CN116515110A - Modified polybenzimidazole and preparation method thereof - Google Patents
Modified polybenzimidazole and preparation method thereof Download PDFInfo
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- 229920002480 polybenzimidazole Polymers 0.000 title claims abstract description 76
- 239000004693 Polybenzimidazole Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 30
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 20
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 16
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 7
- 125000001424 substituent group Chemical group 0.000 claims description 72
- 125000004432 carbon atom Chemical group C* 0.000 claims description 68
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 150000003233 pyrroles Chemical class 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- -1 halogenated alkoxy compound Chemical class 0.000 claims description 4
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 150000003852 triazoles Chemical class 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000001345 alkine derivatives Chemical class 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000005600 alkyl phosphonate group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 125000002541 furyl group Chemical group 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 125000002757 morpholinyl group Chemical group 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 229960005489 paracetamol Drugs 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000001425 triazolyl group Chemical group 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims 1
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 125000001918 phosphonic acid ester group Chemical group 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 7
- 239000003431 cross linking reagent Substances 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 239000000446 fuel Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000012528 membrane Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical class CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- HCGYTFXTHWTYFK-UHFFFAOYSA-N 5-(chloromethyl)-1h-imidazole Chemical compound ClCC1=CN=CN1 HCGYTFXTHWTYFK-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003536 tetrazoles Chemical group 0.000 description 1
Classifications
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/18—Polybenzimidazoles
-
- 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]
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a modified polybenzimidazole, which belongs to the field of fuel cells and is prepared from raw materials of p-aminophenol, triethylamine, formaldehyde solution, polybenzimidazole, halogenated hydrocarbon, potassium carbonate and potassium iodide by a simple preparation process. The modified polybenzimidazole prepared by the invention can be crosslinked and cured under the heating condition, and a crosslinking agent is not required to be added, so that the preparation process of the crosslinked polybenzimidazole is simplified, the crosslinked polybenzimidazole can be uniformly mixed in a state of solution or powder, the uniformity of the crosslinking density of a cured product is improved, and the quality stability of the product is improved. In addition, the functional groups on the branched chains of the prepared modified polybenzimidazole can help to improve the compatibility, the solubility and the crystallinity of the modified polybenzimidazole, and can also increase the proton conductivity, so that the dependence on the doping amount of the modified polybenzimidazole is reduced, and the problem of acid leakage is further alleviated.
Description
Technical Field
The invention relates to the fields of material chemistry and fuel cells, in particular to modified polybenzimidazole and a preparation method thereof.
Background
Polybenzimidazole is one of the main materials of proton exchange membranes for high temperature proton exchange membrane fuel cells at present. However, polybenzimidazole membranes must be doped with a proton acid, usually phosphoric acid, to achieve proton conduction, and the proton conductivity is closely related to the doping amount of the acid. However, the higher the acid doping amount, the more the mechanical strength and thermal stability of the film are reduced. In addition, the problems of acid leakage and the like also become main bottlenecks for limiting the application of the PBI proton exchange membrane.
The traditional method mainly improves the mechanical strength, the thermal stability and the chemical stability of the polybenzimidazole proton exchange membrane and the composite membrane after doping acid. In general, polybenzimidazoles require the addition of organic acids having di-or poly-functional groups or their halide crosslinking agents to achieve crosslinking. The process is complicated, and when the process is used as powder, the problem of uneven mixing exists, so that the cross-linking density is uneven after curing, and the quality stability of a product is affected.
Disclosure of Invention
Based on the problems of complex process, uneven mixing as powder and further influence on the quality stability of products in the prior art, the invention provides modified polybenzimidazole, which has the following specific technical scheme:
a modified polybenzimidazole having the chemical structural formula:
wherein R is 1 The method comprises the following steps:and +.>One of the following; r is R 2 Is a hydrogen atom or a substituent T, and the same molecular chain at least comprises one R 2 Is a substituent T.
