CN114524912B - Side chain piperidine cation grafted poly biphenyl alkaline membrane and preparation method thereof - Google Patents
Side chain piperidine cation grafted poly biphenyl alkaline membrane and preparation method thereof Download PDFInfo
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- CN114524912B CN114524912B CN202210250840.8A CN202210250840A CN114524912B CN 114524912 B CN114524912 B CN 114524912B CN 202210250840 A CN202210250840 A CN 202210250840A CN 114524912 B CN114524912 B CN 114524912B
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- piperidine
- side chain
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- biphenyl
- cation
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 125
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000012528 membrane Substances 0.000 title claims abstract description 76
- -1 piperidine cation Chemical class 0.000 title claims abstract description 72
- 239000004305 biphenyl Substances 0.000 title claims abstract description 67
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 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 17
- 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 22
- 239000007787 solid Substances 0.000 claims description 22
- 239000002244 precipitate Substances 0.000 claims description 14
- 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 11
- 239000003513 alkali Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- KVZQVTSNCUIGMU-UHFFFAOYSA-N 1,1'-biphenyl;piperidine Chemical compound C1CCNCC1.C1=CC=CC=C1C1=CC=CC=C1 KVZQVTSNCUIGMU-UHFFFAOYSA-N 0.000 claims description 9
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000005956 quaternization reaction Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 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
- 239000011521 glass Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000376 reactant Substances 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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000002585 base 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
- 238000001914 filtration Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 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
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-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
- 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
- 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
- 238000009987 spinning Methods 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229930184652 p-Terphenyl Natural products 0.000 claims 1
- 239000003011 anion exchange membrane Substances 0.000 abstract description 20
- 239000000446 fuel Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 description 7
- 125000002091 cationic group Chemical group 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000012670 alkaline solution Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000002994 raw material Substances 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
- 230000008859 change Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 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
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- 238000012360 testing method Methods 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 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
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- 230000001737 promoting 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
Classifications
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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]
-
- 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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- 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
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a side chain piperidine cation grafted poly biphenyl alkaline membrane and a preparation method thereof, belonging to the technical field of preparation of anion exchange membranes of fuel cells; the method comprises the following steps: (1) preparation of a poly-biphenyl skeleton; (2) preparation of side chain piperidine cations; (3) And preparing the side chain piperidine cation grafted polybiphenyl alkaline membrane. The side chain piperidine cation grafted polybiphenyl alkaline membrane has higher ion conductivity and chemical stability, the hydroxyl ion conductivity can reach 117.1mS/cm at 80 ℃, and the ion conductivity is only reduced by less than 13.6% after being soaked in 2M NaOH solution for 1500 hours at 80 ℃, so that the side chain piperidine cation grafted polybiphenyl alkaline membrane has good chemical stability. 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 poly-biphenyl alkaline membrane and a preparation method thereof, belonging to the technical field of preparation of anion exchange membranes of fuel cells.
Technical Field
In recent years, anion Exchange Membrane Fuel Cells (AEMFCs) have received attention because of their advantages in allowing the use of non-noble metal catalysts and rapid redox kinetics. As a key component for transporting hydroxyl ions and isolating fuel and oxidant in Anion Exchange Membrane Fuel Cells (AEMFCs), 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 mainly dependent on the nature of the membrane material itself, especially based on the polymer backbone and grafted functional cationic groups. Currently, commonly used as polymer backbones are: polyphenylene Oxide (PPO), polyethersulfone (PES), polyetheretherketone (PEEK), and the like. However, the aromatic ether bond contained in the main chain of the polymer skeleton has an electron-withdrawing effect, and promotes 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 backbones have been used to develop highly stable Anion Exchange Membranes (AEMs).
Cationic groups are a further key factor limiting the chemical stability of Anion Exchange Membranes (AEMs), compared to Anion Exchange Membranes (AEMs) based on cationic groups such as trimethylamine, imidazolium, etc., which exhibit superior chemical stability under the same basic conditions because the low cyclic strain of cyclic amine onium and conformational constraints imposed by the cyclic structure increase the transition state energy of the substitution and elimination reactions during degradation with higher chemical stability.
