CN116396469A - Piperidine tertiary amine group polymer containing space three-dimensional cross-linked central carbon-based skeleton structure - Google Patents
Piperidine tertiary amine group polymer containing space three-dimensional cross-linked central carbon-based skeleton structure Download PDFInfo
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- CN116396469A CN116396469A CN202310393688.3A CN202310393688A CN116396469A CN 116396469 A CN116396469 A CN 116396469A CN 202310393688 A CN202310393688 A CN 202310393688A CN 116396469 A CN116396469 A CN 116396469A
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- Prior art keywords
- formula
- anion exchange
- tertiary amine
- structural unit
- amine group
- Prior art date
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- -1 piperidine tertiary amine Chemical class 0.000 claims abstract description 20
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Abstract
The invention provides a piperidine tertiary amine group polymer containing a space three-dimensional cross-linking center carbon-based skeleton structure, which at least comprises one of tetraphenyl methane or triptycene structural units and piperidine tertiary amine structural units, wherein the main chain chemical structure contains tetraphenyl methyl groups or aromatic hydrocarbon triptycene, the prepared polymer has light cross-linking, so that the prepared material has excellent mechanical strength, and due to the supporting effect of the carbon-based skeleton structure on the main chain, the formation of a folding chain segment of the polymer is reduced, the pi-pi effect of an aromatic hydrocarbon structure of the polymer after film formation is reduced, the formation of a crystallization area is reduced, and the construction of a hydrophilic phase is facilitated, so that the ionic conductivity of the film is remarkably improved.
Description
Technical Field
The invention relates to the field of new energy electrochemical devices, in particular to a piperidyl tertiary amine group polymer containing a space three-dimensional cross-linking center carbon-based skeleton structure, an anion exchange membrane prepared by using the piperidyl tertiary amine group polymer containing the space three-dimensional cross-linking center carbon-based skeleton structure, and application of an anion exchange polymer adhesive.
Background
In recent years, along with the continuous increase of the demand for alternative energy sources in the world, the application of anion exchange membranes and anion exchange polymer binders in new energy electrochemical devices is also receiving more and more attention from researchers, and the anion exchange membranes and the anion exchange polymer binders can be applied to the fields of alkaline fuel cells, electrolyzed water, carbon dioxide reduction, flow batteries and the like, have good development prospects, play a role in the conventional industries of chlor-alkali industry, heavy metal recovery, water treatment, hydrometallurgy and the like, and are very widely concerned. Anion exchange membranes and anion exchange polymer binders are a class of high molecular polymers containing cationic functional groups and having selective permeability to anions, however, the current application scenario demands that anion exchange membranes have higher conductivity and better mechanical, thermal and chemical stability.
Patent CN107910576a discloses a preparation method of an anionic polymer film with high chemical stability, which adopts aryl monomers and N-alkyl-4-piperidone to obtain a polymerization product with a main chain without ether bond, and then uses halogenated alkane to carry out quaternization reaction to obtain an anionic exchange polymer, wherein the main chain of the anionic exchange polymer does not contain polar groups, and piperidine ring with high chemical stability is used as quaternary ammonium cation, so that the anionic exchange polymer has good chemical stability. Patent CN109070022a discloses a poly (aryl piperidine) polymer used as a hydroxide exchange membrane and an ionomer, based on aryl monomers and N-alkyl-4-piperidones, trifluoroacetophenone monomers are added to copolymerize to obtain a polymerization product with a main chain free of ether linkages, and then a quaternization reaction is performed using halogenated alkanes to prepare an anion exchange polymer with good chemical stability. Patent CN111269401a discloses an anion exchange polymer comprising piperidine quaternary ammonium structural units and fluorene groups and aromatic monomers. The invention ensures that the material has excellent mechanical strength, the tortuosity and the rotatability of benzene rings on the main chain are weak, and the microstructure regularity of the polymer after film formation is higher, thereby having good chemical stability. Although an anion exchange polymer having good chemical stability can be obtained by using the above-mentioned patent, the mechanical strength and ionic conductivity of the anion exchange polymer are to be further improved.
In summary, although the chemical stability of the anion exchange polymer or the anion exchange membrane on the market at present is good, the mechanical strength and the ionic conductivity still cannot meet the requirements of special application scenes, and particularly in large-size large-scale application, the durability and the efficiency of devices such as alkaline fuel cells, electrolyzed water, carbon dioxide reduction, flow batteries and the like are directly determined by the strong mechanical strength and the high ionic conductivity. There is thus a need to develop an anion exchange polymer having excellent mechanical strength, high ionic conductivity and high chemical stability, thereby improving the performance of the related electrochemical device.
Disclosure of Invention
The invention aims to provide a piperidine tertiary amine group polymer containing a space three-dimensional cross-linking center carbon-based skeleton structure, which can be applied to manufacturing anion exchange membranes and anion exchange polymeric membranes and has excellent mechanical strength, high ion conductivity and high chemical stability.
To achieve the above object, in a first aspect, the present technical solution provides a piperidyl tertiary amine group polymer containing a steric cross-linked central carbon-based skeleton structure, comprising: a tetraphenyl methane structural unit represented by formula (1) or one of triptycene structural units represented by formula (2), and a piperidine tertiary amine structural unit represented by formula (3);
the invention relates to a piperidine tertiary amine group polymer containing a space three-dimensional cross-linked center carbon-based skeleton structure, which also comprises: one or a combination of at least two of a trifluoromethyl unit structure shown in formula (4), aryl group structural units shown in formula (5) and formula (6), fluorene structural unit shown in formula (7) and diphenyl alkane structural unit shown in formula (8); wherein n in the formula (5) is an integer of 0 to 10; wherein n in the formula (8) is an integer of 1 to 20:
in some embodiments, the molar ratio of the tetraphenyl methane building block (1) to the piperidyl tertiary amine building block (3) is (0.001 to 1): 1.