Further, the structural formula of the substituent T is as follows:
wherein R is 3 Is a hydrogen atom or a substituent M, wherein the substituent M is a substituent alkyl group with 1-30 carbon atoms, a substituent alkoxy group with 1-30 carbon atoms, a substituent aryl group with 6-30 carbon atoms, a substituent aralkyl group with 7-40 carbon atoms, a substituent alkenyl group with 2-30 carbon atoms, a substituent alkynyl group with 2-30 carbon atoms, a substituent phosphonic acid group with 1-20 carbon atoms, a substituent phosphonic acid ester with 1-20 carbon atoms1 to 20 sulfonic acid group having a substituent of a carboxylic acid group having a carbon number of 1 to 20, a carboxylic acid ester group having a substituent of a carbon number of 1 to 20, an imidazole group having a substituent of a carbon number of 1 to 20, a pyridyl group having a substituent of a carbon number of 1 to 20, a pyranyl group having a substituent of a carbon number of 1 to 20, a furyl group having a substituent of a carbon number of 1 to 20, a triazolyl group having a substituent of a carbon number of 1 to 20, a tetrazolyl group having a substituent of a carbon number of 1 to 20, a thienyl group having a substituent of a carbon number of 1 to 20, a pyrrolyl group having a substituent of a carbon number of 1 to 20, and a morpholinyl group having a substituent of a carbon number of 1 to 20.
In addition, the application also provides a preparation method of the modified polybenzimidazole, which comprises the following steps:
dissolving para-aminophenol, triethylamine and formaldehyde solution in an organic solvent, and stirring in nitrogen at 5-10 ℃ for 30-120 min to obtain solution A;
dissolving polybenzimidazole in an organic solvent, and uniformly mixing to obtain a solution B;
adding formaldehyde solution accounting for 1/3 of the addition amount of the formaldehyde solution and the solution B into the solution A, heating to 90 ℃ within 40min, then adding the rest formaldehyde solution, continuously stirring for 1-4 h in nitrogen, then pouring into deionized water, precipitating, filtering, and repeatedly washing with water to obtain a polymer;
dissolving the polymer in an organic solvent to obtain a solution C;
adding halohydrocarbon, potassium carbonate and potassium iodide into the solution C, stirring for 12-72 h in nitrogen at 20-70 ℃, then pouring into deionized water, precipitating, filtering, and repeatedly washing with ethanol to obtain the modified polybenzimidazole.
Further, the organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
Further, in the solution A, the proportion of the paracetamol, the triethylamine, the formaldehyde solution and the organic solvent is 98:4:35:480 according to the weight ratio.
Further, in the solution B, the ratio of the polybenzimidazole to the formaldehyde solution is (52 to 125) to 70 in terms of parts by weight.
Further, the formaldehyde solution has a mass percentage concentration of 37%.
Further, the amount of the polymer added to the solution C is 0.05g/mL to 0.5g/mL.
Further, the mass ratio of the halogenated hydrocarbon to the potassium carbonate to the potassium iodide is 1 (1-3) (0.02-0.06).
Further, the halogenated hydrocarbon is a halogenated alkane with a substituent of 1 to 30 carbon atoms, a halogenated alkoxide with a substituent of 1 to 30 carbon atoms, a halogenated aromatic hydrocarbon with a substituent of 6 to 30 carbon atoms, a halogenated aromatic alkane with a substituent of 7 to 40 carbon atoms, a halogenated olefin with a substituent of 2 to 30 carbon atoms, a halogenated alkyne with a substituent of 2 to 30 carbon atoms, a halogenated alkylphosphonic acid with a substituent of 1 to 20 carbon atoms, a halogenated alkylphosphonate with a substituent of 1 to 20 carbon atoms, a halogenated carboxylic acid with a substituent of 1 to 20 carbon atoms, a halogenated alkylcarboxylate with a substituent of 1 to 20 carbon atoms, a halogenated imidazole with a substituent of 1 to 20 carbon atoms, a halogenated pyridine with a substituent of 1 to 20 carbon atoms, a halogenated pyran with a substituent of 1 to 20 carbon atoms, a halogenated furan with a substituent of 1 to 20 carbon atoms, a halogenated triazole with a substituent of 1 to 20 carbon atoms, a halogenated pyrrole with a substituent of 1 to 20 carbon atoms, a substituted pyrrole with a substituent of 1 to 20 carbon atoms.
