CN117209807A - Method for improving solubility of heterocyclic aromatic polymer and application thereof - Google Patents
Method for improving solubility of heterocyclic aromatic polymer and application thereof Download PDFInfo
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- CN117209807A CN117209807A CN202311483720.3A CN202311483720A CN117209807A CN 117209807 A CN117209807 A CN 117209807A CN 202311483720 A CN202311483720 A CN 202311483720A CN 117209807 A CN117209807 A CN 117209807A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 413
- 125000006615 aromatic heterocyclic group Chemical group 0.000 title claims abstract description 242
- 238000000034 method Methods 0.000 title claims abstract description 66
- 239000002904 solvent Substances 0.000 claims abstract description 131
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 65
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 61
- 238000001035 drying Methods 0.000 claims abstract description 40
- 239000007787 solid Substances 0.000 claims abstract description 39
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 30
- 238000010008 shearing Methods 0.000 claims abstract description 10
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 230000000171 quenching effect Effects 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 54
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 39
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 27
- 239000001257 hydrogen Chemical group 0.000 claims description 22
- 229910052739 hydrogen Chemical group 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 16
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 14
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 13
- 239000000446 fuel Substances 0.000 claims description 13
- -1 tetramethyl sulfoxide Chemical class 0.000 claims description 13
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- 238000002360 preparation method Methods 0.000 claims description 11
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000002798 polar solvent Substances 0.000 claims description 10
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
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- 238000009835 boiling Methods 0.000 description 10
- 230000008876 conformational transition Effects 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
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- 238000004090 dissolution Methods 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 5
- 101000927773 Homo sapiens Rho guanine nucleotide exchange factor 9 Proteins 0.000 description 5
- 102100033221 Rho guanine nucleotide exchange factor 9 Human genes 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229920006125 amorphous polymer Polymers 0.000 description 4
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
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- 231100000419 toxicity Toxicity 0.000 description 3
- RMGHERXMTMUMMV-UHFFFAOYSA-N 2-methoxypropane Chemical compound COC(C)C RMGHERXMTMUMMV-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RMOUBSOVHSONPZ-UHFFFAOYSA-N Isopropyl formate Chemical compound CC(C)OC=O RMOUBSOVHSONPZ-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention discloses a method for improving the solubility of heterocyclic aromatic polymers and application thereof, wherein the method for improving the solubility of the heterocyclic aromatic polymers comprises the following steps: adding the heterocyclic aromatic hydrocarbon polymer solution into a low-temperature first poor solvent for quenching, and separating out polymer solids; cleaning the polymer solids with a low temperature second poor solvent; and drying the cleaned polymer solid at a low temperature to obtain the high-solubility heterocyclic aromatic polymer. The polymer molecular chain conformation of the high-solubility heterocyclic aromatic polymer is mainly disordered and is easier to dissolve. When the polymer is dissolved in a solvent, the polymer and the solvent can be prevented from forming gel at a higher concentration, the solution state is kept, the shearing viscosity is lower and the gel is not easy to be formed at the same concentration, the processability of the heterocyclic aromatic polymer is improved, and the chemical structure of the heterocyclic aromatic polymer is not changed. The ion exchange membrane prepared from the high-solubility heterocyclic aromatic polymer has better uniformity and excellent electrochemical performance and mechanical performance.
Description
Technical Field
The invention relates to the technical field of high molecular materials, in particular to a method for improving solubility of heterocyclic aromatic hydrocarbon polymers and application thereof.
Background
Heterocyclic aromatic polymers have become a class of high performance materials. Common heterocyclic aromatic polymers include benzimidazole polymers, benzoxazole polymers, and benzothiazole polymers, which all have high chemical resistance, flame retardancy, radiation stability, and excellent mechanical strength, as well as a wide range of operating temperatures. Most heterocyclic aromatic polymers do not melt at the decomposition temperature and are generally soluble only in strong acids or highly polar solvents. The heterocyclic aromatic polymer has the characteristics of large molecular structure rigidity, strong hydrogen bonding effect of functional groups, large shearing viscosity and easy gelation in the dissolution of a high-polarity solvent, and is unfavorable for the solution processing and forming.
The emerging development field of fuel cell proton exchange membranes as heterocyclic aromatic hydrocarbon polymer materials is the main competitive field of the market in the current stage. The current common method is to dissolve the heterocyclic aromatic polymer in a highly polar solvent for preparing the proton exchange membrane of the fuel cell. The method improves the solubility of the heterocyclic aromatic polymer in the high-polarity solvent, obviously reduces the processing difficulty of the film, improves the processing efficiency and better meets the preparation requirement of the proton exchange membrane of the fuel cell.
Methods for improving the poor processability of heterocyclic aromatic polymers are generally chemical modification of the polymer backbone. For benzimidazole polymers, the common chemical modification method is to replace N-H active sites of imidazole or introduce flexible groups into the main chain of the polymer molecule. However, this modification always results in improved solubility at the expense of the properties of the heterocyclic aromatic polymer, and the chemical resistance, mechanical strength and operating temperature range of the modified polymer are reduced to varying degrees.
The gel mechanism of heterocyclic aromatic polymers in highly polar solvents depends on the interactions between the polymer and the solvent, which lead to crystallization and conformational transition of the polymer molecule. The gel temperature of the heterocyclic aromatic polymer and the solvent mainly depends on the concentration and molecular weight of the polymer, and the polymer molecules are subjected to chain segment self-assembly in the solvent, so that the polymer molecules can undergo conformational transition, and random coils are converted into regular conformations, so that crystals with specific structures are formed by aggregation. The process of converting gel or crystal/semi-crystal benzimidazole polymer of heterocyclic aromatic polymer into solution is to break the crystal of polymer, change conformation, change ordered structure into disordered high molecular coil, and further obtain polymer solution.
The solvent has double functions of inducing and destroying the crystallization of the heterocyclic aromatic polymer, and the heterocyclic aromatic polymer can be crystallized and separated out in the solvent by utilizing the inducing function of the crystallization, so that the heterocyclic aromatic polymer solid with specific size and shape is obtained. In another aspect, the solvent and polymer form a solution during which the polymer crystallizes and undergoes disruption and conformational changes, which process is largely dependent upon the chemical structure and concentration of the polymer. When the molecular structure, the crystallization state and the molecular weight distribution of the polymer are determined, the dissolution process mainly depends on the concentration of the polymer, and when the concentration is too high, the crystallization is difficult to break and the conformation transition is slow, the polymer solid forms gel with the solvent, and the further conformation transition is difficult to obtain the polymer solution with certain processability. However, low concentration polymer solutions do not meet all processing requirements, and gelled dispersions are difficult to process.
Disclosure of Invention
The present invention has been made based on the findings and knowledge of the inventors regarding the following facts and problems: the rigid structure and strong hydrogen bonding of heterocyclic aromatic polymers gives them high chemical stability, excellent mechanical properties and broad service temperatures, but such rigidity and hydrogen bonding make polymer dissolution and processing difficult. At present, the main method for improving the solubility of the heterocyclic aromatic polymers is to modify the polymer skeleton, and the essence of the method is to reduce the rigidity and hydrogen bonding effect of polymer molecules, improve the solubility of the polymers and reduce the performance of the materials. The rigid structure of the heterocyclic aromatic polymer molecule and the strong hydrogen bonding of the functional groups make the polymer very susceptible to crystallization at room temperature and higher, and dissolution of the polymer in the crystalline state in a solvent requires both a process of crystallization disruption and conformational transition of the molecular segments, wherein the rate of conformational transition is extremely slow and reversible. With the increase of the molecular weight and concentration of the polymer, the molecular chains are easier to self-assemble under the action of hydrogen bonds, so that the conformation of the molecular chains is more ordered, the polymer with high molecular weight is more difficult to dissolve into a solution, and gel with high shear viscosity and difficult processing is formed when the concentration is increased. The heterocyclic aromatic polymer is used as an ion exchange membrane for a fuel cell, and the polymer solution is required to be processed into a film in the preparation process, so that the processing efficiency and the product quality can be effectively improved by improving the solubility of the heterocyclic aromatic polymer on the premise of not changing the chemical structure of the heterocyclic aromatic polymer.