In some embodiments, the molar ratio of the tri-discoene structural unit (14) to the piperidinetertiary amine structural unit (3) is (0.001 to 1): 1.
Preferably, the molar ratio of one or a combination of at least two of the trifluoromethyl unit structure represented by the formula (4), the aryl group structural units represented by the formulas (5) and (6), the fluorene group structural unit represented by the formula (7) and the diphenylalkane structural unit represented by the formula (8) to the piperidinetertiary amine structural unit (3) is (0.001-2): 1.
Preferably, the number average molecular weight of the polymer containing piperidine tertiary amine groups is 0.1 to 100 tens of thousands.
Preferably, R in the formula (3) 1 Selected from any one of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or phenyl.
Preferably, R in the formula (4) 2 Any one or at least two of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and phenyl, methanol, 1-ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-bromomethane, 1-bromoethane, 1-bromopropane, 1-bromobutane, 1-bromopentane, 1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-ethylene, 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene.
R in the formula (7) 3 And R is 4 Each independently selected from any one of hydrogen, C1-C10 chain alkyl or C3-C10 cycloalkyl, preferably, the R 3 And R is 4 Each independently selected from any one of hydrogen, methyl, ethyl, propyl, butyl, pentyl and hexyl.
In addition, in a second aspect, the present invention also provides a preparation method of a piperidine tertiary amine group polymer containing a space three-dimensional cross-linked central carbon-based skeleton structure, which comprises the following steps:
polymerizing monomers including one of a tetraphenyl methane monomer of formula (9) or a triptycene monomer of formula (10), a piperidone monomer of formula (11):
preferably, R in the formula (11) 1 Any one of hydrogen, C1-C10 chain alkyl, C3-C10 cycloalkyl, benzene ring and other aromatic compounds.
Preferably, the piperidone monomer shown in the formula (9) comprises any one or at least two of N-methyl-4-piperitone , N-ethyl-4-piperitone , N-propyl-4-piperitone , 4-piperidone or N-isopropyl-4-piperidone.
In some embodiments, the monomers further comprise one or a combination of at least two of a trifluoromethyl ketone monomer represented by formula (12), an aryl monomer represented by formula (13) and formula (14), a fluorene monomer represented by formula (15), and a benzhydryl alkane monomer represented by formula (16); wherein n in the formula (13) is an integer of 0 to 10; wherein n in the formula (16) is an integer of 1 to 20:
preferably, R in the trifluoromethyl ketone monomer represented by the formula (12) 2 Including methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and phenyl, methanol, 1-ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-bromomethane, 1-bromoethane, 1-bromopropane, 1-bromobutane, 1-bromopentane, 1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-ethylene, 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, or a combination of at least two of any of them.
Preferably, the aromatic monomer represented by the formula (13) and the formula (14) includes any one or a combination of at least two of biphenyl, para-terphenyl, meta-terphenyl, and para-terphenyl.
Preferably, R in the fluorene structural monomer represented by formula (15) 3 And R is 4 Each independently selected from any one of hydrogen, C1-C10 chain alkyl or C3-C10 cycloalkyl, preferably, the R 3 And R is 4 Each independently selected from any one of hydrogen, methyl, ethyl, propyl, butyl, pentyl and hexyl.
Preferably, the diphenylalkane monomer represented by the formula (16) contains any one or a combination of at least two of diphenylmethane, 1, 2-diphenylethane, 1, 3-diphenylpropane, 1, 4-diphenylbutane, 1, 5-diphenylpentane, 1, 6-diphenylhexane, 1, 7-diphenylheptane and 1, 8-diphenyloctane.
Preferably, the solvent for the polymerization reaction comprises any one or a combination of at least two of dichloromethane, chloroform, tetrachloroethane, toluene, trifluoroacetic acid or trifluoromethanesulfonic acid.
Preferably, the polymerization reaction is carried out in the presence of a catalyst comprising any one or a combination of at least two of trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid, or heptafluorobutyric acid; preferably, the polymerization reaction temperature is
Preferably, the polymerization reaction is carried out for a period of time of
In a third aspect, the use of the above prepared piperidyl tertiary amine group polymers containing a sterically stereo cross-linked central carbon-based backbone structure can be applied to water processors, gas separators or to the preparation of anion exchange polymers.
In a fourth aspect, when a piperidinetertiary amine group containing a sterically stereo cross-linked central carbon-based backbone structure of a polymer is used in the preparation of an anion exchange polymer, the structure of the piperidinetertiary amine group containing a carbon-based backbone structure of the anion exchange polymer comprises:
one of the tetraphenyl methane-based structural unit of formula (17) or the tri-dish alkene monomer structure of formula (18), and the piperidine quaternary amine-based structural unit of (19) and/or (20):
preferably, said R in formula (19) 1 And R is 2 Each independently selected from any one of hydrogen, C1-C10 chain alkyl or C3-C10 cycloalkyl.
Preferably, said R in formula (19) 1 Selected from hydrogen, methyl, ethyl, propylAny one of butyl, pentyl, phenyl or hexyl.
Preferably, said R in formula (19) 2 Any one selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, methanol, 1-ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, and 1-octanol.
Preferably, said X in said formula (19) - Is anionic.
Preferably, said X in formula (19) - Selected from OH - 、Cl - 、Br - 、I - 、BF 4 - 、HCO 3 - More preferably OH - 。
Preferably, said X in formula (19) - Is OH - The ion exchange capacity of the anion exchange polymer is 0.1-10 mmol/g.
Preferably, said X in formula (20) - Is anionic.
Preferably, said n in formula (20) is
Is an integer of (a).
