CN114957657A - Method for preparing polybenzimidazole based on domestic cheap raw materials - Google Patents
Method for preparing polybenzimidazole based on domestic cheap raw materials Download PDFInfo
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- 239000004693 Polybenzimidazole Substances 0.000 title claims abstract description 75
- 229920002480 polybenzimidazole Polymers 0.000 title claims abstract description 75
- 239000002994 raw material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 claims description 34
- 239000000047 product Substances 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 14
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 7
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 20
- 239000000446 fuel Substances 0.000 abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 230000017525 heat dissipation Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0677—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8668—Binders
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/329—Phosphorus containing acids
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Abstract
The invention discloses a method for preparing polybenzimidazole based on domestic cheap raw materials, belonging to the field of proton exchange membrane fuel cells. The invention effectively inhibits the occurrence of side reaction in the polycondensation reaction process by carrying out series simple pretreatment on cheap domestic raw materials for synthesizing polybenzimidazole, thereby obtaining high-purity polybenzimidazole, and the synthesized polybenzimidazole has proper molecular weight distribution and is suitable for being used as raw materials of proton exchange membranes and catalyst layer binders in the field of high-temperature proton exchange membrane fuel cells. The polybenzimidazole prepared by the method can be applied to high-temperature proton exchange membrane fuel cells, water electrolysis, electrochemical sensors, other electrochemical devices and the like, and is used for preparing polybenzimidazole/phosphoric acid composite membranes or binders.
Description
Technical Field
The invention relates to the technical field of high-temperature proton exchange membrane fuel cells, in particular to a method for preparing polybenzimidazole based on domestic cheap raw materials.
Background
Under the current technical conditions, due to the limitation of the operation temperature of the conventional proton membrane fuel cell, the heat dissipation system configured for the fuel cell vehicle is still very large. In order to simplify a heat dissipation system, the peak value of the operating temperature of the electric pile of the Toyota Mirai automobile reaches 95 ℃, which is close to the limit of the conventional perfluorosulfonic acid proton exchange membrane, and the Toyota, Honda and the like are developing proton exchange membranes capable of working at higher temperature so as to further improve the operating temperature of the electric pile. According to the hydrothermal balance, when the operation temperature of the galvanic pile reaches about 130 ℃, the waste heat generated by the galvanic pile power generation can be taken away by the galvanic pile drainage, and the heat dissipation system is greatly simplified. In addition to simplifying the heat dissipation system, high temperature proton membrane fuel cells have other significant advantages, such as the elimination of humidification; the purity requirement on the fuel is low; the water in the electric pile is gaseous single phase, and the water management is simplified; after the shutdown, the water residue in the galvanic pile and the auxiliary components is low, and the low-temperature starting performance of the battery system is greatly improved.
High temperature proton exchange membrane and proton conductor materials capable of working at high temperature are key core materials of high temperature proton exchange membrane fuel cells. Currently, polybenzimidazole/phosphoric acid composite membranes (PBI/H) 3 PO 4 ) As the high-temperature proton exchange membrane which is closest to practical internationally, the performance at high temperature is close to the performance of the conventional perfluorosulfonic acid proton exchange membrane at low temperature (60-95 ℃). The company PBI Performance Products, USA, has implemented the aggregationThe commercial sale of benzimidazoles. PBI/H has been implemented by BASF and Fumatech in Germany 3 PO 4 And (3) producing a composite membrane and a high-temperature membrane electrode.
However, currently, commercially available polybenzimidazole or PBI/H imported from foreign countries 3 PO 4 The price of the composite film is very high, such as that sold on the market by the company PBI Performance Products of the United states
The price of polybenzimidazole resin powder is as high as 130 yuan per gram. The polybenzimidazole is synthesized by itself and is technically not difficult. Many domestic researchers have realized the synthesis of polybenzimidazole, but basically all have adopted imported raw materials. However, the price of imported synthetic raw materials is very high, for example, the price of the commonly used raw material 3, 3' -diaminobenzidine is as high as 90 RMB per gram, and the purpose of reducing the use cost of polybenzimidazole cannot be realized. In contrast, the 3, 3' -diaminobenzidine provided by domestic suppliers is only 4-5 yuan per gram, and the cost is low. However, the previous experimental results show that when domestic cheap 3,3 '-diaminobenzidine is used as a raw material, certain impurities possibly exist in domestic cheap 3, 3' -diaminobenzidine to interfere the polycondensation reaction of polybenzimidazole synthesis, so that qualified polybenzimidazole cannot be synthesized. If the problem of synthesizing polybenzimidazole by domestic cheap raw materials can be solved, the cost of the polybenzimidazole can be completely and greatly reduced, so that the further application of the polybenzimidazole in a high-temperature proton exchange membrane fuel cell is powerfully promoted.