Despite the great progress that has been made in research on polymer backbones and cationic groups, developing a practically useful Anion Exchange Membrane (AEM) remains a great challenge. In order to obtain better Anion Exchange Membrane (AEM) performance, more and more research is focused on optimizing the way the framework is connected to the cations. The long and flexible alkyl spacer chain enables cations to be far away from the framework, so that 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 groups, is favorable for self aggregation of the cationic groups, and can be used for manufacturing a high-efficiency ion transmission channel and promoting the formation of a hydrophilic and hydrophobic microphase separation form, so that the ion conductivity is improved.
Therefore, the lateral 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 the strong alkali-resistant piperidine cation is grafted to the skeleton through the flexible alkyl lateral chain, the lateral chain piperidine cation grafted polybiphenyl alkaline membrane is prepared, the ion conductivity and the chemical stability of an Anion Exchange Membrane (AEM) are effectively improved, the preparation method is simple and direct, and the lateral chain piperidine cation grafted polybiphenyl alkaline membrane has wide application prospect in an alkaline membrane fuel cell.
Disclosure of Invention
Aiming at the defects of the prior art, one of the purposes of the invention is to provide a side chain piperidine cation grafted poly-biphenyl alkaline membrane with the advantages of high thermal stability, high chemical stability, high ion 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 biphenyl is 1- (3-bromopropyl) -1-methylpiperidine cation-grafted biphenyl (PBP-3-Pip), 1- (6-bromohexyl) -1-methylpiperidine cation-grafted biphenyl (PBP-6-Pip) or 1- (8-bromooctyl) -1-methylpiperidine cation-grafted biphenyl (PBP-8-Pip).
Preferably, the molecular weight of the side chain piperidine cation-grafted biphenyl is between 1 and 50 ten thousand.
Preferably, the poly biphenyl is poly-bi-or poly-p-terpiperidine or poly-m-terpiperidine.
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.
Another object of the present invention is to provide a method for preparing the above-mentioned side chain piperidine cation-grafted polybiphenyl alkaline membrane.
The above object of the present invention is achieved by the following technical solutions:
the preparation process of side chain piperidine cation grafted polybiphenyl alkaline film includes the following steps:
(1) Preparation of Polybiphenylpiperidine
Dissolving a certain amount of biphenyl in dichloromethane, adding excessive N-methylpiperidone, mixing uniformly, and dripping sufficient amounts of trifluoromethanesulfonic acid and trifluoroacetic acidCarrying out polycondensation reaction on the mixed solution of the components; after the reaction, the polymer solution was stirred at K 2 CO 3 Precipitating in 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 poly (biphenyl 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 proportion, introducing nitrogen, fully reacting to obtain a white solid precipitate, carrying out suction filtration, purifying with ethyl acetate, removing excessive reactants, and carrying out vacuum drying to obtain side chain piperidine cations;
(3) Preparation of side chain piperidine cation grafted poly biphenyl
Dissolving the poly (biphenyl piperidine) polymer prepared in the step (1) in a first organic solvent, and adding side chain piperidine cations obtained in the step (2) after the polymer is completely dissolved for quaternization; after the full reaction, spinning the solution to obtain crude product side chain piperidine cation grafted poly biphenyl solid; washing the crude product by deionized water, washing off redundant side chain piperidine cations, carrying out suction filtration and drying to obtain a pure side chain piperidine cation grafted poly-biphenyl polymer;
(4) Preparation of side chain piperidine cation grafted poly biphenyl alkaline membrane
Dissolving the side chain piperidine cation-grafted biphenyl polymer prepared in the step (3) in a second organic solvent to prepare a casting solution with a certain concentration, and then casting or casting the casting solution on a substrate, solidifying and stripping; and finally, soaking the obtained alkaline membrane in alkali liquor to obtain the final side chain piperidine cation grafted poly biphenyl alkaline membrane.
Preferably, the weight ratio of the mixed solution of the trifluoromethanesulfonic acid and the trifluoroacetic acid in the step (1) is 10:1.