The modified polybenzimidazole prepared by the scheme can be crosslinked and cured under the heating condition, and a crosslinking agent is not required to be added, so that the preparation process of the crosslinked polybenzimidazole is simplified, the crosslinked polybenzimidazole can be uniformly mixed in a state of solution or powder, the uniformity of the crosslinking density of a cured product is improved, and the quality stability of the product is improved. In addition, the functional groups on the branched chains of the prepared modified polybenzimidazole can help to improve the compatibility, the solubility and the crystallinity of the modified polybenzimidazole, and can also increase the proton conductivity, so that the dependence on the doping amount of the modified polybenzimidazole is reduced, and the problem of acid leakage is further alleviated.
Detailed Description
The present invention will be described in further detail with reference to the following examples thereof in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In one embodiment of the invention, a modified polybenzimidazole has a chemical structural formula:
wherein R is 1 The method comprises the following steps:and +.>One of the following; r is R 2 Is a hydrogen atom or a substituent T, and the same molecular chain at least comprises one R 2 Is a substituent T.
In one embodiment, the substituent T is of the formula:
wherein R is 3 Is a hydrogen atom or a substituent M, and the substituent M is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 40 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a phosphonic acid group having 1 to 20 carbon atoms, a phosphonate group having 1 to 20 carbon atoms, a sulfonic acid group having 1 to 20 carbon atoms, a carboxylic acid group having 1 to 20 carbon atoms, an imidazole group having 1 to 20 carbon atoms, a pyridyl group having 1 to 20 carbon atoms, a pyran group having 1 to 20 carbon atoms, a furanyl group having 1 to 20 carbon atoms, a triazole group having 1 to 20 carbon atoms, a tetrazole group having 1 to 20 carbon atoms, a thiophene group having 1 to 20 carbon atoms, and a morpholine group having 1 to 20 carbon atoms.
In addition, the application also provides a preparation method of the modified polybenzimidazole, which comprises the following steps:
dissolving para-aminophenol, triethylamine and formaldehyde solution in an organic solvent, and stirring in nitrogen at 5-10 ℃ for 30-120 min to obtain solution A;
dissolving polybenzimidazole in an organic solvent, and uniformly mixing to obtain a solution B;
adding formaldehyde solution accounting for 1/3 of the addition amount of the formaldehyde solution and the solution B into the solution A, heating to 90 ℃ within 40min, then adding the rest formaldehyde solution, continuously stirring for 1-4 h in nitrogen, then pouring into deionized water, precipitating, filtering, and repeatedly washing with water to obtain a polymer;
dissolving the polymer in an organic solvent to obtain a solution C;
adding halohydrocarbon, potassium carbonate and potassium iodide into the solution C, stirring for 12-72 h in nitrogen at 20-70 ℃, then pouring into deionized water, precipitating, filtering, and repeatedly washing with ethanol to obtain the modified polybenzimidazole.
In one embodiment, the organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone.
In one embodiment, in the solution a, the proportion of the para-aminophenol, the triethylamine, the formaldehyde solution and the organic solvent is 98:4:35:480 in parts by weight.
In one embodiment, the ratio of the polybenzimidazole to the formaldehyde solution in the solution B is (52-125) to 70 in parts by weight.
In one embodiment, the formaldehyde solution has a concentration of 37% by mass.
In one embodiment, the polymer in the solution C is added in an amount of 0.05g/mL to 0.5g/mL.
In one embodiment, the mass ratio of the halogenated hydrocarbon to the potassium carbonate to the potassium iodide is 1 (1-3) (0.02-0.06).
