremely excellent ion conductivity.
The membrane samples prepared in examples 1-3 of the present invention were immersed in 2M NaOH lye for a period of time at 80 ℃ and the membranes were removed and washed several times with deionized water to remove the residual lye. Subsequently, the alkali-resistant life of the membrane sample was evaluated by recording the change in ionic conductivity of the membrane sample by a four-electrode ac impedance method of an electrochemical workstation (Zahner Ennium) at room temperature. As shown in fig. 8, the conductivity of all membranes showed a more similar downward trend, with more severe degradation during the first 350h and then gradual degradation. After 1500h, PBP-3-Pip, PBP-6-Pip and PBP-8-Pip also retained about 64.14%, 84.04% and 86.37% of the initial conductivity, respectively, showing superior alkali resistance.
The inventor aims to solve the problems of performance and service life of the basic membrane and successfully introduces long-side-chain piperidine cations onto a polybiphenyl skeleton without electron-withdrawing groups to prepare the side-chain piperidine cation-grafted polybiphenyl basic membrane with high conductivity and long service life.
Firstly, biphenyl and piperidone are taken as raw materials, dichloromethane is taken as a solvent, and a high molecular weight polybiphenyl skeleton is prepared under the condition of super acid catalysis; then, halogenated alkanes with different carbon chain lengths are selected to respectively prepare long-side-chain piperidine cations through quaternization with N-methylpiperidine; and finally grafting the long side chain piperidine cations to the polybiphenyl skeleton to successfully prepare the side chain piperidine cation grafted polybiphenyl alkaline membrane.
The side-chain piperidine cation grafted polybiphenyl alkaline membrane provided by the invention has the characteristics of excellent alkali resistance, high ionic conductivity and thermal stability, and the hydroxide ion conductivity can reach 117.1mS/cm at 80 ℃. In addition, the alkaline membrane also has the characteristics of simple preparation process, low cost and the like.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
Claims (10)
1. The side chain piperidine cation grafted polybiphenyl alkaline membrane is characterized in that the side chain piperidine cation grafted polybiphenyl contains a polybiphenyl piperidine polymer skeleton and side chain piperidine cations.
2. The side-chain piperidine cation-grafted polybiphenyl basic film according to claim 1, wherein: the molecular weight of the side-chain piperidine cation graft type polybiphenyl is between 1 and 50 ten thousand.
3. The side-chain piperidine cation-grafted polybiphenyl basic film according to claim 1, wherein: the poly biphenyl piperidine is poly biphenyl piperidine or poly terphenyl piperidine or poly m-terphenyl piperidine; the side-chain piperidine cation is 1- (2-bromoethyl) -1-methylpiperidine, 1- (3-bromopropyl) -1-methylpiperidine, 1- (4-bromobutyl) -1-methylpiperidine, 1- (5-bromopentyl) -1-methylpiperidine, 1- (6-bromohexyl) -1-methylpiperidine, 1- (7-bromoethylheptyl) -1-methylpiperidine, 1- (8-bromooctyl) -1-methylpiperidine or 1- (9-bromononyl) -1-methylpiperidine.
4. The side-chain piperidine cation-grafted polybiphenyl basic film according to claim 3, wherein: the side chain piperidine cation graft type polybiphenyl is 1- (3-bromopropyl) -1-methylpiperidine cation graft type polybiphenyl, 1- (6-bromohexyl) -1-methylpiperidine cation graft type polybiphenyl or 1- (8-bromooctyl) -1-methylpiperidine cation graft type polybiphenyl.