Preferably, the reaction temperature in step (1) is 0 ℃, the reaction time is 5-12h, and the K 2 CO 3 The concentration of the aqueous solution was 2M.
Preferably, the poly (biphenyl piperidine) polymer in step (1) is poly (biphenyl piperidine) or poly (p-terphenyl piperidine) or poly (m-terphenyl piperidine);
preferably, the haloalkane in 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, in the step (3), the first organic solvent is any one or a mixture of at least two of dimethyl sulfoxide, N dimethylformamide, N-methylpyrrolidone, acetonitrile, acetone and chloroform.
Preferably, the quaternization reaction in step (3) takes place for 72 hours at a reaction temperature of 90 ℃.
Preferably, in the step (4), the second organic solvent is any one or a mixture of at least two of dimethyl sulfoxide, N dimethylformamide, N-methylpyrrolidone, dimethylacetamide, methanol, ethanol or isopropanol in any proportion.
Preferably, the side-chain piperidine cation-grafted polybiphenyl alkaline membrane in the step (4) is a side-chain piperidine cation-grafted polybiphenyl alkaline membrane or a side-chain piperidine cation-grafted poly-p-terphenyl alkaline membrane or a side-chain piperidine cation-grafted poly-m-terphenyl alkaline membrane.
Preferably, the concentration of the casting solution in the step (4) is 0.1g/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 alkaline film in step (4) has a thickness of 10 to 100. Mu.m.
Preferably, the alkaline membrane in the step (4) is soaked in an alkaline solution, wherein the alkaline solution is an aqueous NaOH solution, 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 poly-biphenyl alkaline membrane has super-strong alkali resistance, and degradation is not more than 15% after soaking in alkali liquor 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 drawings and the specific examples, which are not meant to limit the scope of the invention.
Drawings
FIG. 1 is a flow chart showing the preparation of 1- (3-bromopropyl) -1-methylpiperidine cation grafted poly (biphenyl) (PBP-3-Pip) alkaline membrane according to the invention in example 1.
FIG. 2 is a flow chart showing the preparation of 1- (6-bromohexyl) -1-methylpiperidine cation grafted poly (biphenyl) (PBP-6-Pip) alkaline membrane in example 2 of the present invention.
FIG. 3 is a flow chart showing the preparation of 1- (8-bromooctyl) -1-methylpiperidine cation grafted poly (biphenyl) (PBP-8-Pip) alkaline membrane in example 3 of the present invention.
FIG. 4-1 shows the general structure of 1- (3-bromopropyl) -1-methylpiperidine cation grafted poly (biphenyl) (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 grafted poly (biphenyl) (PBP-6-Pip) polymer prepared in example 2 of the present invention.
FIGS. 4-3 are general structures of 1- (8-bromooctyl) -1-methylpiperidine cation grafted poly (biphenyl) (PBP-8-Pip) polymers prepared in example 3 of the present invention.
FIG. 5 is a nuclear magnetic structure diagram of the polydibiphenyls and the respective side-chain piperidine cation-grafted polydiphenyl polymers prepared in examples 1-3 of the present invention.
FIG. 6 is a graph showing the comparison of thermal stability of the side chain piperidine cation-grafted polybiphenyl alkaline membranes prepared in examples 1-3 of the present invention.
FIG. 7 is a graph showing the relationship between conductivity and temperature of the side chain piperidine cation-grafted polybiphenyl alkaline membranes prepared in examples 1-3 of the present invention.
FIG. 8 is a graph showing the change in ionic conductivity with time of immersion at 80℃in 2M NaOH solution of the side chain piperidine cation-grafted polybiphenyl base films prepared in examples 1 to 3 of the present invention.
Detailed Description
Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available raw materials, the equipment used is conventional equipment in the art, and the methods used are conventional methods in the art.