Disclosure of Invention
In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is to provide a method for preparing polybenzimidazole based on domestic cheap raw materials, which effectively inhibits the occurrence of side reactions during the polycondensation reaction by performing a series of simple pre-treatments on the domestic cheap raw materials for synthesizing polybenzimidazole, so as to obtain high-purity polybenzimidazole, and the synthesized polybenzimidazole has a suitable molecular weight distribution, and is suitable for being used as a raw material of proton exchange membranes and catalyst layer binders in the field of high-temperature proton exchange membrane fuel cells.
In order to achieve the above object, the present invention provides a method for preparing polybenzimidazole based on domestic cheap raw materials, comprising the following steps:
step 1, sequentially adding deionized water and 3, 3' -diaminobenzidine into a round-bottom flask, and mixing according to a certain proportion to obtain a mixed solution;
step 2, adding a certain amount of activated carbon powder into the mixed solution;
step 3, heating the liquid mixture to 80-110 ℃, and stirring the liquid mixture for 4-10 hours to completely dissolve the 3, 3' -diaminobenzidine;
step 4, filtering the hot liquid mixture, removing filter residues, cooling the obtained filtrate to 0-25 ℃, and keeping for 6-30 hours until crystals of the 3, 3' -diaminobenzidine are fully precipitated;
step 5, filtering the filtrate after cooling and standing for the second time, and drying the obtained filter residue at 60-90 ℃ for 3-8 hours in vacuum to obtain pretreated 3, 3' -diaminobenzidine;
and step 10, filtering again to obtain a polybenzimidazole primary product, crushing the polybenzimidazole primary product, sequentially and repeatedly washing the polybenzimidazole primary product with deionized water and ethanol for multiple times, and drying the polybenzimidazole primary product in vacuum at 100-150 ℃ to obtain polybenzimidazole powder.
Further, in step 1, 15 to 40g of the 3, 3' -diaminobenzidine was added per 1000ml of the deionized water.
Further, the weight of the activated carbon powder added in the step 2 is 0-10% of the weight of the 3, 3' -diaminobenzidine in the step 1.
Further, in step 2, the activated carbon powder is VULCAN XC-72 or VULCAN XC-72R manufactured by CABOT company.
Further, in steps 4 and 5, filtration was performed using a sand core funnel.
Further, in step 7, the mass ratio of the pretreated 3, 3' -diaminobenzidine to the polyphosphoric acid is 1: 20-60.
Further, in step 8, the molar ratio of the pretreated 3,3 '-diaminobenzidine to the isophthalic acid is 1:0.85 to 1.2, and the molar ratio of the pretreated 3, 3' -diaminobenzidine to the phosphorus pentoxide is 1:0.8 to 1.25.
Further, in the step 9, the concentration of the sodium bicarbonate solution is 0.3-1 mol/L.
Further, in step 9, the polybenzimidazole primary product is in the form of a filament.
On the basis of a large number of tests, the invention provides a series of simple pre-treatments on cheap domestic raw material 3, 3' -diaminobenzidine for synthesizing polybenzimidazole, which can effectively inhibit the occurrence of side reactions in the polycondensation reaction process, thereby obtaining high-purity polybenzimidazole.
The conception, specific structure and technical effects of the present invention will be further described in conjunction with the accompanying drawings to fully understand the purpose, characteristics and effects of the present invention.
Drawings
FIG. 1 is an infrared spectrum of polybenzimidazole obtained in examples 1 and 2 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of polybenzimidazole obtained in example 1 and example 2 of the present invention;
FIG. 3 is a graph comparing the initial products of the polybenzimidazole synthesized in example 2 (left) and comparative example 1 (right).