Preferably, said X in formula (20) - Selected from OH - 、Cl - 、Br - 、I - 、BF 4 - 、HCO 3 - More preferably OH - 。
Preferably, said X in formula (20) - Is OH - The ion exchange capacity of the anion exchange polymer is 0.1-10 mmol/g.
Preferably, the anion exchange polymer further comprises one or more combinations of a trifluoromethyl unit structure represented by formula (21), aryl-based structural units represented by formulas (22) and (23), fluorene-based structural units represented by formula (24), and diphenylalkane-based structural units represented by formula (25);
preferably, said R in said formula (18) 3 Any one or at least two of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and phenyl, methanol, 1-ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-bromomethane, 1-bromoethane, 1-bromopropane, 1-bromobutane, 1-bromopentane, 1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-ethylene, 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene.
Preferably, n in the formula (22) is
Is an integer of (a).
Preferably, R in the formula (24) 4 And R is 5 Each independently selected from any one of hydrogen, C1-C10 chain alkyl or C3-C10 cycloalkyl, R in the fluorene structure of formula (24) 4 And R is 5 Each independently selected from any one of hydrogen, methyl, ethyl, propyl, butyl, pentyl and hexyl.
Preferably, the molar ratio of the tetraphenyl methane structural unit (25) to the piperidine quaternary amine structural unit (19) and/or (20) is (0.001-1): 1.
Preferably, the molar ratio of one or a combination of at least two of the trifluoromethyl unit structure represented by the formula (21), the aryl group structural units represented by the formulas (22) and (23), the fluorene group structural unit represented by the formula (24) and the benzhydryl alkane structural unit represented by the formula (25) to the piperidinetertiary amine structural unit (19) and/or (20) is (0.001-2): 1.
Preferably, n in the diphenylalkane structural unit represented by the formula (25) is an integer of 1 to 20.
Preferably, the diphenylalkane structural unit represented by the formula (25) contains any one or a combination of at least two of diphenylmethane, 1, 2-diphenylethane, 1, 3-diphenylpropane, 1, 4-diphenylbutane, 1, 5-diphenylpentane, 1, 6-diphenylhexane, 1, 7-diphenylheptane and 1, 8-diphenyloctane.
Preferably, the number average molecular weight of the polymer containing the space stereo cross-linked center piperidine tertiary amine group is 0.1 ten thousand-100 ten thousand;
in a fifth aspect, the present disclosure provides a method for preparing a piperidine tertiary amine group anion exchange polymer containing a sterically stereo cross-linked central carbon-based backbone structure, comprising the steps of:
1) Polymerizing monomers including one of a tetraphenyl methane monomer of formula (9) or a tri-dish alkene monomer structure of formula (10), a piperidone monomer of formula (11):
preferably, in 1), R1 is selected from any one of hydrogen, C1-C10 chain alkyl, C3-C10 cycloalkyl, benzene ring and other aromatic compounds;
preferably, the piperidone monomer of formula (11) in 1) comprises any one or at least two of N-methyl-4-piperitone , N-ethyl-4-piperitone , N-propyl-4-piperitone , 4-piperidone or N-isopropyl-4-piperidone;
polymerizing monomers, wherein the monomers further comprise one or a combination of at least two of trifluoromethyl ketone monomers shown in a formula (12), aryl monomers shown in a formula (13) and a formula (14), fluorene monomers shown in a formula (15) and diphenyl alkane monomers shown in a formula (16); wherein (13) n is an integer of 0 to 10; wherein (16) n is an integer of 1 to 20:
preferably, R in the formula (12) in 1) 2 Selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and phenyl, methanol, 1-ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-bromomethane, 1-bromoethane, 1-bromopropane, 1-bromobutane, 1-bromopentane, 1-bromohexane, 1-bromoheptane, 1-bromooctylAny one or at least two of alkane, 1-ethylene, 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene;
preferably, the aromatic monomer represented by the formula (13) and the formula (14) in the 1) comprises any one or at least two of biphenyl, para-terphenyl, meta-terphenyl or para-terphenyl;
preferably, R in the fluorene-based structural monomer represented by the formula (15) in 1) 3 And R is 4 Each independently selected from any one of hydrogen, C1-C10 chain alkyl or C3-C10 cycloalkyl, preferably, the R 3 And R is 4 Each independently selected from any one of hydrogen, methyl, ethyl, propyl, butyl, pentyl and hexyl; .
Preferably, the diphenylalkane monomer represented by the formula (16) in 1) contains any one or a combination of at least two of diphenylmethane, 1, 2-diphenylethane, 1, 3-diphenylpropane, 1, 4-diphenylbutane, 1, 5-diphenylpentane, 1, 6-diphenylhexane, 1, 7-diphenylheptane and 1, 8-diphenyloctane.
Preferably, the solvent for the polymerization reaction in 1) comprises any one or at least two of dichloromethane, chloroform, tetrachloroethane, toluene, trifluoroacetic acid or trifluoromethanesulfonic acid;
preferably, the polymerization reaction in 1) is carried out in the presence of a catalyst comprising any one or a combination of at least two of trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid, or heptafluorobutyric acid; preferably, the polymerization reaction temperature is
Preferably, the polymerization reaction time in 1) is
2) Reacting the piperidine tertiary amine group polymer containing the space three-dimensional cross-linking center carbon-based skeleton structure in the step 1) with an alkylating reagent, thereby obtaining the piperidine tertiary amine group anion exchange polymer containing the space three-dimensional cross-linking center carbon-based skeleton structure.
Preferably, the alkylating agent comprises any one or at least two of methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, propyl bromide, butyl bromide, 1, 2-dibromoethane, 1, 3-dibromopropane, 1, 4-dibromobutane, 1-5-dibromopentane, 1-6-dibromohexane, 1, 2-diiodoethane, 1, 3-diiodopropane, 1, 4-diiodobutane, 1-5-diiodopentane, 1-6-diiodohexane;
preferably, the reaction solvent in 2) comprises any one or at least two of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol or water;
preferably, the reaction time in 2) is 0.1 to 120 hours.