5. A method for preparing the side-chain piperidine cation-grafted polybiphenyl basic membrane as claimed in any one of claims 1 to 4, which comprises the following steps:
(1) preparation of polybiphenylpiperidines
Taking a certain amountDissolving the biphenyl in dichloromethane, adding excessive N-methylpiperidinone, uniformly mixing, dropwise adding sufficient mixed solution of trifluoromethanesulfonic acid and trifluoroacetic acid, and carrying out polycondensation reaction; after the reaction is finished, the polymer solution is placed in K2CO3Precipitating in an aqueous solution, soaking for 12-36h at room temperature, filtering to obtain a white solid sample, fully washing with deionized water, and drying to obtain a polybiphenyl piperidine polymer;
(2) preparation of side-chain piperidine cations
Adding halogenated alkane, N-methylpiperidine and ethyl acetate into a round-bottom flask according to a certain proportion, introducing nitrogen, fully reacting to obtain white solid precipitate, performing suction filtration, purifying with ethyl acetate, removing excessive reactant, and performing vacuum drying to obtain side-chain piperidine cation;
(3) preparation of side chain piperidine cation graft type polybiphenyl
Dissolving the polybiphenyl piperidine polymer prepared in the step (1) in a first organic solvent, and after the polymer is completely dissolved, adding the side chain piperidine cation obtained in the step (2) to perform quaternization; after full reaction, spin-drying the solution to obtain a crude product side chain piperidine cation grafted polybiphenyl solid; washing the crude product by deionized water, washing off redundant side chain piperidine cations, performing suction filtration and drying to obtain a pure side chain piperidine cation grafted polybiphenyl polymer;
(4) preparation of side-chain piperidine cation grafted polybiphenyl alkaline membrane
Dissolving the side chain piperidine cation graft polybiphenyl polymer prepared in the step (3) in a second organic solvent to prepare a casting solution with a certain concentration, and then casting or curtain coating the casting solution on a substrate, curing and stripping; and finally, soaking the obtained alkaline membrane in alkaline liquor to obtain the final side-chain piperidine cation grafted polybiphenyl alkaline membrane.
6. The method for preparing the side-chain piperidine cation-grafted polybiphenyl basic film according to claim 5, wherein the method comprises the following steps: in the step (1), the weight ratio of the trifluoromethanesulfonic acid to the trifluoroacetic acid in the mixed solution is 10: 1.
7. The method for preparing the side-chain piperidine cation-grafted polybiphenyl basic membrane according to claim 6, wherein the method comprises the following steps: in the step (1), the reaction temperature is 0 ℃, the reaction time is 5-12h, and the reaction time K is2CO3The concentration of the aqueous solution is 2M; the poly biphenyl piperidine polymer is poly biphenyl piperidine or poly terphenyl piperidine or poly m terphenyl piperidine.
8. The method for preparing the side-chain piperidine cation-grafted polybiphenyl basic membrane according to claim 7, wherein the method comprises the following steps: in the step (2), the halogenated alkane is any one of 1, 2-dibromoethane, 1, 3-dibromopropane, 1, 4-dibromobutane, 1, 5-dibromopentane, 1, 6-dibromohexane, 1, 7-dibromoheptane, 1, 8-dibromooctane or 1, 9-dibromononane; the first organic solvent is any one or the mixture of at least two of dimethyl sulfoxide, N dimethylformamide, N-methyl pyrrolidone, acetonitrile, acetone or trichloromethane in any proportion; the reaction time of the quaternization reaction is 72 hours, and the reaction temperature is 90 ℃.
9. The method for preparing the side-chain piperidine cation-grafted polybiphenyl basic membrane according to claim 8, wherein the method comprises the following steps: in the step (4), the second organic solvent is any one of or a mixture of at least two of dimethyl sulfoxide, N dimethylformamide, N-methylpyrrolidone, dimethylacetamide, methanol, ethanol or isopropanol in any proportion.
10. The method for preparing a side-chain piperidine cation-grafted polybiphenyl basic membrane according to claim 9, wherein: in the step (4), the side chain piperidine cation graft type polybiphenyl alkaline membrane is a side chain piperidine cation graft type polydibiphenyl alkaline membrane, a side chain piperidine cation graft type polyparaterphenyl alkaline membrane or a side chain piperidine cation graft type poly-m-terphenyl alkaline membrane; the concentration of the casting solution is 0.1 g/mL; the substrate includes, but is not limited to, a heat resistant glass plate, a steel plate, or a polytetrafluoroethylene plate; the thickness of the alkaline film is 10-100 μm; the alkaline membrane is soaked in an alkaline solution, the alkaline solution is a NaOH aqueous solution, the concentration of the alkaline solution is 2M, and the soaking time is 48 hours.
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