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the embodiment of the invention provides a method for improving the solubility of heterocyclic aromatic hydrocarbon polymers and application thereof, wherein the polymer molecular chain conformation of the high-solubility heterocyclic aromatic hydrocarbon polymers is mainly disordered and is easier to dissolve compared with the heterocyclic aromatic hydrocarbon polymers before treatment. When the polymer is dissolved in a solvent, the polymer and the solvent can be prevented from forming gel at a higher concentration, the solution state is kept, the shearing viscosity is lower and the gel is not easy to be formed at the same concentration, the processability of the heterocyclic aromatic polymer is improved, the chemical structure of the heterocyclic aromatic polymer is not changed, and the material performance is not reduced due to the change of the chemical structure. The ion exchange membrane prepared from the high-solubility heterocyclic aromatic polymer has better uniformity and excellent electrochemical performance and mechanical performance.
The embodiment of the invention provides a method for improving the solubility of heterocyclic aromatic hydrocarbon polymers, which comprises the following steps:
(1) Adding the heterocyclic aromatic hydrocarbon polymer solution into a low-temperature first poor solvent, quenching and separating out polymer solids;
(2) Washing the polymer solids with a low temperature second poor solvent;
(3) And (3) drying the polymer solid washed in the step (2) at a low temperature to obtain the high-solubility heterocyclic aromatic polymer.
The method for improving the solubility of the heterocyclic aromatic polymer provided by the embodiment of the invention has the advantages and technical effects that: in the solution of the untreated heterocyclic aromatic polymer, the heterocyclic aromatic polymer has dissolved, disrupting the crystallization of the heterocyclic aromatic polymer during dissolution and converting the ordered polymer molecular conformation to a disordered conformation. And then pouring the heterocyclic aromatic polymer solution into the first poor solvent at low temperature to separate out, washing and drying at low temperature to obtain the high-solubility heterocyclic aromatic polymer. The precipitation and washing steps in the preparation process of the high-solubility heterocyclic aromatic polymer can effectively remove micromolecular impurities which are difficult to volatilize, and residual solvents, auxiliary agents and impurities in polymer solids are removed by washing.
In the embodiment of the invention, the method for improving the solubility of the heterocyclic aromatic polymer requires that the temperature of the whole process control system is low, and the low temperature control of the whole process is to prevent the heterocyclic aromatic polymer molecules from being converted into an ordered conformation and further form crystals, so that the solubility is poor. The rigid structure and hydrogen bonding of the heterocyclic aromatic polymer enable the heterocyclic aromatic polymer to be converted from an amorphous state to a crystalline state at room temperature, and the molecular level is that the molecular structure of the polymer is converted from disorder to order. In polymer solutions and melts, the structure of the polymer molecules is disordered, and in this state, quenching to obtain amorphous or low crystallinity polymer solids is a common method in the polymer arts. Since the decomposition temperature of the heterocyclic aromatic polymer is typically below the melting temperature, amorphous or low crystallinity polymer solids cannot be obtained by melt quenching the heterocyclic aromatic polymer. In the case of a heterocyclic aromatic polymer, cold crystallization occurs at room temperature due to hydrogen bonding, and it is impossible to obtain a polymer having low crystallinity or an amorphous polymer by precipitation treatment and drying treatment at a temperature lower than the glass transition temperature as in most polymers, and precipitation and drying at a temperature lower than room temperature are required to prevent the heterocyclic aromatic polymer from being recrystallized to deteriorate the solubility.
In the embodiment of the invention, compared with the heterocyclic aromatic hydrocarbon polymer before treatment, the polymer molecular chain conformation of the high-solubility heterocyclic aromatic hydrocarbon polymer is mainly disordered, the disorder degree of the molecular chain segment is high, the polymer molecular conformation is more similar to that of the polymer in solution, the amorphous polymer is easier to dissolve than the crystalline polymer, and the solubility is improved. When the high-solubility heterocyclic aromatic polymer is dissolved in a solvent, the polymer and the solvent can be prevented from forming gel at a higher concentration, the solution state is kept, the shearing viscosity is lower and the gel is not easy to form at the same concentration, and the processability of the heterocyclic aromatic polymer is improved. The heterocyclic aromatic polymer solution is treated at a low temperature to obtain the high-solubility heterocyclic aromatic polymer, the chemical structure of the heterocyclic aromatic polymer is not changed, and the material performance is not reduced due to the change of the chemical structure.
In some embodiments, in step (1), the heterocyclic aromatic polymer comprises at least one of benzimidazole polymer, benzoxazole polymer, benzothiazole polymer;
and/or, in the step (1), the number average molecular weight of the heterocyclic aromatic polymer is 5000-1000000;
And/or, in the step (1), the solvent of the heterocyclic aromatic hydrocarbon polymer solution includes at least one of a strong acid or a highly polar solvent; preferably, the strong acid comprises at least one of sulfuric acid, methanesulfonic acid or trifluoromethanesulfonic acid; the high-polarity solvent comprises at least one of DMF, DMAc, DMSO, hexamethylphosphoric triamide, tetramethyl sulfoxide or NMP;
and/or, in the step (1), the shearing viscosity of the heterocyclic aromatic polymer solution is less than or equal to 800 mPa.s.
In some embodiments, in the step (1), the temperature of the low-temperature first poor solvent is-110 to 10 ℃;
and/or, in the step (1), the first poor solvent comprises at least one of water, hydrocarbon, halogenated hydrocarbon, alcohol, ether, acetal, ketone, and ester;
and/or, in the step (1), the volume of the first poor solvent is 2-10 times of the volume of the heterocyclic aromatic polymer solution.
In some embodiments, in step (1), the heterocyclic aromatic polymer solution contains an auxiliary agent comprising at least one of a lithium salt or a hydrogen bond breaker; preferably, the lithium salt comprises lithium chloride; the hydrogen bond breaker comprises at least one of urea, fatty acid and trifluoroacetic acid; the mass content of the auxiliary agent in the heterocyclic aromatic polymer solution is 0% -5%.
In some embodiments, in step (1), the preparation of the heterocyclic aromatic hydrocarbon polymer solution comprises: dissolving heterocyclic aromatic hydrocarbon polymer in a solvent to obtain heterocyclic aromatic hydrocarbon polymer solution;
and/or, in the step (1), the heterocyclic aromatic polymer solution is a solution after the synthesis reaction of the heterocyclic aromatic polymer is finished.
In some embodiments, in step (2), the second poor solvent comprises at least one of water, hydrocarbons, halogenated hydrocarbons, alcohols, ethers, acetals, ketones, esters;
and/or, in the step (2), the temperature of the low-temperature second poor solvent is-110-10 ℃;
and/or, in the step (3), the low temperature is-110-10 ℃;
and/or, in the step (3), the drying is vacuum drying;
and/or, in the step (3), the mass percentage of volatile matters in the high-solubility heterocyclic aromatic hydrocarbon polymer is less than or equal to 12%.
The embodiment of the invention provides a high-solubility heterocyclic aromatic polymer, which is prepared by the method for improving the solubility of the heterocyclic aromatic polymer. In the embodiment of the invention, compared with the heterocyclic aromatic hydrocarbon polymer before treatment, the polymer molecular chain conformation of the high-solubility heterocyclic aromatic hydrocarbon polymer is mainly disordered, the solubility is high, when the high-solubility heterocyclic aromatic hydrocarbon polymer is dissolved in a solvent, the high-solubility heterocyclic aromatic hydrocarbon polymer can avoid the polymer and the solvent to form gel at a higher concentration, the solution state is maintained, the shearing viscosity is lower and the gel is not easy to be formed at the same concentration, the processability of the heterocyclic aromatic hydrocarbon polymer is improved, the chemical structure of the heterocyclic aromatic hydrocarbon polymer is not changed, and the material performance is not reduced due to the change of the chemical structure.