Preferably, the reaction in 2) is stabilized as
In a sixth aspect, the present disclosure provides an anion exchange membrane, where the anion exchange membrane is prepared by dissolving a piperidine tertiary amine group anion exchange polymer containing a sterically stereo cross-linked central carbon-based framework structure in a solution for curing or casting a membrane machine, or by blending the piperidine tertiary amine group anion exchange polymer containing a sterically stereo cross-linked central carbon-based framework structure with other high molecular materials, such as polyphenylene ether, polytetrafluoroethylene, polyvinyl alcohol, polysulfone, etc. (including but not limited to other anion exchange polymers, such as polyimidazolium salt type anion exchange polymers, polypiperidine tertiary amine type anion exchange polymers, etc.), and then dissolving in the solution for curing or casting a membrane machine.
Preferably, the solution for dissolving the anion exchange membrane comprises any one or at least two of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol or water.
Preferably, the above-described anion exchange polymer solution is cast or cast on a substrate and dried.
Preferably, the substrate comprises any one or a combination of at least two of a glass plate, a polytetrafluoroethylene plate, a ceramic plate, a steel strip, a polyethylene terephthalate based film, a polyamide based film, a polytetrafluoroethylene porous film, a polyethylene porous film, a polypropylene porous film, glass fibers, or carbon fibers.
Preferably, the drying temperature is one or more of 80-280 ℃ for stepwise drying;
preferably, the drying time is 0.1 to 120 hours.
Preferably, the above-described anion exchange polymer is placed in a casting film machine to prepare a flat film. In some embodiments, the film has a specific thickness of 1 to 500 μm.
In a seventh aspect, the present invention provides a method of preparing a piperidine tertiary amine group anion exchange polymer binder comprising a sterically hindered central carbon-based backbone structure by spraying or dripping onto a metal substrate catalyst or onto a metal substrate or carbon-based conductive substrate after blending with a powder catalyst by means of an anion exchange polymer solution as described above.
Preferably, the substrate comprises nickel mesh, nickel fiber felt, foam nickel, stainless steel mesh, stainless steel felt, foam stainless steel, titanium mesh, titanium fiber felt, foam titanium, copper mesh, PTFE-based magnetron sputtered copper, copper sheet, carbon paper, carbon cloth, and the like.
The application of the anion exchange membrane and the anion exchange polymer adhesive provided by the scheme can be used for alkaline electrolyzed water, alkaline fuel cells, carbon dioxide reduction and flow batteries.
Compared with the prior art, the technical proposal provides a piperidine tertiary amine group polymer containing a space three-dimensional cross-linked central carbon-based skeleton structure, which comprises tetraphenylmethyl on the main chain chemical structureAlkyl groups or aromatic triptycenes, the prepared polymer has light crosslinking, so that the prepared material has more excellent mechanical strength. When the polymer contains a tetraphenylmethyl group in the main chain chemical structure, the piperidinetertiary amine group polymer contains sp 3 A carbon-based backbone structure; when the polymer contains an aromatic hydrocarbon triptycene in the main chain chemical structure, the piperidinetertiary amine group polymer contains sp 2 The carbon-based skeleton structure reduces pi-pi action of an aromatic hydrocarbon structure after film formation of the polymer due to the supporting action of the carbon-based skeleton structure on the main chain, so that the formation of a crystallization area is reduced, the actual utilization rate of hydroxyl exchange of piperidine quaternary ammonium salt in the polymer structure is increased, the construction of a hydrophilic phase is facilitated, and the ionic conductivity of the film is remarkably improved.
Drawings
FIG. 1 is a nuclear magnetic H spectrum of an anion exchange polymer obtained in example 1 of the present invention.
FIG. 2 is a nuclear magnetic H spectrum of the anion exchange polymer obtained in example 2 of the present invention.
FIG. 3 is a nuclear magnetic H spectrum of an anion exchange polymer obtained in example 4 of the present invention.
FIG. 4 is a nuclear magnetic H spectrum of the anion exchange polymer obtained in comparative example 1.
FIG. 5 is an embodiment of the present invention
Compared with comparative example->
OH at 80℃of the anion exchange polymer of (C) - Ion conductivity versus graph.
FIG. 6 is an embodiment of the present invention
Compared with comparative example->
Tensile strength at room temperature.
FIG. 7 is an embodiment of the present invention
Compared with comparative example->
Comparison of cation residual rate by soaking in 1M (mol/L) NaOH solution at 80 ℃ for 2000 h.
FIG. 8 is a schematic of a carbon dioxide electrochemical reduction flow cell.
FIG. 9 is a schematic view of an electrolytic water membrane electrode cell.
Fig. 10 is a schematic diagram of a membrane electrode fuel cell.
FIG. 11 is a schematic diagram of a flow cell.
FIG. 12 is a graph of examples of application of example 1 and comparative examples 1-2 to electrochemical reduction of carbon dioxide flow cells.
FIG. 13 is a graph of example 4 applied to electrochemical reduction of carbon dioxide flow cells.
Fig. 14 is a graph of example cell pressure versus current density for example 1 and comparative example 2 and comparative example 3 applied to an alkaline electrolyzed water MEA cell.
FIG. 15 is a graph of cell pressure versus current density for an example 4 application to an alkaline electrolyzed water MEA cell.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
It will be understood that the terms "a" and "an" should be interpreted as referring to "at least one" or "one or more," i.e., in one embodiment, the number of elements may be one, while in another embodiment, the number of elements may be plural, and the term "a" should not be interpreted as limiting the number.