In one embodiment, the halogenated hydrocarbon is a substituted C1-30 halogenated alkane, a substituted C1-30 halogenated alkane oxide, a substituted C6-30 halogenated arene, a substituted C7-40 halogenated aralkyl, a substituted C2-30 halogenated alkene, a substituted C2-30 halogenated alkyne, a substituted C1-20 halogenated alkylphosphonic acid, a substituted C1-20 halogenated alkylphosphonate, a substituted C1-20 halogenated alkylsulfonic acid, a substituted C1-20 halogenated alkylcarboxylic acid, a substituted C1-20 halogenated alkylcarboxylate, a substituted C1-20 halogenated arylcarboxylic acid, a substituted C1-20 halogenated methylimidazole, a substituted C1-20 halogenated alkylpyridine, a substituted C1-20 halogenated alkylpyran, a substituted C1-20 halogenated alkylparaffin, a substituted C1-20 halogenated triazole, a substituted C1-20 halogenated pyrrole, or a substituted C1-20 halogenated pyrrole.
In one embodiment, the modified polybenzimidazole has a thermal crosslinking temperature of 100℃to 180 ℃.
In one embodiment, the modified polybenzimidazole is thermally crosslinked to provide a polybenzimidazole crosslinked polymer.
The modified polybenzimidazole prepared by the scheme can be crosslinked and cured under the heating condition, and a crosslinking agent is not required to be added, so that the preparation process of the crosslinked polybenzimidazole is simplified, the crosslinked polybenzimidazole can be uniformly mixed in a state of solution or powder, the uniformity of the crosslinking density of a cured product is improved, and the quality stability of the product is improved. In addition, the functional groups on the branched chains of the prepared modified polybenzimidazole can help to improve the compatibility, the solubility and the crystallinity of the modified polybenzimidazole, and can also increase the proton conductivity, so that the dependence on the doping amount of the modified polybenzimidazole is reduced, and the problem of acid leakage is further alleviated.
Embodiments of the present invention will be described in detail below with reference to specific examples.
Example 1:
a preparation method of modified polybenzimidazole comprises the following steps:
98 parts of p-aminophenol, 4 parts of triethylamine and 35 parts of formaldehyde solution are dissolved in N, N-dimethylformamide and stirred for 60min in nitrogen at 10 ℃ to obtain solution A;
dissolving 70 parts of polybenzimidazole in N, N-dimethylformamide, and uniformly mixing to obtain 0.1g/mL of solution B;
adding 35 parts of formaldehyde solution and the solution B into the solution A, heating to 90 ℃ within 40min, adding 35 parts of formaldehyde solution, continuously stirring for 2h in nitrogen, pouring into deionized water, precipitating, filtering, and repeatedly washing with water to obtain a polymer;
dissolving the polymer in N, N-dimethylformamide to obtain 0.1g/mL of solution C;
adding halohydrocarbon, potassium carbonate and potassium iodide in a molar ratio of 1:1:1:0.02 into the solution C, stirring for 72 hours in nitrogen at 25 ℃, then pouring into deionized water, precipitating, filtering, and repeatedly washing with ethanol to obtain the modified polybenzimidazole.
The structural formula of the modified polybenzimidazole in example 1 is as follows:
r in example 1 2 Is hydrogen atom or substituent T, and the structure of the substituent T is as follows:
r in example 1 3 Is hydrogen atom or substituent M, and the structure of the substituent M is as follows:
example 2:
a preparation method of modified polybenzimidazole comprises the following steps:
98 parts of p-aminophenol, 4 parts of triethylamine and 35 parts of formaldehyde solution are dissolved in N, N-dimethylformamide and stirred for 120min in nitrogen at 8 ℃ to obtain solution A;
dissolving 90 parts of polybenzimidazole in N, N-dimethylformamide, and uniformly mixing to obtain 0.05g/mL of solution B;
adding 35 parts of formaldehyde solution and the solution B into the solution A, heating to 90 ℃ within 40min, adding 35 parts of formaldehyde solution, continuously stirring for 4 hours in nitrogen, pouring into deionized water, precipitating, filtering, and repeatedly washing with water to obtain a polymer;
dissolving the polymer in N, N-dimethylformamide to obtain 0.05g/mL of solution C;
adding 1-bromo-n-hexane, potassium carbonate and potassium iodide in a molar ratio of 1:2:2:0.04 into the solution C, stirring for 12 hours in nitrogen at 70 ℃, then pouring into deionized water, precipitating, filtering, and repeatedly washing with ethanol to obtain the modified polybenzimidazole.