The embodiment of the invention provides a storage method of a high-solubility heterocyclic aromatic polymer, which is characterized in that the high-solubility heterocyclic aromatic polymer is stored in a low-temperature environment, and the temperature of the low-temperature environment is less than or equal to 4 ℃. In the embodiment of the invention, the high-solubility heterocyclic aromatic hydrocarbon polymer is stored at low temperature, so that the polymer molecular chain segment is prevented from moving to be more orderly or even crystallizing under the action of self rigidity and hydrogen bond, and the good solubility of the polymer can be maintained.
The embodiment of the invention provides application of a high-solubility heterocyclic aromatic polymer, which is used for a fuel cell. In the embodiment of the invention, the ion exchange membrane prepared from the high-solubility heterocyclic aromatic polymer has better uniformity and excellent electrochemical performance and mechanical performance, and can be applied to fuel cells.
The embodiment of the invention provides an ion exchange membrane, which comprises the high-solubility heterocyclic aromatic polymer. In the embodiment of the invention, the ion exchange membrane prepared from the high-solubility heterocyclic aromatic polymer has better uniformity and excellent electrochemical performance and mechanical performance, and can be applied to a proton exchange membrane of a medium-temperature fuel cell.
The embodiment of the invention provides a preparation method of an ion exchange membrane, which comprises the following steps:
1) Dispersing a high-solubility heterocyclic aromatic hydrocarbon polymer in a solvent to obtain a polymer solution;
2) Shaping and drying the polymer solution to obtain a heterocyclic aromatic polymer film;
3) And soaking the heterocyclic aromatic polymer membrane in a phosphoric acid solution for adsorption to obtain the phosphoric acid doped ion exchange membrane.
In the embodiment of the invention, the high-solubility heterocyclic aromatic hydrocarbon polymer is dissolved in a high-polarity solvent to obtain a polymer solution, and the polymer solution is molded and dried to obtain a polymer film, and the polymer film is doped with phosphoric acid to obtain the ion exchange membrane. The ion exchange membrane prepared by the method has low processing difficulty, high forming quality and better mechanical property.
In some embodiments, in the step 1), the mass percentage concentration of the polymer solution is 2% -30%;
and/or, in the step 2), the drying temperature is 60-220 ℃; the drying time is 0.1-48 h;
and/or, in the step 2), the thickness of the heterocyclic aromatic hydrocarbon polymer film is 15-200 μm;
and/or, in the step 3), the mass percentage concentration of the phosphoric acid solution is more than or equal to 50%; the soaking time is 12-48 h.
Drawings
FIG. 1 is an infrared spectrum of PBI-1, G-PBI-1 and H-PBI-1.
FIG. 2 is a DSC temperature rise curve of PBI-1.
FIG. 3 is a DSC temperature rise curve of G-PBI-1.
FIG. 4 is a DSC temperature rise curve of H-PBI-1.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The method for improving the solubility of the heterocyclic aromatic polymer provided by the embodiment of the invention comprises the following steps:
(1) Adding the heterocyclic aromatic hydrocarbon polymer solution into a low-temperature first poor solvent, quenching and separating out polymer solids;
(2) Washing the polymer solids with a low temperature second poor solvent;
(3) And (3) drying the polymer solid washed in the step (2) at a low temperature to obtain the high-solubility heterocyclic aromatic polymer.
According to the method for improving the solubility of the heterocyclic aromatic polymer, disclosed by the embodiment of the invention, in the solution of the untreated heterocyclic aromatic polymer, the heterocyclic aromatic polymer is dissolved, the crystallization of the heterocyclic aromatic polymer is destroyed in the dissolving process, and the ordered polymer molecular conformation is converted into the disordered conformation. And then pouring the heterocyclic aromatic polymer solution into the first poor solvent at low temperature to separate out, washing and drying at low temperature to obtain the high-solubility heterocyclic aromatic polymer. The precipitation and washing steps in the preparation process of the high-solubility heterocyclic aromatic polymer can effectively remove micromolecular impurities which are difficult to volatilize, and residual solvents, auxiliary agents and impurities in polymer solids are removed by washing.
In the embodiment of the invention, the method for improving the solubility of the heterocyclic aromatic polymer requires that the temperature of the whole process control system is low, and the low temperature control of the whole process is to prevent the heterocyclic aromatic polymer molecules from being converted into an ordered conformation and further form crystals, so that the solubility is poor. The rigid structure and hydrogen bonding of the heterocyclic aromatic polymer enable the heterocyclic aromatic polymer to be converted from an amorphous state to a crystalline state at room temperature, and the molecular level is that the molecular structure of the polymer is converted from disorder to order. In polymer solutions and melts, the structure of the polymer molecules is disordered, and in this state, quenching to obtain amorphous or low crystallinity polymer solids is a common method in the polymer arts. Since the decomposition temperature of the heterocyclic aromatic polymer is typically below the melting temperature, amorphous or low crystallinity polymer solids cannot be obtained by melt quenching the heterocyclic aromatic polymer. In the case of a heterocyclic aromatic polymer, cold crystallization occurs at room temperature due to hydrogen bonding, and it is impossible to obtain a polymer having low crystallinity or an amorphous polymer by precipitation treatment and drying treatment at a temperature lower than the glass transition temperature as in most polymers, and precipitation and drying at a temperature lower than room temperature are required to prevent the heterocyclic aromatic polymer from being recrystallized to deteriorate the solubility.
In the embodiment of the invention, compared with the heterocyclic aromatic hydrocarbon polymer before treatment, the polymer molecular chain conformation of the high-solubility heterocyclic aromatic hydrocarbon polymer is mainly disordered, the disorder degree of the molecular chain segment is high, the polymer molecular conformation is more similar to that of the polymer in solution, the amorphous polymer is easier to dissolve than the crystalline polymer, and the solubility is improved. When the high-solubility heterocyclic aromatic polymer is dissolved in a solvent, the polymer and the solvent can be prevented from forming gel at a higher concentration, the solution state is kept, the shearing viscosity is lower and the gel is not easy to form at the same concentration, and the processability of the heterocyclic aromatic polymer is improved. The heterocyclic aromatic polymer solution is treated at a low temperature to obtain the high-solubility heterocyclic aromatic polymer, the chemical structure of the heterocyclic aromatic polymer is not changed, and the material performance is not reduced due to the change of the chemical structure.
In some embodiments, in the step (1), the heterocyclic aromatic hydrocarbon polymer comprises at least one of benzimidazole polymer, benzoxazole polymer, benzothiazole polymer, preferably benzimidazole polymer;
the benzimidazole polymer comprises a polymer containing benzimidazole repeating units and/or modified benzimidazole repeating units.
The structural formula of the benzimidazole repeating unit is as follows:
；
as the-NH on the benzimidazole repeating unit has reactivity, different groups can be grafted to chemically modify the benzimidazole repeating unit, so as to obtain benzimidazole polymer containing modified benzimidazole repeating unit;
the structural formula of the modified benzimidazole repeating unit is as follows:
wherein R is 1 Selected from alkyl, fluoroalkyl, aryl, and n-propylSulfonic acid or an alkali metal salt thereof, n-butyl sulfonic acid or an alkali metal salt thereof, wherein the alkali metal comprises at least one of lithium, sodium and potassium; alkyl is selected from C 1 ~C 12 Alkyl of (a); the fluoroalkyl is selected from trifluoromethyl, pentafluoroethyl, heptafluoropropyl; the aryl is selected from phenyl, benzyl, phenethyl, phenylpropyl, p-trifluoromethylphenyl, p-methylphenyl.