Embodiment one:
an anion exchange polymer is provided having the structure shown below:
the preparation method of the anion exchange polymer comprises the following steps:
(1) 2.0g (8.68 mmo1) of terphenyl was weighed into a 100mL flask, 1.02g (mmol) of N-methyl-4-piperidone was added, 54.53mg (0.17 mmol) of tetraphenyl methane was added, and then 8.8mL of methylene chloride was added to dissolve and disperse the reaction. 1.5mL of trifluoroacetic acid and 8.8mL of trifluoromethanesulfonic acid were added at 0deg.C and reacted for 6 hours. Pouring the viscous purple product into 1M (mol/L) K 2 CO 3 Soaking in the solution for 24 hours at room temperature, filtering to obtain a white solid product, fully washing with deionized water, and drying to obtain a target product.
(2) Quaternization reaction. 1.0g of the above intermediate polymer was weighed, 20mL of dimethyl sulfoxide was added, followed by 1.0mL of methyl iodide, and the mixture was reacted at room temperature for 12 hours, followed by raising the temperature to 60℃for 12 hours. Pouring the reaction product into ethyl ether (volume ratio of ethyl ether to ethanol is 6:1) solvent containing ethanol, precipitating to obtain yellow precipitate, washing with ethyl acetate three times, washing with water, and oven drying to obtain anion I - Is an anion exchange polymer of (a).
(3) Film formation and ion exchange. 120mg of the above anion exchange polymer was weighed, 5mL of dimethyl sulfoxide was added, and after sufficient dissolution, the mixture was poured into a glass petri dish having a diameter of 6cm, and the film was dried at 120℃to form a film, and the film was peeled from the glass. Soaking the anion exchange membrane in 1M KOH solution, and ion-exchanging at 80deg.C for 12 hr to obtain anion OH - Is a basic film of (a).
The resulting anion exchange polymer was characterized by means of a nuclear magnetic resonance spectrometer model Bruker AVANCE NEO (500 MHz), the hydrogen profile nuclear magnetic pattern of which is shown in figure 1, and deuterated dimethyl sulfoxide (d 6-DMS 0) was used to dissolve the sample during the test.
Embodiment two:
an anion exchange polymeric membrane is provided having the structure:
the preparation method of the anion exchange membrane comprises the following steps:
1) 2.0g (8.68 mmo 1) of terphenyl was weighed into a 100mL flask, 0.92g (8.12 mmol) of N-methyl-4-piperidone was added, 54.53mg (0.17 mmol) of tetraphenyl methane was added, 156.70mg (0.90 mmol) of 2, 2-trifluoroacetophenone was added, and then 8.8mL of methylene chloride was added to dissolve and disperse the reaction. 1.5mL of trifluoroacetic acid and 8.8mL of trifluoromethanesulfonic acid were added at 0deg.C and reacted for 6 hours. Pouring the viscous purple product into 1M (mol/L) K 2 CO 3 Soaking in the solution for 24 hours at room temperature, filtering to obtain a white solid product, fully washing with deionized water, and drying to obtain a target product.
2) Quaternization reaction. 1.0g of the above intermediate polymer was weighed, 20mL of dimethyl sulfoxide was added, followed by 1.0mL of methyl iodide, and the mixture was reacted at room temperature for 12 hours, followed by raising the temperature to 60℃for 12 hours. The reaction product was poured into an ethyl ether (volume ratio of ethyl ether to ethanol: 6:1) solvent containing ethanol, and a yellow precipitate was obtained by precipitation, followed by washing with ethyl acetate three times, washing with water and drying to obtain an anion-exchange polymer having an anion of I-.
3) Film formation and ion exchange. 120mg of the above anion exchange polymer was weighed, 5mL of dimethyl sulfoxide was added, and after sufficient dissolution, the mixture was poured into a glass petri dish having a diameter of 6cm, and the film was dried at 120℃to form a film, and the film was peeled from the glass. Soaking the anion exchange membrane in 1M KOH solution, and ion-exchanging at 80deg.C for 12 hr to obtain anion OH - Is a basic film of (a).
The resulting anion exchange polymer was characterized by means of a nuclear magnetic resonance spectrometer model Bruker AVANCE NEO (500 MHz), and the hydrogen profile nuclear magnetic pattern is shown in fig. 2.
Embodiment III:
a mixture of anion exchange polymers prepared from a mixture of polymers of the following two structures.
60mg of each of the above two anion exchange polymers was weighed, 5mL of dimethyl sulfoxide was added thereto, and after sufficient dissolution, the mixture was poured into a 6cm diameter glass petri dish, and the film was dried at 120℃to form a film, and the film was peeled from the glass. Soaking the anion exchange membrane in 1MKOH solution, and ion-exchanging at 80deg.C for 12 hr to obtain anion OH - Is a basic film of (a).
Fourth embodiment;
an anion exchange polymeric membrane is provided having the structure:
1) 2.0g (8.68 mmo 1) of terphenyl was weighed into a 100mL flask, 0.92g (8.12 mmol) of N-methyl-4-piperidone was added, 43.24mg (0.17 mmol) of triptycene was added, and then 8.8mL of methylene chloride was added to dissolve and disperse the reaction. 1.5mL of trifluoroacetic acid and 8.8mL of trifluoromethanesulfonic acid were added at 0deg.C and reacted for 6 hours. Pouring the viscous purple product into 1M (mol/L) K 2 CO 3 Soaking in the solution for 24 hours at room temperature, filtering to obtain a white solid product, fully washing with deionized water, and drying to obtain a target product.
2) Quaternization reaction. 1.0g of the above intermediate polymer was weighed, 20mL of dimethyl sulfoxide was added, followed by 1.0mL of methyl iodide, and the mixture was reacted at room temperature for 12 hours, followed by raising the temperature to 60℃for 12 hours. The reaction product was poured into an ethyl ether (volume ratio of ethyl ether to ethanol: 6:1) solvent containing ethanol, and a yellow precipitate was obtained by precipitation, followed by washing with ethyl acetate three times, washing with water and drying to obtain an anion-exchange polymer having an anion of I-.