The structural formula of the modified polybenzimidazole in example 2 is as follows:
r in example 2 2 Is hydrogen atom or substituent T, and the structure of the substituent T is as follows:
r in example 2 3 Is hydrogen atom or substituent M, and the structure of the substituent M is as follows:
example 3:
a preparation method of modified polybenzimidazole comprises the following steps:
98 parts of p-aminophenol, 4 parts of triethylamine and 35 parts of formaldehyde solution are dissolved in N-methylpyrrolidone and stirred for 120min in nitrogen at 8 ℃ to obtain solution A;
60 parts of polybenzimidazole is dissolved in N-methyl pyrrolidone and uniformly mixed to obtain 0.3g/mL of solution B;
adding 35 parts of formaldehyde solution and the solution B into the solution A, heating to 90 ℃ within 40min, adding 35 parts of formaldehyde solution, continuously stirring for 1h in nitrogen, pouring into deionized water, precipitating, filtering, and repeatedly washing with water to obtain a polymer;
dissolving the polymer in N-methyl pyrrolidone to obtain 0.3g/mL of solution C;
adding 4-chloromethylimidazole, potassium carbonate and potassium iodide in a molar ratio of 1:3:3:0.06 into the solution C, stirring for 24 hours in nitrogen at 50 ℃, then pouring into deionized water, precipitating, filtering, and repeatedly washing with ethanol to obtain the modified polybenzimidazole.
The structural formula of the modified polybenzimidazole in example 3 is as follows:
example 3R 2 Is hydrogen atom or substituent T, and the structure of the substituent T is as follows:
R 3 is hydrogen atom or substituent M, and the structure of the substituent M is as follows:
application example 1:
the modified polybenzimidazole obtained in example 1 was cured at 120℃for 24 hours to obtain a crosslinked modified polybenzimidazole film.
Application example 2:
the modified polybenzimidazole obtained in example 2 was cured at 180℃for 24 hours to obtain a crosslinked modified polybenzimidazole film.
Application example 3:
the modified polybenzimidazole obtained in example 3 was cured at 150℃for 24 hours to obtain a crosslinked modified polybenzimidazole film.
The conventional linear polybenzimidazole, the modified polybenzimidazole of example 1 and the crosslinked modified polybenzimidazole film of application example 1 were tested, and the tensile strength and the anhydrous proton conductivity at 150 ℃ were as shown in the following table 1.
Table 1:
the modified polybenzimidazole of example 2 and the crosslinked modified polybenzimidazole film of application example 2 were tested for tensile strength as shown in table 2 below.
Table 2:
the conventional linear polybenzimidazole, the modified polybenzimidazole of example 3 and the crosslinked modified polybenzimidazole film of application example 3 were tested, and the tensile strength and proton conductivity results are shown in the following table 3, wherein the proton conductivity test method was measured by drying the surface after immersing the crosslinked modified polybenzimidazole film in 15mol/L phosphoric acid for 48 hours at room temperature.
Table 3:
from the analysis in tables 1 to 3, it is shown that the modified polybenzimidazole of the present application has an excellent crosslinking effect without adding a crosslinking agent, can be crosslinked into a film at 100 to 180 ℃, can be used as a proton exchange membrane, and has excellent tensile strength and conductivity.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The modified polybenzimidazole is characterized by having a chemical structural formula:
wherein R is 1 The method comprises the following steps:andOne of the following; r is R 2 Is a hydrogen atom or a substituent T, and the same molecular chain at least comprises one R 2 Is a substituent T.