Preferably, the benzimidazole polymer has a structural formula:
wherein R is 0 And R is 5 Each independently selected from H, alkyl, fluoroalkyl, aryl, n-propyl sulfonic acid or an alkali metal salt thereof, n-butyl sulfonic acid or an alkali metal salt thereof, wherein the alkali metal comprises at least one of lithium, sodium and potassium; alkyl is selected from C 1 ~C 12 Alkyl of (a); the fluoroalkyl is selected from trifluoromethyl, pentafluoroethyl, heptafluoropropyl; aryl is selected from phenyl, benzyl, phenethyl, phenylpropyl, p-trifluoromethylphenyl, p-methylphenyl;
R 2 And R is 3 Each independently selected from-CH 2 -、-O-、-SO 2 -, -CO-, -S-or direct bonding; r is R 4 Selected from alkyl, aryl or heteroatom-containing groups; the alkyl group is selected from the group consisting of-CH 2 -、-(CH 2 ) 2 -、-C(CH 3 ) 2 CH 2 -、-CH(CH 3 )CH 2 -、-CH(CH 2 CH 3 )CH 2 -; the aryl group is selected from、/>、/>The method comprises the steps of carrying out a first treatment on the surface of the The heteroatom-containing group is selected from the group consisting of-O-, -SO 2 -、-CO-、-S-、/>、/>、、/>；
In specific embodiments, the benzimidazole polymer includes at least one of the following structural formulas:
。
the benzoxazole polymer is a polymer containing benzoxazole repeating units, and the structural formula of the benzoxazole repeating units is as follows:
。
the benzothiazole polymer is a polymer containing benzothiazole repeating units, and the benzothiazole repeating units have the structural formula:
。
in some embodiments, in step (1), the heterocyclic aromatic polymer has a number average molecular weight (M n ) 5000-1000000 is preferably 10000 to 800000, more preferably 20000 to 600000, and even more preferably 30000 to 500000. In the embodiment of the invention, the heterocyclic aromatic hydrocarbon polymer with lower molecular weight has better solubility, and the formed polymer solution has low shearing viscosity, so that the solubility is not required to be further improved to improve the processing performance. Higher molecular weight heterocyclic aromatic polymers are generally insoluble and cannot be processed through the form of polymer solutions.
In some embodiments, in step (1), the solvent of the heterocyclic aromatic polymer solution comprises at least one of a strong acid or a highly polar solvent; preferably, the strong acid comprises at least one of sulfuric acid, methanesulfonic acid or trifluoromethanesulfonic acid; the high polarity solvent includes at least one of DMF, DMAc, DMSO, hexamethylphosphoric triamide, tetramethyl sulfoxide or NMP.
In some embodiments, in step (1), the heterocyclic aromatic polymer solution has a shear viscosity of 800 mPas or less, preferably 400 mPas or less, more preferably 200 mPas or less. In the embodiment of the invention, the fluidity of the heterocyclic aromatic polymer solution is characterized by shear viscosity, the viscosity is too high, a dispersion system formed by the polymer and the solvent mixture is closer to a gel state, and the higher the regularity of polymer molecular chain segments in the dispersion system is, the polymer solubility cannot be effectively improved even if precipitation and drying are carried out at low temperature.
In some embodiments, in the step (1), the heterocyclic aromatic polymer solution is 0.1% -20% by mass. In the examples of the present invention, the concentration range of the heterocyclic aromatic polymer is mainly determined by the shear viscosity of the solution, and the shear viscosity and the polymer concentration are positively correlated.
In some embodiments, in the step (1), the temperature of the low-temperature first poor solvent is-110 to 10 ℃, preferably-100 to 5 ℃, more preferably-80 to 2 ℃, and even more preferably-80 to-10 ℃. In the embodiment of the invention, the temperature of the low-temperature first poor solvent is optimized, which is favorable for improving the solubility of the heterocyclic aromatic polymer. If the temperature is further increased, the heterocyclic aromatic polymer molecules may undergo conformational transition or even recrystallize under the action of hydrogen bonds, while further temperature reduction increases the cost drastically without further improvement in the final effect.
In some embodiments, in step (1), the first poor solvent comprises at least one of water, hydrocarbons, halogenated hydrocarbons, alcohols, ethers, acetals, ketones, esters; in view of the freezing point, toxicity, cost and miscibility of the solvent with a highly polar solvent, it is preferable that the first poor solvent include at least one of cyclohexane, methylcyclohexane, toluene, xylene, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, acetone, butanone, pentanone, diethyl ether, isopropyl ether, propyl ether, methyl isopropyl ether, tetrahydrofuran, tetrahydropyran, carbon tetrachloride or a C1 to C8 fatty alcohol; more preferably, the first poor solvent includes at least one of cyclohexane, ethyl acetate, acetone, butanone, isopropyl ether, tetrahydrofuran, methanol, ethanol, isopropanol, and n-propanol.
In some embodiments, in step (1), the first poor solvent is an ice-water mixture. In the embodiment of the invention, the effect of using ice water for the polymer with strong part rigidity is very small, but the ice water has low cost, good safety and good effect of removing inorganic salt.
In some embodiments, in the step (1), the first poor solvent is a water-alcohol mixture, preferably the alcohol includes C 1 ~C 8 More preferably, the alcohol comprises at least one of methanol, ethanol, isopropanol, n-propanol; the temperature of the first poor solvent is not higher than-10 ℃, preferably from-40 ℃ to-10 ℃; preferably, the mass content of water in the hydroalcoholic mixture is not less than 10%; in a specific embodiment, the first poor solvent is a mixture of water, isopropanol, and n-propanol at-10 ℃. In the embodiment of the invention, the toxicity of the reagent used in the water-alcohol mixture precipitation system is low, water-soluble and oil-soluble small molecule impurities can be dispersed in the precipitation process, the separation of the small molecule impurities and the polymer is convenient, and the vacuum drying speed is far faster than that of water.
In some embodiments, in the step (1), the volume of the first poor solvent is 2 to 10 times, specifically, for example, 2 times, 4 times, 6 times, 8 times, 10 times, the volume of the heterocyclic aromatic hydrocarbon polymer solution. In the embodiment of the invention, too little amount of the first poor solvent can cause incomplete precipitation of the polymer, and too much amount of residual solvent in precipitated solids can not improve precipitation effect.
In some embodiments, in step (1), the heterocyclic aromatic polymer solution contains an auxiliary agent comprising at least one of a lithium salt or a hydrogen bond breaker; preferably, the lithium salt comprises lithium chloride; the hydrogen bond breaker comprises at least one of urea, fatty acid and trifluoroacetic acid, and the fatty acid comprises at least one of formic acid or acetic acid; the mass content of the auxiliary agent in the heterocyclic aromatic polymer solution is 0% -5%, specifically, for example, 1%,2%,3%,4% and 5%. In the embodiment of the invention, the additive is added into the heterocyclic aromatic polymer solution, so that the additive can improve the solubility, reduce the dosage of the solvent and the precipitant, and can be dissolved to obtain the heterocyclic aromatic polymer solution with higher concentration. In general, adjuvants can have an adverse effect on the properties of the fabricated product while improving the solubility of the heterocyclic aromatic polymer. However, the polymer solution prepared by the method can separate out the polymer in the first poor solvent, and can remove the auxiliary agent and other impurities together after washing and purification, so that the obtained high-solubility heterocyclic aromatic polymer is not influenced by the auxiliary agent in the subsequent processing process.
In some embodiments, in step (1), the preparation of the heterocyclic aromatic hydrocarbon polymer solution comprises: dissolving a heterocyclic aromatic polymer in a solvent to obtain a heterocyclic aromatic polymer solution, preferably dissolving the heterocyclic aromatic polymer in the solvent, and adding an auxiliary agent to obtain the heterocyclic aromatic polymer solution; optionally, the temperature of dissolution is 20-60 ℃. In the embodiment of the invention, the additive is added into the heterocyclic aromatic polymer solution, and the additive can improve the solubility to obtain the heterocyclic aromatic polymer solution.
In some embodiments, in the step (1), the heterocyclic aromatic polymer solution is a solution after the synthesis reaction of the heterocyclic aromatic polymer is completed, preferably, the solution after the synthesis reaction of the heterocyclic aromatic polymer is a solution after the synthesis reaction of the heterocyclic aromatic polymer is completed by solution polymerization. In the embodiment of the invention, the method for improving the solubility can be used as a post-treatment method in the preparation process of the heterocyclic aromatic polymer to prepare the high-solubility heterocyclic aromatic polymer.