Example 1
The preparation of the 1- (3-bromopropyl) -1-methylpiperidine cation grafted poly (biphenyl) (PBP-3-Pip) alkaline membrane, as shown in FIG. 1, is a preparation flow of the 1- (3-bromopropyl) -1-methylpiperidine cation grafted poly (biphenyl) (PBP-3-Pip) alkaline membrane in example 1 of the invention, and comprises the following specific steps:
(1) Preparation of Polydiphenoxylate (PBP)
Biphenyl (1 g) and N-methylpiperidone (0.83 mL) were dissolved in dichloromethane (5 mL); subsequently, a mixed liquid of trifluoromethanesulfonic acid (5 mL) and trifluoroacetic acid (0.5 mL) was dropwise added thereto, and reacted at 0℃for 6 hours to obtain a reddish-colored viscous liquid, and the above mixture was stirred at 2M K 2 CO 3 Precipitating in aqueous solution, soaking for 24 hours at room temperature, filtering to obtain a white solid sample, fully washing with deionized water, and drying to obtain a poly (biphenyl piperidine) (PBP) polymer;
(2) Preparation of 1- (3-bromopropyl) -1-methylpiperidine (Br-3-Pip)
1, 3-dibromopropane (1.25 mL), N-methylpiperidine (1 mL) and ethyl acetate (20 mL) are added into a round-bottomed flask, nitrogen is introduced, the mixture is fully reacted to obtain white solid precipitate, the white solid precipitate is filtered, the white solid precipitate is purified by ethyl acetate, excessive reactant is removed, and the white solid precipitate is dried to obtain side chain piperidine cation 1- (3-bromopropyl) -1-methylpiperidine (Br-3-Pip);
(3) Preparation of 1- (3-bromopropyl) -1-methylpiperidine cationic graft poly (PBP-3-Pip) polymer
Dissolving PBP (1 g) prepared in the step (1) in dimethyl sulfoxide (DMSO) (50 mL), adding excessive side chain piperidine cation 1- (3-bromopropyl) -1-methylpiperidine (Br-3-Pip) obtained in the step (2) after the polymer is completely dissolved, and carrying out quaternization reaction; after reacting for 72 hours at 90 ℃, spin-drying the solution to obtain crude product side chain piperidine cation grafted poly biphenyl solid; washing the crude product through ethyl acetate and deionized water, removing residual Br-3-Pip, carrying out suction filtration and drying to obtain a pure 1- (3-bromopropyl) -1-methylpiperidine cation grafted poly biphenyl (PBP-3-Pip) polymer; as shown in FIG. 4-1, the general structure of the 1- (3-bromopropyl) -1-methylpiperidine cation graft type poly (PBP-3-Pip) polymer prepared in example 1 of the present invention;
(4) Preparation of 1- (3-bromopropyl) -1-methylpiperidine cation grafted poly (PBP-3-Pip) alkaline membrane
Dissolving 1g of the 1- (3-bromopropyl) -1-methylpiperidine cation grafted poly biphenyl (PBP-3-Pip) polymer (1 g) prepared in the step (3) in dimethyl sulfoxide (DMSO) (10 mL) to prepare a casting solution with a certain concentration, and then casting or casting the casting solution on a heat-resistant glass plate, solidifying and stripping; finally, the obtained alkaline membrane is soaked in 2M NaOH aqueous solution for 48 hours, and the final 1- (3-bromopropyl) -1-methylpiperidine cation grafted poly biphenyl (PBP-3-Pip) alkaline membrane in the form of hydroxide is obtained.