Detailed Description
The technical contents of the preferred embodiments of the present invention will be made clear and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
Example 1
A method for preparing polybenzimidazole based on domestic cheap raw materials comprises the following steps:
(1) 500mL of deionized water, 8g of domestic 3,3 '-diaminobenzidine, and 0.2g of carbon powder (XC-72) were sequentially added to a round-bottom flask, and the mixture was heated to 100 ℃ while stirring the mixture at 500rpm to sufficiently dissolve the 3, 3' -diaminobenzidine. After stirring for 5 hours, the mixture was filtered while it was hot, and the obtained filtrate was left to cool at 10 ℃ for 20 hours until a solid precipitated. Filtering the filtrate again at 10 deg.C, and drying the obtained solid residue at 70 deg.C for 6 hr to obtain pretreated 3, 3' -diaminobenzidine.
(2) Adding 110g of polyphosphoric acid and 5g of the pretreated 3, 3' -diaminobenzidine into a round-bottom flask, introducing nitrogen, setting the flow rate at 150ml/min, heating the solution at 150 ℃, and stirring the solution at 300 rpm; 4g of isophthalic acid and 3.5g of phosphorus pentoxide are added at intervals of 2 hours; the temperature is adjusted to 200 ℃, after 5 hours of reaction, the reaction mixture in the round-bottom flask is poured into deionized water, stirring is carried out while chamfering, and the polybenzimidazole primary product is separated out in a filament strip shape.
(3) Taking out the filament strip polybenzimidazole, and soaking in 0.5mol/L sodium bicarbonate solution to remove acid; and filtering again, crushing the primary polybenzimidazole product, washing the crushed product for 5 times by using ethanol and deionized water, and drying the product for 6 hours at the temperature of 120 ℃ to obtain polybenzimidazole resin powder.
Example 2
A method for preparing polybenzimidazole based on domestic cheap raw materials comprises the following steps:
(1) a round-bottom flask was charged with 200mL of deionized water, 4g of domestic 3,3 '-diaminobenzidine, and 0.1g of carbon powder (XC-72), and the mixture was heated to 100 ℃ while stirring at 450rpm to sufficiently dissolve the 3, 3' -diaminobenzidine. After stirring for 6 hours, the mixture was filtered while hot, and the filtered filtrate was left to cool at 20 ℃ for 28 hours until a solid precipitated. And (3) filtering again at the temperature of 20 ℃, and drying the obtained solid filter residue at the temperature of 75 ℃ for 6 hours to obtain the pretreated 3, 3' -diaminobenzidine.
(2) Adding 120g of polyphosphoric acid and 4g of pretreated 3, 3' -diaminobenzidine into a round-bottom flask, introducing nitrogen, setting the flow rate at 200ml/min, the heating temperature at 150 ℃, and the stirring speed at 500 rpm; adding 3g of isophthalic acid and 2.75g of phosphorus pentoxide at an interval of 1 hour; adjusting the temperature to 210 ℃, reacting for 4 hours, pouring the product into deionized water while stirring, and separating out the polybenzimidazole primary product in a filament shape.
(3) Taking out the filament-shaped polybenzimidazole, and pouring the filament-shaped polybenzimidazole into 1mol/L sodium bicarbonate solution for soaking to remove redundant acid; and (3) filtering again, crushing the primary polybenzimidazole product, washing the crushed product for 4 times by using ethanol and deionized water, and drying the product for 5 hours at the temperature of 140 ℃ to obtain polybenzimidazole resin powder.
The characterization methods of FIGS. 1 and 2 illustrate that the process synthesized is indeed polybenzimidazole.
Comparative example 1
For comparison with example 2, the following procedure was carried out:
(1) adding 120g of polyphosphoric acid and 4g of domestic 3, 3' -diaminobenzidine into a round-bottom flask, introducing nitrogen, setting the flow rate at 200ml/min, the heating temperature at 150 ℃, and the stirring speed at 500 rpm; 3g of isophthalic acid and 2.75g of phosphorus pentoxide were added at intervals of 1 hour; adjusting the temperature to 210 ℃, reacting for 4 hours, and pouring the product into deionized water;
(2) filtering the primary product of the polybenzimidazole polymer, and then pouring the filtered primary product into a 1mol/L sodium bicarbonate solution for soaking to remove redundant acid; and filtering again, crushing the primary polybenzimidazole product, washing the crushed product for 4 times by using ethanol and deionized water, and drying the product for 5 hours at the temperature of 140 ℃ to obtain polybenzimidazole resin powder.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments based on the prior art according to the concepts of the present invention should be within the scope of protection determined by the claims.