In some embodiments, in step (2), the second poor solvent comprises at least one of water, hydrocarbons, halogenated hydrocarbons, alcohols, ethers, acetals, ketones, esters; in view of the freezing point, toxicity, cost and miscibility of the solvent with a highly polar solvent, preferably, the second poor solvent includes at least one of cyclohexane, methylcyclohexane, toluene, xylene, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, acetone, butanone, pentanone, diethyl ether, isopropyl ether, propyl ether, methyl isopropyl ether, tetrahydrofuran, tetrahydropyran, carbon tetrachloride or a C1 to C8 fatty alcohol; more preferably, the second poor solvent includes at least one of cyclohexane, ethyl acetate, acetone, butanone, isopropyl ether, tetrahydrofuran, methanol, ethanol, isopropanol, and n-propanol. In the embodiment of the invention, the second poor solvent is preferably a volatile solvent or a solvent with a higher three-phase temperature, so that the low-temperature drying is facilitated.
In some embodiments, in step (2), the second poor solvent is an ice-water mixture. In the embodiment of the invention, the effect of using ice water for the polymer with strong part rigidity is very small, but the ice water has low cost, good safety and good effect of removing inorganic salt.
In some embodiments, in step (2), the second poor solvent is a hydroalcoholic mixture, preferably the alcohol comprises C 1 ~C 8 More preferably, the alcohol comprises at least one of methanol, ethanol, isopropanol, n-propanol; the temperature of the second poor solvent is not higher than-10 ℃, preferably from-40 ℃ to-10 ℃; preferably, the hydroalcoholicThe mass content of water in the mixture is not less than 10%. In the embodiment of the invention, the water-alcohol mixture can disperse water-soluble and oil-soluble small molecular impurities, is convenient for separating the small molecular impurities from the polymer, and has a vacuum drying speed far faster than that of water.
In some embodiments, in the step (2), the temperature of the low-temperature second poor solvent is-110 to 10 ℃, preferably-100 to 5 ℃, and more preferably-80 to 2 ℃. In the embodiment of the invention, the temperature of the low-temperature second poor solvent is optimized, which is beneficial to improving the solubility of the polymer. If the temperature is further increased, the heterocyclic aromatic polymer molecules may undergo conformational transition or even recrystallize under the action of hydrogen bonds, while further temperature reduction increases the cost drastically without further improvement in the final effect.
In some embodiments, in step (2), the precipitated polymer solids are alternately washed in a second, different poor solvent, preferably 2-5 times; preferably, the ice-water mixture and methanol below-5 ℃ are used for cleaning alternately; alternatively cleaning with ice water and acetone at a temperature below-5 ℃. In the embodiment of the invention, for the cleaning step, the precipitated polymer solids are alternately cleaned in different second poor solvents, and the non-polymer components in the polymer solids are removed as thoroughly as possible by utilizing the difference of the poor solvents on the dispersibility of the solvents, the auxiliary agents and the impurities, so as to realize the purification purpose.
In some embodiments, in step (2), the second poor solvent is more volatile than the solvent of the heterocyclic aromatic polymer solution. In the embodiment of the invention, the second poor solvent has high volatility and is easier to remove by low-temperature drying.
In some embodiments, in the step (3), the low temperature is-110 to 10 ℃, preferably-100 to 5 ℃, further preferably-80 to 2 ℃, and more preferably-2 to-50 ℃. In the embodiment of the invention, the low-temperature drying temperature is optimized, which is beneficial to improving the solubility of the polymer. If the temperature is further increased, the heterocyclic aromatic polymer molecules may undergo conformational transition or even recrystallize under the action of hydrogen bonds, while further temperature reduction increases the cost drastically without further improvement in the final effect.
In some embodiments, in step (3), the drying is vacuum drying; the vacuum drying adopts a freeze dryer; optionally, the vacuum drying pressure is less than 100Pa. In the embodiment of the invention, the vacuum drying efficiency is higher, the solvent residue at the drying end point is less, and the vacuum drying is preferred in the low-temperature drying process in consideration of the volatilization efficiency and the content of residual volatile matters.
In some embodiments, in step (3), the high-solubility heterocyclic aromatic hydrocarbon polymer has a volatile content of 12% or less, preferably 8% or less, and more preferably 6% or less by mass. In the examples of the present invention, volatiles other than polymer remain in the final highly soluble heterocyclic aromatic polymer product.
In some embodiments, a method of increasing the solubility of a heterocyclic aromatic polymer comprises directly drying a heterocyclic aromatic polymer solution at low temperature to yield a high solubility heterocyclic aromatic polymer. In the embodiment of the invention, the efficiency is low, and the solvent is not thoroughly removed.
The heterocyclic aromatic polymer with high solubility is prepared by the method for improving the solubility of the heterocyclic aromatic polymer. In the embodiment of the invention, compared with the heterocyclic aromatic hydrocarbon polymer before treatment, the polymer molecular chain conformation of the high-solubility heterocyclic aromatic hydrocarbon polymer is mainly disordered, the solubility is high, when the high-solubility heterocyclic aromatic hydrocarbon polymer is dissolved in a solvent, the high-solubility heterocyclic aromatic hydrocarbon polymer can avoid the polymer and the solvent to form gel at a higher concentration, the solution state is maintained, the shearing viscosity is lower and the gel is not easy to be formed at the same concentration, the processability of the heterocyclic aromatic hydrocarbon polymer is improved, the chemical structure of the heterocyclic aromatic hydrocarbon polymer is not changed, and the material performance is not reduced due to the change of the chemical structure.
According to the storage method of the high-solubility heterocyclic aromatic hydrocarbon polymer, the high-solubility heterocyclic aromatic hydrocarbon polymer is stored in a low-temperature environment, wherein the temperature of the low-temperature environment is less than or equal to 4 ℃, preferably less than or equal to 0 ℃, and more preferably less than or equal to-5 ℃. In the embodiment of the invention, the high-solubility heterocyclic aromatic hydrocarbon polymer is stored at low temperature, so that the polymer molecular chain segment is prevented from moving to be more orderly or even crystallizing under the action of self rigidity and hydrogen bond, and the good solubility of the polymer can be maintained.
The application of the high-solubility heterocyclic aromatic polymer is that the high-solubility heterocyclic aromatic polymer is used for a fuel cell, preferably a medium-temperature fuel cell proton exchange membrane. In the embodiment of the invention, the ion exchange membrane prepared from the high-solubility heterocyclic aromatic polymer has better uniformity and excellent electrochemical performance and mechanical performance, and can be applied to fuel cells.
The ion exchange membrane comprises the high-solubility heterocyclic aromatic polymer. In the embodiment of the invention, the ion exchange membrane prepared from the high-solubility heterocyclic aromatic polymer has better uniformity and excellent electrochemical performance and mechanical performance, and can be applied to a proton exchange membrane of a medium-temperature fuel cell.
In some embodiments, the ion exchange membrane is doped with phosphoric acid.
The preparation method of the ion exchange membrane provided by the embodiment of the invention comprises the following steps:
1) Dispersing a high-solubility heterocyclic aromatic hydrocarbon polymer in a solvent to obtain a polymer solution;
2) Shaping and drying the polymer solution to obtain a heterocyclic aromatic polymer film;
3) And soaking the heterocyclic aromatic polymer membrane in a phosphoric acid solution for adsorption, preferably, adsorbing to a saturated state, so as to obtain the phosphoric acid doped ion exchange membrane.
In the embodiment of the invention, the high-solubility heterocyclic aromatic hydrocarbon polymer is dissolved in a high-polarity solvent to obtain a polymer solution, and the polymer solution is molded and dried to obtain a polymer film, and the polymer film is doped with phosphoric acid or a small molecular organic phosphonic acid compound to obtain the ion exchange membrane. The ion exchange membrane prepared by the method has low processing difficulty, high forming quality and better mechanical property.
In some embodiments, in the step 1), the mass percentage concentration of the polymer solution is 2% -30%, specifically, for example, 2%,5%,10%,20%,30%; in the step 1), the solvent includes a highly polar solvent; the high polarity solvent includes at least one of DMF, DMAc, DMSO, hexamethylphosphoric triamide, tetramethyl sulfoxide or NMP.
In some embodiments, in step 1), the shaping comprises at least one of coating, casting, or pouring.