3) Film formation and ion exchange. 120mg of the above anion exchange polymer was weighed, 5mL of dimethyl sulfoxide was added, and after sufficient dissolution, the mixture was poured into a glass petri dish having a diameter of 6cm, and the film was dried at 120℃to form a film, and the film was peeled from the glass. Soaking the anion exchange membrane in 1M KOH solution, and ion-exchanging at 80deg.C for 12 hr to obtain anion OH - Is a basic film of (a).
The resulting anion exchange polymer was characterized by means of a nuclear magnetic resonance spectrometer model Bruker AVANCE NEO (500 MHz), and the hydrogen profile nuclear magnetic pattern is shown in fig. 3.
Comparative example one
An anion exchange polymer having the structure:
the preparation route is as follows:
1) 2.0g (8.68 mmo 1) of terphenyl was weighed into a 100mL flask, 0.98g (8.68 mmole) of N-methyl-4-piperidone was added, followed by 8.8mL of methylene chloride to dissolve and disperse the reaction. 1.5mL of trifluoroacetic acid and 8.8mL of trifluoromethanesulfonic acid were added at 0deg.C and reacted for 6 hours. Pouring the viscous purple product into 1M (mol/L) K 2 CO 3 Soaking in the solution for 24 hours at room temperature, filtering to obtain a white solid product, fully washing with deionized water, and drying to obtain a target product.
2) Quaternization reaction. 1.0g of the above intermediate polymer was weighed, 20mL of dimethyl sulfoxide was added, followed by 1.0mL of methyl iodide, and the mixture was reacted at room temperature for 12 hours, followed by raising the temperature to 60℃for 12 hours. Pouring the reaction product into ethyl ether (volume ratio of ethyl ether to ethanol is 6:1) solvent containing ethanol, precipitating to obtain yellow precipitate,then washed three times with ethyl acetate, then washed with water and dried to obtain the anion I - Is an anion exchange polymer of (a).
3) Film formation and ion exchange. 120mg of the above anion exchange polymer was weighed, 5mL of dimethyl sulfoxide was added, and after sufficient dissolution, the mixture was poured into a glass petri dish having a diameter of 6cm, and the film was dried at 120℃to form a film, and the film was peeled from the glass. Soaking the anion exchange membrane in 1M KOH solution, and ion-exchanging at 80deg.C for 12 hr to obtain anion OH - Is a basic film of (a).
The resulting anion exchange polymer was characterized by means of a nuclear magnetic resonance spectrometer model Bruker AVANCE NEO (500 MHz), and the hydrogen profile nuclear magnetic pattern is shown in fig. 4.
Comparative example two
Providing an anion exchange polymer having the structure;
the present solution provides an anion exchange polymer PiperION A40-HCO3, manufactured by Versogen corporation.
Comparative example three
The present solution provides an anion exchange polymer
37-50-grade T, manufactured by Dioxide materials company.
Performance test:
1) Ion exchange Capacity test
The ion exchange capacity of the anion exchange membrane was measured using the H spectrum in the nuclear magnetic test, specifically as follows: the obtained anion exchange polymer was subjected to characterization analysis by using a nuclear magnetic resonance spectrometer model Bruker AVANCE NEO (500 MHz), the hydrogen peak on the methyl group to which the quaternary ammonium nitrogen is attached and the hydrogen peak on the benzene ring of the main chain were respectively subjected to area integration, and the ion exchange capacity was calculated by the peak area ratio of the two.
2) Ion conductivity test
By means ofFour-electrode alternating current impedance method for measuring OH of all-wet anion exchange membrane in pure water - The ionic conductivity, specific test parameters, are as follows: taking an area of 2X2cm 2 Film material with thickness of 25 μm, using Autolab 302N electrochemical workstation, at frequency
And (3) carrying out alternating current impedance test, and fitting a curve to calculate the ion conductivity. The ionic conductivities at 80℃of comparative example 1, comparative example 2, comparative example 3, example 1, example 2, example 3 and example 4 are shown in FIG. 5.
3) Tensile Strength test
The tensile strength of the anion exchange membrane at room temperature was measured by means of a tensile tester (manufacturer: shimadzu corporation, model: AGS-X10 KN). The tensile strengths of comparative example 1, comparative example 2, comparative example 3, example 1, example 2, example 3 and example 4 at room temperature are shown in fig. 6.
4) Stability test
The residual rate of cations in the anion exchange membrane was measured by immersing the anion exchange membrane in a 1M NaOH solution at 80℃and observing the change of the nuclear magnetic pattern of the hydrogen spectrum after 2000 hours. The residual cation rates after soaking in 1M (mol/L) NaOH solution at 80deg.C for 2000 hours in comparative example 1, comparative example 2, comparative example 3, example 1, example 2, example 3 and example 4 are shown in FIG. 7.
As can be seen from fig. 5-7: the ionic conductivities of examples 1-4 are all higher than those of comparative examples 1-3, and the tensile strengths of examples 1-4 are also much higher than those of comparative examples 1-3, indicating that the ionic conductivities and mechanical strengths of the anion exchange membranes provided by the present solution are both improved, and the stability of examples 1-4 is not significantly affected.
Use of the anion exchange membrane shown in example 1 in electrochemical reduction of carbon dioxide.
Based on example 1, the anion exchange membrane prepared in this case was used for CO 2 RR, i.e. CO 2 And (3) reduction:
flow cell equipment was used. Flow cThe concrete structure of the ell electrolytic cell is shown in fig. 8: component (1) 2 A gas flow chamber; a component (2) a silica gel gasket; a component (3) cathode (CO 2 RR) catalyst; a component (4) catholyte flow chamber; an ion transport membrane of the assembly (5); the component (6) anode catalyst; an assembly (7) anolyte flow chamber; the assembly (8) is a backing plate.