Example 2
Preparation of 1- (6-bromohexyl) -1-methylpiperidine cation grafted poly (biphenyl) (PBP-6-Pip) alkaline membrane as shown in FIG. 4-2, which is a flow chart of preparation of 1- (6-bromohexyl) -1-methylpiperidine cation grafted poly (PBP-6-Pip) alkaline membrane in example 2 of the present invention; the preparation process comprises the following steps:
(1) Preparation of Polydiphenoxylate (PBP)
As in example 1;
(2) Preparation of 1- (6-bromohexyl) -1-methylpiperidine (Br-6-Pip)
1, 6-dibromohexane (1.5 mL), N-methylpiperidine (1 mL) and ethyl acetate (20 mL) are added into a round-bottomed flask, nitrogen is introduced, the mixture is fully reacted to obtain a white solid precipitate, the white solid precipitate is filtered by suction, the white solid precipitate is purified by ethyl acetate, excessive reactants are removed, and the white solid precipitate is dried to obtain side chain piperidine cation 1- (6-bromohexyl) -1-methylpiperidine (Br-6-Pip);
(3) Preparation of 1- (6-bromohexyl) -1-methylpiperidine cation grafted poly (biphenyl) (PBP-6-Pip) polymer
Dissolving PBP (1 g) prepared in the step (1) in DMSO (50 mL), and adding excessive side chain piperidine cation Br-6-Pip obtained in the step (2) after the polymer is completely dissolved, so as to carry out quaternization reaction; after reacting for 72 hours at 90 ℃, spin-drying the solution to obtain crude product side chain piperidine cation grafted poly biphenyl solid; washing the crude product by ethyl acetate and deionized water, removing residual Br-6-Pip, carrying out suction filtration and drying to obtain a pure 1- (6-bromohexyl) -1-methylpiperidine cation grafted poly biphenyl (PBP-6-Pip) polymer; as shown in FIG. 4-2, the general structure of the 1- (6-bromohexyl) -1-methylpiperidine cation grafted poly (biphenyl) (PBP-6-Pip) polymer prepared in example 2 of the present invention;
(4) Preparation of 1- (6-bromohexyl) -1-methylpiperidine cation grafted poly (PBP-6-Pip) alkaline membrane
Dissolving 1- (6-bromohexyl) -1-methylpiperidine cation grafted poly (PBP-6-Pip) polymer (1 g) prepared in the step (3) in DMSO (10 mL) to prepare a casting solution with a certain concentration, casting or casting the casting solution on a heat-resistant glass plate, solidifying 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 grafted poly (PBP-6-Pip) alkaline membrane with a hydroxyl form.
Example 3
Preparation of 1- (8-bromooctyl) -1-methylpiperidine cation grafted poly (biphenyl) (PBP-8-Pip) alkaline membrane as shown in FIGS. 4-3, which is a flow chart of the preparation of 1- (8-bromooctyl) -1-methylpiperidine cation grafted poly (PBP-8-Pip) alkaline membrane in example 3 of the present invention; the preparation process comprises the following steps:
(1) Preparation of Polydiphenoxylate (PBP)
As in example 1;
(2) Preparation of 1- (8-bromooctyl) -1-methylpiperidine (Br-8-Pip)
1, 8-dibromooctane (1.75 mL), N-methylpiperidine (1 mL) and ethyl acetate (20 mL) are added into a round-bottomed flask, nitrogen is introduced, the mixture is fully reacted to obtain white solid precipitate, the white solid precipitate is filtered by suction, the white solid precipitate is purified by ethyl acetate, excessive reactant is removed, and the white solid precipitate is dried to obtain side chain piperidine cation 1- (6-bromohexyl) -1-methylpiperidine (Br-8-Pip);
(3) Preparation of 1- (8-bromooctyl) -1-methylpiperidine cation grafted poly (biphenyl) (PBP-8-Pip) polymer
Dissolving PBP (1 g) prepared in the step (1) in DMSO (50 mL), and adding excessive side chain piperidine cation Br-8-Pip obtained in the step (2) after the polymer is completely dissolved, so as to carry out quaternization reaction; after reacting for 72 hours at 90 ℃, spin-drying the solution to obtain crude product side chain piperidine cation grafted poly biphenyl solid; washing the crude product by ethyl acetate and deionized water, removing residual Br-8-Pip, carrying out suction filtration and drying to obtain a pure 1- (8-bromooctyl) -1-methylpiperidine cation grafted poly (PBP-8-Pip) polymer; as shown in FIGS. 4-3, the general structure of the 1- (8-bromooctyl) -1-methylpiperidine cation grafted poly (biphenyl) (PBP-8-Pip) polymer prepared in example 3 of the present invention;
(4) Preparation of 1- (8-bromooctyl) -1-methylpiperidine cation grafted poly (PBP-8-Pip) alkaline membrane
Dissolving the PBP-8-Pip polymer (1 g) prepared in the step (3) in DMSO (10 mL) to prepare a casting solution with a certain concentration, and then casting or casting the casting solution on a heat-resistant glass plate, solidifying and stripping; finally, the obtained alkaline membrane is soaked in 2M NaOH aqueous solution for 48 hours, and the final PBP-8-Pip alkaline membrane in the hydroxyl form is obtained.