In some embodiments, in the step 2), the drying temperature is 60-220 ℃; the drying time is 0.1-48 h; and/or, in the step 2), the thickness of the heterocyclic aromatic hydrocarbon polymer film is 15-200 μm.
In some embodiments, prior to step 3), the heterocyclic aromatic hydrocarbon polymer film obtained in step 2) is subjected to water boiling and then drying; preferably, the temperature of the water boiling is 80-85 ℃; the boiling time is 0.5-3h; the drying temperature is 50-220 ℃; the drying time is 0.1-24 h. In the embodiment of the invention, the residual high-polarity solvent is removed by hot water boiling.
And/or, in the step 3), the mass percentage concentration of the phosphoric acid solution is more than or equal to 50%, preferably 85%; the soaking time is 12-48 h.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
Proton conductivity, tensile strength, tensile strain at break test methods refer to proton exchange membrane fuel cell section 3: proton exchange membrane test methods. The proton conductivity was measured at 160℃under anhydrous conditions.
Shear viscosity: the viscosity was tested using a Haake Mars rheometer, the test method was a constant shear rate test, and the relevant test parameters were as follows: the test time was 60 s, the test temperature was 25℃and the shear rate was 40 1/s. Three sets of effective data were taken for the same sample and the average was the shear viscosity of the sample.
Intrinsic viscosity: the intrinsic viscosity of the polymer was measured using an Ubbelohde viscometer using NMP as the solvent. The intrinsic viscosity of a polymer can reflect the molecular weight and crystallization of the polymer, with higher intrinsic viscosity at higher molecular weights and higher crystallinity before dissolution of the polymer. For the present examples, the chemical structure and molecular weight of the highly soluble heterocyclic aromatic polymer and the untreated heterocyclic aromatic polymer were unchanged, and the main reason for the change in intrinsic viscosity was the change in crystallinity of the polymer.
DSC: the DSC performance curve of the perfluorosulfonic acid resin solid was tested using a differential scanning calorimeter (model DSC 3) of Metrele-tolidol. The heating rate is 10 ℃/min, the heating temperature range is determined according to the properties of the sample, and the sample is prevented from being decomposed.
Preparation of the polymer solution: the dissolution method of the polymers in examples and comparative examples is the same: mixing a polymer with a certain mass and a solvent, and stirring for 3 hours at room temperature to disperse and dissolve. If necessary, the auxiliary agent is added while stirring at room temperature for 0.5 h. Then heating to 60 ℃, and stirring for 21 hours at constant temperature to obtain a polymer solution.
The poor solvents, highly polar solvents and adjuvants used in the examples are all common chemical agents. Benzimidazole polymers are available from the midget energy materials technologies (Dalian) and Shanghai Cheng Jun plastics technologies. The high-solubility heterocyclic aromatic hydrocarbon polymers prepared in the embodiment are all preserved at low temperature in the environment of minus 20 to minus 35 ℃ and are taken out for use when dissolved.
Example 1:
a method of increasing the solubility of a heterocyclic aromatic polymer comprising the steps of:
(1) 5g of PBI-1 polymer was weighed and dissolved in 500 mL of DMSO, and the solution was stirred at 60℃and filtered to remove insoluble matters, thereby obtaining a polymer solution.
(2) The polymer solution was poured into 1500 mL ice water mixture and stirred to precipitate a polymer solid.
(3) The precipitated polymer solids were alternately washed 4 times with an ice-water mixture and methanol. The temperature of the methanol is always below-5 ℃. Finally, the mixture is washed by ice-water mixture.
(4) And finally, after washing by using an ice-water mixture, transferring the solid to a freeze dryer, and vacuum drying at the temperature ranging from minus 2 ℃ to minus 10 ℃ to obtain the high-solubility heterocyclic aromatic polymer G-PBI-1, wherein the volatile content of the G-PBI-1 is 2.4%.
The structural formula of the PBI-1 polymer is as follows:
。
Example 2:
a method of increasing the solubility of a heterocyclic aromatic polymer comprising the steps of:
(1) 5g of PBI-1 polymer and 2g of lithium chloride were weighed into 150 mL of DMAc, and insoluble matters were removed by filtration to obtain a polymer solution.
(2) The polymer solution was poured into a 500 mL ice water mixture and stirred to precipitate a polymer solid.
The polymer solids precipitated in steps (3) and (4) were treated in the same manner as in steps (3) and (4) of example 1.
The volatile content of the high-solubility heterocyclic aromatic polymer G-PBI-2 and the G-PBI-2 is 2.3 percent.
Example 3:
the same procedure as in example 2 was followed, except that: in the step (1), the heterocyclic aromatic hydrocarbon polymer is PBI-2, the auxiliary agent is 0.5 g trifluoroacetic acid, and the solvent of the polymer solution is DMF; in the step (2), the first poor solvent is ethanol at the temperature of minus 80 ℃.
The volatile content of the high-solubility heterocyclic aromatic polymer G-PBI-3, G-PBI-3 is 2.6%.
The structural formula of the PBI-2 polymer is as follows:
。
example 4:
the same procedure as in example 2 was followed, except that: in the step (1), the heterocyclic aromatic polymer is PBI-3, the auxiliary agent is 8g of formic acid, and the solvent of the polymer solution is tetramethyl sulfoxide; in the step (2), the first poor solvent is butanone at the temperature of minus 30 ℃.
The volatile content of the high-solubility heterocyclic aromatic polymer G-PBI-4 is 2.7 percent.
The structural formula of the PBI-3 polymer is as follows:
。
example 5:
the same procedure as in example 2 was followed, except that: in the step (1), the heterocyclic aromatic polymer is PBI-4; in the step (2), the first poor solvent is a mixture of 100mL of isopropyl ether, 100mL of methanol, 100mL of tetrahydrofuran, 100mL of ethyl acetate and 100mL of cyclohexane, the temperature of the first poor solvent is-15 ℃, and the drying temperature is-10 to-20 ℃.
The volatile content of the high-solubility heterocyclic aromatic polymer G-PBI-5, G-PBI-5 is 2.5%.
The structural formula of the PBI-4 polymer is as follows:
。
example 6:
the same procedure as in example 5 was followed, except that: in the step (2), the first poor solvent is a mixture of 200mL of water, 150mL of isopropanol and 150mL of n-propanol, the temperature of the first poor solvent is-10 ℃, and the drying temperature is-30 to-50 ℃.
The volatile content of the high-solubility heterocyclic aromatic polymer G-PBI-6 is 2.2 percent.
Example 7:
the same procedure as in example 6 was followed, except that: in the step (1), the mass of the PBI-4 polymer was 15g.
The volatile content of the obtained high-solubility heterocyclic aromatic polymer G-PBI-7,G-PBI-7 is 2.9%.
Example 8:
(1) 1g of PBI-3 is dissolved in 50mL of DMSO, 0.15g of sodium hydride is added under the protection of inert gas, and the mixture is reacted for 3 hours at 40 ℃; 0.59g of 1, 4-butane sulfonic acid lactone is added into the reaction system, and the reaction is carried out for 8 hours at 40 ℃ to obtain the modified heterocyclic aromatic polymer PBI-5. 1mL of water is added to inactivate the catalyst, the reaction system solution is poured into 150mL of cold acetone for precipitation, and the temperature of the cold acetone is minus 30 ℃.
(2) The product was alternately washed 4 times with ice water and cold acetone at-30 ℃.
(3) Freeze drying at-20deg.C in a freeze dryer to obtain high-solubility heterocyclic aromatic polymer G-PBI-9,G-PBI-9 with volatile content of 5.9%.
The structural formula of the PBI-5 is as follows:
。
example 9:
a method for preparing an ion exchange membrane, comprising the steps of:
1) 0.5G of the G-PBI-1 polymer solid was dissolved in 9.5G of DMSO, the solution was poured into a super petri dish, and the solvent was evaporated by drying at 80℃and 120℃for 3h and 21h, respectively, to obtain a film sample.
2) Stripping the film sample from the culture dish, boiling in 80-85 ℃ hot water for 1h to remove residual DMSO, and finally drying the film sample at 190 ℃ for 1h to obtain the film M-1.