Namely: three-chamber flow electrolytic cells are utilized, and the three-chamber flow electrolytic cells are sequentially CO 2 Gas flow chamber, catholyte flow chamber, and anolyte flow chamber, CO 2 A gas diffusion electrode is arranged between the gas flow chamber and the cathode liquid flow chamber, and CO is generated by the gas diffusion electrode 2 The gas flow chamber is separated from the cathode flow chamber, a watermelon-based biological ion transmission membrane is arranged between the cathode flow chamber and the anode flow chamber, the cathode flow chamber is separated from the anode flow chamber by utilizing an anion exchange membrane, then the anode flow chamber is sealed, an anode counter electrode is arranged in the anode flow chamber, a cathode flow bottle is communicated with the cathode flow chamber through a conduit, the anode flow bottle is communicated with the anode flow chamber through a conduit, and CO 2 The gas flow chamber is made of polytetrafluoroethylene, and finally the positive electrode and the negative electrode of the power supply are respectively connected with the anode counter electrode and the CO 2 The outer surfaces of the gas flow chambers are connected.
1) The anion exchange membrane shown in example 1 was used;
2) KOH solution is used as electrolyte;
3) Water oxidation and CO 2 The reduced anode and cathode catalysts were S (Ni, fe) OOH and cobalt phthalocyanine (CoPc), respectively;
4)CO 2 the flow rate is 20sccm;
5) The flow rates of the anolyte and catholyte were 35ml/min and 10ml/min, respectively.
6) For CO flowing into electrolytic cell in a certain voltage range 2 Reduction is performed. This voltage is set according to the actual operation.
The final results are shown in FIG. 12, which shows that the reduction of CO at different current densities is achieved by comparing the experimental results of example 1 as an anion exchange membrane with the experimental results of comparative example 2 and comparative example 3 as anion transport membranes 2 Corresponding Cell Voltage (Cell Voltage), realThe cell pressure used in example 1 was minimal. The performance was better than that of comparative examples 2 and 3.
Use of the anion exchange membrane shown in example 4 in electrochemical reduction of carbon dioxide.
The overall test procedure was identical to that of the anion exchange membrane of example 1 for electrochemical reduction of carbon dioxide, except that the anion exchange membrane of example 1 was replaced with the anion exchange membrane of example 4, and the test results were shown in fig. 13.
Use of the anion exchange membrane shown in example 1 in alkaline electrolysis of water.
The specific structure of the MEA electrolytic cell is shown in figure 11: the assembly (1) is a stainless steel backing plate; a component (2) copper electrode; the component (3) is a graphite catholyte flow chamber; a component (4) cathode catalyst; an ion transport membrane of the assembly (5); the component (6) anode catalyst; the component (7) is a graphite anode electrolyte flow chamber.
The test uses Fe-Ni 3 S 2 Is an anode gas diffusion electrode (1.0 cm) 2 0.75mm thick) with Ni4Mo/MoO2/NF as cathode gas diffusion electrode (1.0 cm) 2 1mm thick) the above-described Membrane Electrode Assembly (MEA) was assembled into a device using the anion exchange membrane prepared in example 1 as a membrane material. The anode and the cathode are continuously introduced for 50mL min -1 Is activated by Cyclic Voltammetry (CV) for 1h before testing by using Autolab 302N equipped with a 10A current amplifier at a cell operating temperature of 80 ℃ and a sweep rate of 200mV s, voltage in the range of 1.0 to 2.6V -1 The voltage range used in the polarization curve test is 1.0-2.6V, and the sweeping speed is 10mV s -1 Electrochemical impedance spectroscopy was tested at a constant voltage of 1.8V, with a 10mV fluctuating voltage applied, and a perturbation frequency: 1 Hz-100 KHz.
The catalyst preparation process is as follows:
first, for nickel foam (NF, 2.0X13.0 cm 2 ) The specific operation is: firstly placing the foam nickel in 3MHCl, taking out after ultrasonic treatment for 20min, respectively washing with deionized water and absolute ethyl alcohol for several times, and drying for later use.
Fe-Ni 3 S 2 And (3) preparing a catalyst: catalystThe catalyst is typically synthesized by a one-step hydrothermal process as follows: thiourea (2.0 mmol), feSO 4 ·7H 2 O (0.5 mmol) and sodium citrate (25 mg) were dissolved in a mixed solvent of methanol (15 mL) and deionized water (20 mL). After sufficient dissolution, the solution was transferred to a stainless steel autoclave (gauge: 50 mL) and the cleaned NF was immersed in the solution, after the autoclave was sealed, it was transferred to an oven, reacted at 160℃for 8 hours, then naturally cooled to room temperature.
Ni4Mo/MoO2/NF catalyst preparation: ni (NO) 3 ) 2 ·6H 2 O (40 mM) and (NH) 4 ) 6 Mo 7 O 24 (25 mg) was dissolved in deionized water (15 mL), after complete dissolution, the solution was transferred to a stainless steel autoclave (gauge: 50 mL), and the cleaned NF (2.0X12.0 cm) 2 ) Immersing in the solution, sealing, transferring to oven, reacting at 150 deg.C for 6 hr, natural cooling to room temperature, washing the reacted NF with deionized water and absolute alcohol several times, baking, loading it in quartz boat, loading it in tubular furnace, and treating with H 2 Calcining for 2h at 500 ℃ in Ar (v/v, 5/95) atmosphere, cooling to room temperature after calcining, taking out, and putting into a dryer for standby.