The products prepared in examples 1-3 of the present invention were characterized by using a nuclear magnetic resonance spectrometer (Bruker AV 400,400 MHz) with a resonance frequency of 400MHz, as shown in FIG. 5, which is a nuclear magnetic structure diagram of the polydibiphenyls and the respective side-chain piperidine cation-grafted polydiphenyl polymers prepared in examples 1-3 of the present invention; wherein a is a nuclear magnetic structure diagram of the polydibiphenyl (PBP) prepared in the step (1) in the embodiments 1-3; b is a nuclear magnetic structure diagram of the 1- (3-bromopropyl) -1-methylpiperidine cation grafted poly (biphenyl) (PBP-3-Pip) polymer prepared in the step (3) in the embodiment 1 of the invention; c is a nuclear magnetic structure diagram of the 1- (6-bromohexyl) -1-methylpiperidine cation grafted poly (biphenyl) (PBP-6-Pip) polymer prepared in the step (3) in the embodiment 2; d is the nuclear magnetic structure diagram of the 1- (8-bromooctyl) -1-methylpiperidine cation grafted poly (biphenyl) (PBP-8-Pip) polymer prepared in the step (3) in the embodiment 3; the respective polymers can be confirmed by a nuclear magnetic structure diagram.
The thermal stability of the products of examples 1-3 of the present invention was analyzed using a TGA Q500 analyzer (METTLER, TGA/DSC 3+), the samples were dried at 80 ℃ for 48 hours prior to testing, the temperature rise rate during testing was set to 10 ℃/min, the temperature range was 30-800 ℃, and as a result, the alkaline membranes prepared in examples 1-3 had similar degradation curves, which can be roughly divided into three stages, as shown in fig. 6: the first weight-loss stage below 155 ℃ is due to evaporation of the solvent and moisture remaining in the film; the second stage is about 200-370deg.C, and is caused by decomposition of piperidine cation; the third weight loss stage detected above 400 ℃ corresponds to the decomposition of the skeletal PBP. The results show that the PBP-n-Pip series membranes prepared in the embodiments 1-3 have good thermal stability, and can completely meet the temperature requirement of daily operation of the fuel cell.
The hydroxide conductivities of the membranes prepared in examples 1-3 of the present invention were measured by the four electrode alternating current impedance method of the electrochemical workstation (Zahner Ennium) at frequencies ranging from 1MHz to 100Hz, resulting in a graph of ionic conductivity versus temperature, as shown in fig. 7. The alkaline membranes prepared in examples 1-3 were tested to have conductivities of 74.5mS/cm, 117.1mS/cm and 92.6mS/cm, respectively, at 80℃that meet the current requirements for the conductivity of fuel cell alkaline membranes, wherein example 2 (PBP-6-Pip) exhibited extremely superior ion conductivity.
The film samples prepared in examples 1-3 of the present invention were immersed in 2M NaOH lye, after soaking at 80℃for a period of time, the film was removed, washed with deionized water multiple times, and the residual lye was removed. Subsequently, the change in ionic conductivity of the film samples was recorded by the four electrode ac impedance method of the electrochemical workstation (Zahner Ennium) at room temperature, and the alkali-resistant lifetime of the film samples was evaluated. As shown in fig. 8, the conductivities of all the membranes showed a relatively similar decrease trend, with more intense degradation in the first 350h, and then the degradation tended to be gentle. After 1500h, PBP-3-Pip, PBP-6-Pip and PBP-8-Pip also maintained initial conductivities of approximately 64.14%, 84.04% and 86.37%, respectively, showing superior alkali resistance.