3) The membrane M-1 was then immersed in a Phosphoric Acid (PA) solution (85 wt%) at room temperature for 24 hours to ensure that the membrane adsorbed phosphoric acid was saturated, yielding an ion exchange membrane PEM-1. The phosphoric acid doping level was calculated from the mass change of the film before and after doping with phosphoric acid.
Example 10:
a method for preparing an ion exchange membrane, comprising the steps of:
1) 2-g G-PBI-5 Polymer solid was dissolved in 8g of DMAc, the solution was poured into a petri dish, and the solvent was evaporated at 100℃for 24 hours to obtain a film sample.
2) Peeling the film sample from the culture dish, boiling in 80-85deg.C hot water for 1 hr, and drying at 190 deg.C for 1 hr to obtain film M-2.
3) The membrane M-2 was then immersed in a phosphoric acid solution (85 wt%) at room temperature for 24 hours to obtain an ion exchange membrane PEM-2.
Example 11:
G-PBI-1, G-PBI-2, G-PBI-3 and G-PBI-4 were dissolved and dispersed in DMSO solvent at polymer mass contents of 0.5%, 5% and 15%, respectively.
G-PBI-5, G-PBI-6 and G-PBI-7 were dissolved and dispersed in DMAc solvent at polymer contents of 0.5%, 5% and 20%, respectively.
G-PBI-9 was dissolved and dispersed in DMF solvent at a polymer mass content of 5% and 20%, respectively.
Comparative example 1:
the G-PBI-1 of example 1 was heat treated in an oven at 140℃for 1H to give an H-PBI-1 polymer solid.
PBI-1, H-PBI-1 and PBI-3 were dissolved and dispersed in DMSO solvent, respectively, with polymer contents of 0.5%, 5% and 15% by mass, respectively.
PBI-1, H-PBI-1 and PBI-3 at 5% and 15% mass content did not dissolve completely to form a solution, which was a mixture of gel and solid. A0.5% mass content system can form a solution.
Comparative example 2:
PBI-2 was dissolved and dispersed in DMSO solvent at polymer mass contents of 0.5%, 5% and 15%, respectively.
At 15% by mass, it was not completely dissolved to form a solution, which was a mixture of gel and solid.
Comparative example 3:
PBI-4 was dissolved and dispersed in DMAc solvent at polymer mass contents of 0.5%, 5% and 20%, respectively.
At 20% by mass, it is not completely dissolved to form a solution, which is a mixture of gel and solid.
Comparative example 4:
the same procedure as in example 8 was followed, except that: in the step 1), after the reaction, 1mL of water was added to deactivate the catalyst, and the reaction system was poured into 150mL of acetone to precipitate, and the temperature of the acetone was room temperature (about 20 ℃). In said step 2), the product is alternately washed 4 times with water at normal temperature (about 20 ℃) and acetone (about 20 ℃). In the step 3), the modified heterocyclic aromatic polymer PBI-9 is obtained by vacuum drying in a vacuum oven at 45 ℃ for 72 hours.
PBI-9 was dissolved and dispersed in DMF solvent at a polymer mass content of 5% and 20%, respectively.
Comparative example 5:
a method for preparing an ion exchange membrane, comprising the steps of:
1) 0.5 g of PBI-1 solid and 0.05g of lithium chloride auxiliary agent were dissolved in 9.5g of DMSO, the solutions were poured into a super plate, and the solvents were evaporated by drying at 80℃and 120℃for 3h and 21h, respectively, to obtain film samples.
2) And stripping the obtained film sample from the culture dish, boiling the film sample in hot water at 80-85 ℃ for 1h, and finally drying the film sample at 190 ℃ for 1h to obtain the film D-M-1.
3) The membrane D-M-1 was then immersed in a Phosphoric Acid (PA) solution (85 wt%) at room temperature for 24 hours to give an ion exchange membrane D-PEM-1.
Comparative example 6:
a method for preparing an ion exchange membrane, comprising the steps of:
1) 2g of PBI-4 and 0.05g of trifluoroacetic acid were dissolved in 8 g of DMAc, and the solution was poured into a petri dish, and the solvent was evaporated at 100℃for 24 hours to obtain a film sample.
2) And (3) peeling the obtained film sample from the culture dish, boiling the film sample in hot water at 80-85 ℃ for 1h, and finally drying the film sample at 190 ℃ for 1h to obtain the film D-M-2.
3) The membrane D-M-2 was immersed in a phosphoric acid solution (85 wt%) at room temperature for 24 hours to obtain an ion exchange membrane D-PEM-2.
Comparative example 7
The same procedure as in comparative example 5 was followed except that no lithium chloride auxiliary was added in step 1).
PBI-1 forms a mixture of gel and solid in a solvent and cannot be shaped as a solution.
Comparative example 8
The same procedure as in comparative example 6 was followed except that no trifluoroacetic acid aid was added in step 1).
PBI-4 forms a mixture of gel and solid in a solvent and cannot be shaped as a solution.
Table 1 shows the intrinsic viscosities of G-PBI-1, G-PBI-2, G-PBI-3, G-PBI-4, PBI-1, H-PBI-1, PBI-2 and PBI-3 and the shear viscosities of solutions of different concentrations (the solvent is DMSO).
TABLE 1
The high solubility heterocyclic aromatic polymers of the present invention have significantly reduced intrinsic viscosity as compared to untreated heterocyclic aromatic polymers. This change in intrinsic viscosity is not due to a change in chemical structure or molecular weight distribution of the heterocyclic aromatic polymer, but rather is due to physical factors such as polymer crystallinity. H-PBI is that the molecular chain segment is fully rearranged after the high-temperature heat treatment of the G-PBI-1 and crystallized at high temperature, the intrinsic viscosity of the H-PBI is close to that of the PBI-1, and the difference of the intrinsic viscosity and the thermal history of the material are proved to be related. The heterocyclic aromatic polymer has good thermal stability and chemical stability, and the chemical structure of the heterocyclic aromatic polymer is not changed by temperature change and solvent action in the embodiment. The high-solubility heterocyclic aromatic polymer obtained after treatment can form a solution at a higher concentration, and the solutions at different concentrations have lower shear viscosity. The low shear viscosity is beneficial to the flowing and shaping of the solution, and has better processing performance.
FIG. 1 is an infrared spectrum of PBI-1, G-PBI-1 and H-PBI-1, with infrared characteristic peaks and peak intensities of three test samples being substantially identical, indicating that the chemical structures of the three are identical. The PBI-1 is subjected to a series of treatment steps to obtain G-PBI-1 and H-PBI-1, but the chemical structure is not changed all the time.
FIGS. 2 to 4 show DSC temperature rise curves of PBI-1, G-PBI-1 and H-PBI-1, respectively. In the figure, the downward peak is an endothermic peak, and the upward peak is an exothermic peak.
In FIG. 2, PBI-1 has a downward endothermic peak at a temperature of 103 to 187℃and a peak top temperature of 142.59 ℃which is caused by volatilization of the residual high boiling point solvent in the polymer.
In FIG. 3, two absorption peaks appear in the range of 30-145 ℃, the absorption peak in the lower temperature range is caused by volatilization of the low-boiling-point solvent, the absorption peak in the higher temperature range is caused by volatilization of the high-boiling-point solvent, and the absorption peak area of the low-boiling-point solvent is far larger than that of the high-boiling-point solvent, which shows that compared with the PBI-1, the treated G-PBI-1 has the volatile components mainly comprising the low-boiling-point solvent. The G-PBI-1 has obvious exothermic peak at 126-237 deg.C, and the peak top temperature is 174.66 deg.C, which is the crystallization peak of G-PBI-1, indicating that the amorphous structure of G-PBI-1 is transformed into crystalline state.
In FIG. 4, H-PBI-1 shows no obvious endothermic peak and exothermic peak during DSC heating, because the high boiling point solvent is sufficiently removed during the heat treatment at 140℃and thus there is no absorption peak caused by volatilization of the solvent, and both H-PBI-1 and PBI-1 after the heat treatment are sufficiently crystallized polymers and are not melted below the decomposition temperature and thus there is no exothermic peak caused by crystallization and no endothermic peak caused by melting.