The results of the alkaline electrolyzed water MEA test are shown in fig. 14. The results show that the anion exchange membrane based MEA devices shown in example 1 showed higher current densities than the anion exchange membrane based MEA devices shown in comparative example 2 and comparative example 3s ustainion x37-50Grade T at cell pressures of 2.0V and 2.6V, respectively. The superior performance of the anion exchange membrane shown in example 1 was demonstrated.
Use of the anion exchange membrane shown in example 4 in alkaline electrolysis of water.
The overall test procedure was identical to that of the anion exchange membrane shown in example 1 for alkaline electrolyzed water, except that the anion exchange membrane shown in example 1 was replaced with the anion exchange membrane shown in example 4, and the test results were shown in fig. 15.
The present invention is not limited to the above-described preferred embodiments, and any person who can obtain other various products under the teaching of the present invention, however, any change in shape or structure of the product is within the scope of the present invention, and all the products having the same or similar technical solutions as the present application are included.
Claims (15)
1. A piperidyl tertiary amine group polymer containing a sterically hindered central carbon-based backbone structure, comprising:
a tetraphenyl methane structural unit represented by the formula (1) or one of triptycene structural units represented by the formula (2), and a piperidine tertiary amine structural unit represented by the formula (3):
2. the piperidyl tertiary amine group polymer containing a sterically stereo cross-linked central carbon-based backbone structure as described in claim 1, further comprising: one or a combination of at least two of a trifluoromethyl structural unit shown in a formula (4), an aryl structural unit shown in a formula (5), a aryl structural unit shown in a formula (6), a fluorene structural unit shown in a formula (7) and a diphenyl alkane structural unit shown in a formula (8):
3. the polymer of piperidyl tertiary amine groups containing a sterically stereo cross-linked central carbon-based skeleton structure as claimed in claim 1, wherein the molar ratio of the tetraphenyl methane structural unit (1) to the piperidyl tertiary amine structural unit (3) is (0.001-1): 1.
4. The polymer of piperidinetertiary amine groups containing a sterically stereo cross-linked central carbon-based skeleton structure as claimed in claim 1, wherein the molar ratio of the tri-dish alkene structural unit (2) to the piperidinetertiary amine structural unit (3) is (0.001-1): 1.
5. A preparation method of a piperidyl tertiary amine group polymer containing a space three-dimensional cross-linked central carbon-based skeleton structure is characterized by comprising the steps of carrying out polymerization reaction on monomers, wherein the monomers comprise one of a tetraphenyl methane monomer shown in a formula (9) or a triptycene monomer shown in a formula (10), and a piperidone monomer shown in a formula (11):
6. the method for preparing a piperidyl tertiary amine group polymer containing a sterically hindered central carbon-based backbone structure as described in claim 5, wherein said monomers further comprise: one or a combination of at least two of a trifluoromethyl ketone monomer represented by formula (12), an aryl monomer represented by formula (13), formula (14), a fluorene monomer represented by formula (15), and a diphenylalkane monomer represented by formula (16):
7. a piperidine tertiary amine group anion exchange polymer comprising a sterically hindered central carbon-based backbone structure, comprising: one of a tetraphenyl methane-based structural unit represented by formula (17) or a triptycene structural unit represented by formula (18), and a piperidine quaternary amine structural unit represented by formula (19) and/or (20):
8. the piperidine tertiary amine group anion exchange polymer containing a sterically hindered central carbon-based skeleton structure according to claim 7, characterized by comprising one or more combinations of trifluoromethyl structural unit represented by formula (21), aryl structural unit represented by formula (22), aryl structural unit represented by formula (23), fluorene structural unit represented by formula (24), and diphenyl alkane structural unit represented by formula (25):
9. a preparation method of a piperidine tertiary amine group anion-exchange polymer containing a space three-dimensional cross-linked central carbon-based skeleton structure is characterized by comprising the following steps: 1) Polymerizing monomers including one of a tetraphenyl methane monomer of formula (9) or a triptycene monomer of formula (10), a piperidone monomer of formula (11):
2) Reacting the piperidyl tertiary amine group polymer containing the steric cross-linked central carbon-based skeleton structure obtained in the step 1) with an alkylating reagent.
10. The method for producing a piperidine tertiary amine group anion exchange polymer having a spatially stereo cross-linked central carbon-based skeleton structure according to claim 9, wherein the monomer further comprises one or a combination of at least two of a trifluoromethyl ketone monomer represented by formula (12), an aryl monomer represented by formula (13) or formula (14), a fluorene monomer represented by formula (15), and a diphenylalkane monomer represented by formula (16):
11. the anion exchange membrane is characterized in that the anion exchange membrane is prepared by dissolving the piperidine tertiary amine group anion exchange polymer containing the space three-dimensional cross-linked central carbon-based skeleton structure in any one of claims 7-9 in a solvent for curing or casting a membrane machine, or is prepared by blending the piperidine tertiary amine group anion exchange polymer containing the space three-dimensional cross-linked central carbon-based skeleton structure in any one of claims 7-9 with other high molecular materials and then dissolving the mixture in a solution for curing or casting a membrane machine.
12. An anion exchange polymer adhesive, which is characterized in that the anion exchange polymer adhesive solution is prepared by dissolving the piperidine tertiary amine group anion exchange polymer containing the steric cross-linked central carbon based skeleton structure according to any one of claims 7-9 in a solvent.
13. Use of a piperidine tertiary amine group anion exchange polymer comprising a sterically hindered central carbon-based backbone structure according to any of claims 7 to 9 for alkaline electrolysis of water, alkaline fuel cells, carbon dioxide reduction and flow batteries.
14. Use of an anion exchange membrane according to claim 11 for alkaline electrolysis of water, alkaline fuel cells, carbon dioxide reduction and flow batteries.
15. Use of the anion exchange polymer binder according to claim 12 for alkaline electrolyzers, alkaline fuel cells, carbon dioxide reduction and flow batteries.
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