The inventor is based on solving the problems of the performance and the service life of an alkaline membrane, and successfully leading long-side-chain piperidine cations to a biphenyl skeleton without electron withdrawing groups to prepare the high-conductivity long-service-life side-chain piperidine cation grafted biphenyl alkaline membrane.
Firstly, the inventor takes biphenyl and piperidone as raw materials and methylene dichloride as a solvent to prepare a high molecular weight poly-biphenyl skeleton under the condition of super acid catalysis; then, selecting halogenated alkanes with different carbon chain lengths, and respectively preparing long side chain piperidine cations with N-methylpiperidine through quaternization reaction; finally, long side chain piperidine cations are grafted to the biphenyl skeleton, and the side chain piperidine cation grafted biphenyl alkaline membrane is successfully prepared.
The side chain piperidine cation grafted polybiphenyl alkaline membrane provided by the invention has the characteristics of excellent alkali resistance, high ion conductivity and thermal stability, and the hydroxyl ion conductivity at 80 ℃ can reach 117.1mS/cm. In addition, the alkaline membrane has the characteristics of simple preparation process, low cost and the like.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but 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 scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
Claims (10)
1. The preparation process of side chain piperidine cation grafted polybiphenyl alkaline film includes the following steps:
(1) Preparation of Polybiphenylpiperidine
Dissolving a certain amount of biphenyl in dichloromethane, adding excessive N-methylpiperidone, uniformly mixing, and then dropwise adding a sufficient amount of mixed solution of trifluoromethanesulfonic acid and trifluoroacetic acid for polycondensation reaction; after the reaction, the polymer solution was stirred at K 2 CO 3 Precipitating in 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 poly (biphenyl 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 proportion, introducing nitrogen, fully reacting to obtain a white solid precipitate, carrying out suction filtration, purifying with ethyl acetate, removing excessive reactants, and carrying out vacuum drying to obtain side chain piperidine cations;
(3) Preparation of side chain piperidine cation grafted poly biphenyl
Dissolving the poly (biphenyl piperidine) polymer prepared in the step (1) in a first organic solvent, and adding side chain piperidine cations obtained in the step (2) after the polymer is completely dissolved for quaternization; after the full reaction, spinning the solution to obtain crude product side chain piperidine cation grafted poly biphenyl solid; washing the crude product by deionized water, washing off redundant side chain piperidine cations, carrying out suction filtration and drying to obtain a pure side chain piperidine cation grafted poly-biphenyl polymer;
(4) Preparation of side chain piperidine cation grafted poly biphenyl alkaline membrane
Dissolving the side chain piperidine cation-grafted biphenyl polymer prepared in the step (3) in a second organic solvent to prepare a casting solution with a certain concentration, and then casting or casting the casting solution on a substrate, solidifying and stripping; finally, soaking the obtained alkaline membrane in alkali liquor to obtain a final side chain piperidine cation grafted poly biphenyl alkaline membrane;
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.
2. The method for preparing the side-chain piperidine cation-grafted polybiphenyl alkaline membrane according to claim 1, wherein the method comprises the following steps: the weight ratio of the mixed solution of the trifluoromethanesulfonic acid and the trifluoroacetic acid in the step (1) is 10:1.
3. Preparation of a side chain piperidine cation-grafted polybiphenyl alkaline membrane according to claim 2The method is characterized in that: the reaction temperature in the step (1) is 0 ℃, the reaction time is 5-12h, and the K is 2 CO 3 The concentration of the aqueous solution is 2M; the poly (biphenyl piperidine) polymer is poly (biphenyl piperidine) or poly (p-terphenyl piperidine) or poly (m-terphenyl piperidine).
4. The method for preparing the side-chain piperidine cation-grafted polybiphenyl alkaline membrane according to claim 3, wherein the method comprises the following steps: the first organic solvent in the step (2) is any one or mixture of at least two of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, acetone or chloroform in any proportion; the reaction time of the quaternization reaction is 72h, and the reaction temperature is 90 ℃.