During low temperature processing, the crystalline structure of PBI-1 is transformed into an amorphous structure, which allows G-PBI-1 to have lower intrinsic viscosity and higher solubility. After the high temperature heat treatment, the amorphous structure of the G-PBI-1 is converted into a crystalline state again to obtain H-PBI-1. The intrinsic viscosity and solubility of H-PBI-1 are similar to those of PBI-1. The heterocyclic aromatic polymer may undergo slow cold crystallization at room temperature due to the rigidity and hydrogen bonding, so that the solubility gradually decreases, and in order to maintain good solubility, the high-solubility heterocyclic aromatic polymer should be stored under low temperature conditions.
Table 2 shows the shear viscosity (DMAc solvent) of solutions of different concentrations of G-PBI-5, G-PBI-6, G-PBI-7 and PBI-4.
TABLE 2
The main chain structure of PBI-4 contains a large amount of ether bonds, and the ether bonds can be used as flexible groups to improve the solubility of the heterocyclic aromatic polymer, but untreated PBI-4 cannot form a solution with 20% mass content. G-PBI-5, G-PBI-6 and G-PBI-7 are capable of forming 20% by mass polymer solutions and have lower shear rates at 0.5% and 5% concentrations and are easier to process.
Table 3 shows the shear viscosity of solutions of different concentrations of G-PBI-9 and PBI-9 (DMF as solvent).
TABLE 3 Table 3
G-PBI-9 and PBI-9 are heterocyclic aromatic polymers obtained by modification of active sites (N-H) of sultone and imidazole groups. The solubility of the modified polymer is improved, and compared with PBI-9, the G-PBI-9 treated at low temperature has lower shear viscosity and better processability at different concentrations.
Table 4 shows the tensile strength and elongation at break of M-1, M-2, PEM-1, PEM-2, D-M-1, D-M-2, D-PEM-1 and D-PEM-2.
TABLE 4 Table 4
The M-1 and M-2 prepared using the high solubility heterocyclic aromatic polymers in the examples have better tensile strength and elongation at break than D-M-1 and D-M-2. Although the auxiliary agents such as lithium chloride and trifluoroacetic acid can improve the solubility of the heterocyclic aromatic polymer, the molding quality of the product can be adversely affected. After doping phosphoric acid, the elongation at break of the film increases and the tensile strength decreases. But PEM-1 has better mechanical properties than D-PEM-1 and PEM-2.
Table 5 shows the phosphoric acid doping levels and conductivities of PEM-1, PEM-2, D-PEM-1 and D-PEM-2.
TABLE 5
The doping level of phosphoric acid is slightly lower in PEM-1 compared with D-PEM-1, but the conductivity is higher, and the electrochemical performance is more excellent. The difference in the doping levels of phosphoric acid may be that the auxiliary lithium chloride causes voids or defects inside the film that enable the film to be doped with more phosphoric acid, but higher doping levels of phosphoric acid do not impart higher electrochemical performance.
The contrast of PEM-2 with D-PEM-2 is substantially identical to PEM-1 and D-PEM-1. Trifluoroacetic acid as an auxiliary agent increases the solubility of the heterocyclic aromatic polymer, but itself may cause adverse effects as an impurity of the molded product.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While the above embodiments have been shown and described, it should be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations of the above embodiments may be made by those of ordinary skill in the art without departing from the scope of the invention.
Claims (12)
1. A method for improving the solubility of a heterocyclic aromatic polymer comprising the steps of:
(1) Adding the heterocyclic aromatic hydrocarbon polymer solution into a low-temperature first poor solvent, quenching and separating out polymer solids;
(2) Washing the polymer solids with a low temperature second poor solvent;
(3) And (3) drying the polymer solid washed in the step (2) at a low temperature to obtain the high-solubility heterocyclic aromatic polymer.
2. The method for improving the solubility of a heterocyclic aromatic hydrocarbon polymer according to claim 1, wherein in the step (1), the heterocyclic aromatic hydrocarbon polymer comprises at least one of benzimidazole polymer, benzoxazole polymer and benzothiazole polymer;
and/or, in the step (1), the number average molecular weight of the heterocyclic aromatic polymer is 5000-1000000;
and/or, in the step (1), the solvent of the heterocyclic aromatic hydrocarbon polymer solution includes at least one of a strong acid or a highly polar solvent; the strong acid comprises at least one of sulfuric acid, methanesulfonic acid or trifluoromethanesulfonic acid; the high-polarity solvent comprises at least one of DMF, DMAc, DMSO, hexamethylphosphoric triamide, tetramethyl sulfoxide or NMP;
And/or, in the step (1), the shearing viscosity of the heterocyclic aromatic polymer solution is less than or equal to 800 mPa.s.
3. The method for improving the solubility of a heterocyclic aromatic polymer according to claim 1, wherein in the step (1), the temperature of the low-temperature first poor solvent is-110 to 10 ℃;
and/or, in the step (1), the first poor solvent comprises at least one of water, hydrocarbon, halogenated hydrocarbon, alcohol, ether, acetal, ketone, and ester;
and/or, in the step (1), the volume of the first poor solvent is 2-10 times of the volume of the heterocyclic aromatic polymer solution.
4. The method of claim 1, wherein in step (1), the heterocyclic aromatic polymer solution contains an auxiliary agent comprising at least one of a lithium salt or a hydrogen bond breaker; the lithium salt comprises lithium chloride; the hydrogen bond breaker comprises at least one of urea, fatty acid and trifluoroacetic acid; the mass content of the auxiliary agent in the heterocyclic aromatic polymer solution is 0% -5%.
5. The method for improving the solubility of a heterocyclic aromatic polymer according to claim 1, wherein in the step (1), the preparation of the heterocyclic aromatic polymer solution comprises: dissolving heterocyclic aromatic hydrocarbon polymer in a solvent to obtain heterocyclic aromatic hydrocarbon polymer solution;
And/or, in the step (1), the heterocyclic aromatic polymer solution is a solution after the synthesis reaction of the heterocyclic aromatic polymer is finished.
6. The method of claim 1, wherein in step (2), the second poor solvent comprises at least one of water, hydrocarbons, halogenated hydrocarbons, alcohols, ethers, acetals, ketones, esters;
and/or, in the step (2), the temperature of the low-temperature second poor solvent is-110-10 ℃;
and/or, in the step (3), the low temperature is-110-10 ℃;
and/or, in the step (3), the drying is vacuum drying;
and/or, in the step (3), the mass percentage of volatile matters in the high-solubility heterocyclic aromatic hydrocarbon polymer is less than or equal to 12%.
7. A high solubility heterocyclic aromatic polymer prepared by the method of improving the solubility of a heterocyclic aromatic polymer according to any one of claims 1 to 6.
8. A method of storing the high-solubility heterocyclic aromatic hydrocarbon polymer according to claim 7, wherein the high-solubility heterocyclic aromatic hydrocarbon polymer is stored in a low-temperature environment at a temperature of 4 ℃ or less.
9. Use of the high solubility heterocyclic aromatic polymer according to claim 7 for fuel cells.
10. An ion exchange membrane comprising the high solubility heterocyclic aromatic polymer according to claim 7.
11. A method of preparing the ion exchange membrane of claim 10, comprising the steps of:
1) Dispersing a high-solubility heterocyclic aromatic hydrocarbon polymer in a solvent to obtain a polymer solution;
2) Shaping and drying the polymer solution to obtain a heterocyclic aromatic polymer film;
3) And soaking the heterocyclic aromatic polymer membrane in a phosphoric acid solution for adsorption to obtain the phosphoric acid doped ion exchange membrane.
12. The method for preparing an ion exchange membrane according to claim 11, wherein in the step 1), the mass percentage concentration of the polymer solution is 2% -30%;
and/or, in the step 2), the drying temperature is 60-220 ℃; the drying time is 0.1-48 h;
and/or, in the step 2), the thickness of the heterocyclic aromatic hydrocarbon polymer film is 15-200 μm;
and/or, in the step 3), the mass percentage concentration of the phosphoric acid solution is more than or equal to 50%; the soaking time is 12-48 h.
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