2. The modified polybenzimidazole according to claim 1 where said substituent T has the following structural formula:
wherein R is 3 Is a hydrogen atom or a substituent M, and the substituent M is a substituted C1-30 alkyl group, a substituted C1-30 alkoxy group, a substituted C6-30 aryl group, a substituted C7-40 aralkyl group, a substituted C2-30 alkenyl group, a substituted C2-30 alkynyl group a substituted C1-20 phosphonic acid group, a substituted C1-20 phosphonic acid ester group, a substituted C1-20 sulfonic acid group, a catalyst for the preparation of a catalyst for the medical use of a medical instrument a C1-20 carboxylic acid group having a substituent, a C1-20 carboxylic acid ester group having a substituent, a carboxylic acid ester having a carboxylic acid esterImidazolyl group having 1 to 20 carbon atoms of the substituent, pyridyl group having 1 to 20 carbon atoms of the substituent, pyranyl group having 1 to 20 carbon atoms of the substituent, furyl group having 1 to 20 carbon atoms of the substituent, triazolyl group having 1 to 20 carbon atoms of the substituent, tetrazolyl group having 1 to 20 carbon atoms of the substituent, thienyl group having 1 to 20 carbon atoms of the substituent, pyrrolyl group having 1 to 20 carbon atoms of the substituent, morpholinyl group having 1 to 20 carbon atoms of the substituent.
3. A process for the preparation of a modified polybenzimidazole according to claim 1 or 2, said process comprising the steps of:
dissolving para-aminophenol, triethylamine and formaldehyde solution in an organic solvent, and stirring in nitrogen at 5-10 ℃ for 30-120 min to obtain solution A;
dissolving polybenzimidazole in an organic solvent, and uniformly mixing to obtain a solution B;
adding formaldehyde solution accounting for 1/3 of the addition amount of the formaldehyde solution and the solution B into the solution A, heating to 90 ℃ within 40min, then adding the rest formaldehyde solution, continuously stirring for 1-4 h in nitrogen, then pouring into deionized water, precipitating, filtering, and repeatedly washing with water to obtain a polymer;
dissolving the polymer in an organic solvent to obtain a solution C;
adding halohydrocarbon, potassium carbonate and potassium iodide into the solution C, stirring for 12-72 h in nitrogen at 20-70 ℃, then pouring into deionized water, precipitating, filtering, and repeatedly washing with ethanol to obtain the modified polybenzimidazole.
4. The method according to claim 3, wherein the organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone.
5. The method according to claim 3, wherein the ratio of the paracetamol, the triethylamine, the formaldehyde solution and the organic solvent in the solution A is 98:4:35:480 in parts by weight.
6. The process according to claim 3, wherein the ratio of the polybenzimidazole to the formaldehyde solution in the solution B is (52 to 125) to 70 in parts by weight.
7. A method of preparing as claimed in claim 3, wherein the formaldehyde solution has a concentration of 37% by mass.
8. The method according to claim 3, wherein the polymer in the solution C is added in an amount of 0.05g/mL to 0.5g/mL.
9. The process according to claim 3, wherein the mass ratio of the halogenated hydrocarbon to the potassium carbonate to the potassium iodide is 1 (1 to 3) (0.02 to 0.06).
10. The method according to claim 9, wherein, the halogenated hydrocarbon is halogenated alkane with 1-30 carbon atoms, halogenated alkoxy compound with 1-30 carbon atoms, halogenated aromatic hydrocarbon with 6-30 carbon atoms, halogenated aromatic alkane with 7-40 carbon atoms, halogenated olefin with 2-30 carbon atoms, halogenated alkyne with 2-30 carbon atoms, halogenated alkylphosphonic acid with 1-20 carbon atoms, halogenated alkylphosphonate with 1-20 carbon atoms, halogenated alkylsulfonic acid with 1-20 carbon atoms, halogenated alkylcarboxylic acid ester with 1-20 carbon atoms, halogenated alkylimidazole with 1-20 carbon atoms, halogenated alkylpyridine with 1-20 carbon atoms, halogenated alkylpyran with 1-20 carbon atoms, halogenated haloalkylfuran with 1-20 carbon atoms, halogenated triazole with 1-20 carbon atoms, halogenated pyrrole with 1-20 carbon atoms, and halogenated pyrrole with 1-20 carbon atoms.
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