5. The method for preparing the side-chain piperidine cation-grafted polybiphenyl alkaline membrane according to claim 4, wherein the method comprises the following steps: the second organic solvent in the step (4) is any one or mixture of at least two of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone, dimethylacetamide, methanol, ethanol and isopropanol in any proportion.
6. The method for preparing the side-chain piperidine cation-grafted polybiphenyl alkaline membrane according to claim 5, wherein the method comprises the following steps: in the step (4), the side chain piperidine cation grafted poly (biphenyl) alkaline membrane is a side chain piperidine cation grafted poly (biphenyl) alkaline membrane or a side chain piperidine cation grafted poly (p-terphenyl) alkaline membrane or a side chain piperidine cation grafted poly (m-terphenyl) alkaline membrane; the concentration of the casting film solution is 0.1g/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 mu m; the alkaline membrane is soaked in alkali liquor, the alkali liquor is NaOH aqueous solution, the concentration of the alkali liquor is 2M, and the soaking time is 48 hours.
7. A side chain piperidine cation-grafted polybiphenyl alkaline membrane prepared by the method for preparing a side chain piperidine cation-grafted polybiphenyl alkaline membrane of any of claims 1-6.
8. The side chain piperidine cation-grafted polybiphenyl base film of claim 7 wherein: the molecular weight of the side chain piperidine cation grafted poly (biphenyl) polymer is between 1 and 50 ten thousand.
9. The side chain piperidine cation-grafted polybiphenyl base film of claim 7 wherein: the poly-biphenyl piperidine is poly-biphenyl piperidine or poly-p-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-bromoputyl) -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.
10. The side chain piperidine cation-grafted polybiphenyl base film of claim 9, wherein: the side chain piperidine cation grafted biphenyl is 1- (3-bromopropyl) -1-methylpiperidine cation grafted biphenyl, 1- (6-bromohexyl) -1-methylpiperidine cation grafted biphenyl or 1- (8-bromooctyl) -1-methylpiperidine cation grafted biphenyl.
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| CN111732717A (en) * | 2020-06-04 | 2020-10-02 | 东莞理工学院 | Polymer containing polyaryl piperidyl side chain, preparation method thereof, anion exchange membrane and preparation method thereof |
| CN111921566A (en) * | 2020-09-08 | 2020-11-13 | 长春工业大学 | Polyarylpiperidine type anion exchange membrane and preparation method and application thereof |
| CN112778558A (en) * | 2021-02-05 | 2021-05-11 | 长春工业大学 | Polyether bond-free anion exchange membrane of polyarylpiperidine for fuel cell and preparation method thereof |
| CN112898539A (en) * | 2020-09-22 | 2021-06-04 | 北京化工大学 | Long-side-chain polyaromatic hydrocarbon isatin alkaline membrane for fuel cell and preparation method thereof |
| CN113801300A (en) * | 2021-09-30 | 2021-12-17 | 惠州市亿纬新能源研究院 | Anion exchange polymer, preparation method and application thereof |
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| CN111732717A (en) * | 2020-06-04 | 2020-10-02 | 东莞理工学院 | Polymer containing polyaryl piperidyl side chain, preparation method thereof, anion exchange membrane and preparation method thereof |
| CN111921566A (en) * | 2020-09-08 | 2020-11-13 | 长春工业大学 | Polyarylpiperidine type anion exchange membrane and preparation method and application thereof |
| CN112898539A (en) * | 2020-09-22 | 2021-06-04 | 北京化工大学 | Long-side-chain polyaromatic hydrocarbon isatin alkaline membrane for fuel cell and preparation method thereof |
| CN112778558A (en) * | 2021-02-05 | 2021-05-11 | 长春工业大学 | Polyether bond-free anion exchange membrane of polyarylpiperidine for fuel cell and preparation method thereof |
| CN113801300A (en) * | 2021-09-30 | 2021-12-17 | 惠州市亿纬新能源研究院 | Anion exchange polymer, preparation method and application thereof |
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