Claims (9)
1. A method for preparing polybenzimidazole based on domestic cheap raw materials is characterized by comprising the following steps:
step 1, sequentially adding deionized water and 3, 3' -diaminobenzidine into a round-bottom flask, and mixing according to a certain proportion to obtain a mixed solution;
step 2, adding a certain amount of activated carbon powder into the mixed solution;
step 3, heating the liquid mixture to 80-110 ℃, and stirring the liquid mixture for 4-10 hours to completely dissolve the 3, 3' -diaminobenzidine;
step 4, filtering the hot liquid mixture, removing filter residues, cooling the obtained filtrate to 0-25 ℃, and keeping for 6-30 hours until crystals of the 3, 3' -diaminobenzidine are fully precipitated;
step 5, filtering the filtrate after cooling and standing for the second time, and drying the obtained filter residue at 60-90 ℃ for 3-8 hours in vacuum to obtain pretreated 3, 3' -diaminobenzidine;
step 6, repeating the steps 1 to 5 for 1 to 3 times;
step 7, adding polyphosphoric acid and the pretreated 3, 3' -diaminobenzidine in a reactor according to a certain proportion, introducing nitrogen or argon as a protective gas into the reactor, heating the mixture to 150-210 ℃, stirring while heating, and keeping for 5-12 hours;
step 8, adding a certain amount of isophthalic acid and phosphorus pentoxide into the reactor, setting the heating temperature to be 150-210 ℃, and reacting for 3-9 hours;
step 9, pouring the mixture obtained by the reaction into deionized water, standing for 12-48 hours, filtering to obtain a polybenzimidazole primary product, and pouring the polybenzimidazole primary product into a sodium bicarbonate solution to soak for 12-48 hours to remove redundant acid;
and step 10, filtering again to obtain a polybenzimidazole primary product, crushing the polybenzimidazole primary product, sequentially and repeatedly washing the polybenzimidazole primary product with deionized water and ethanol for multiple times, and drying the polybenzimidazole primary product in vacuum at the temperature of 100-150 ℃ to obtain polybenzimidazole powder.
2. The method for preparing polybenzimidazole based on domestic cheap raw materials according to claim 1, wherein in step 1, 15-40g of 3, 3' -diaminobenzidine is added per 1000ml of the deionized water.
3. The method for preparing polybenzimidazole based on domestic cheap raw materials according to claim 1, wherein the weight of the activated carbon powder charged in step 2 is 0-10% of the weight of the 3, 3' -diaminobenzidine in step 1.
4. The method for preparing polybenzimidazole based on domestic cheap raw materials according to claim 1, wherein in step 2, the activated carbon powder is VULCAN XC-72 or VULCAN XC-72R manufactured by cabat.
5. The method for preparing polybenzimidazole based on domestic inexpensive raw materials according to claim 1, characterized in that in steps 4 and 5, filtration is performed using a sand core funnel.
6. The method for preparing polybenzimidazole based on domestic cheap raw materials according to claim 1, wherein in step 7, the mass ratio of the pretreated 3, 3' -diaminobenzidine to the polyphosphoric acid is 1: 20-60.
7. The method for producing polybenzimidazole based on domestic inexpensive raw materials according to claim 1, wherein in step 8, the molar ratio of the pretreated 3,3 '-diaminobenzidine to the isophthalic acid is 1:0.85 to 1.2, and the molar ratio of the pretreated 3, 3' -diaminobenzidine to the phosphorus pentoxide is 1:0.8 to 1.25.
8. The method for preparing polybenzimidazole based on domestic cheap raw materials according to claim 1, wherein the concentration of the sodium bicarbonate solution in step 9 is 0.3-1 mol/L.
9. The method for preparing polybenzimidazole based on domestic cheap raw materials according to claim 1, wherein the polybenzimidazole primary product in step 9 is in the form of filament.
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| CN116970136A (en) * | 2023-09-20 | 2023-10-31 | 山西大学 | Benzimidazolyl covalent organic framework, preparation method and application thereof, proton conductor, and preparation method and application thereof |
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| US20060211844A1 (en) * | 2005-03-17 | 2006-09-21 | Hyoung-Juhn Kim | Polybenzimidazole based polymer and method for preparing the same |
| CN110592712A (en) * | 2019-09-27 | 2019-12-20 | 北京化工大学 | High-performance polybenzimidazole fiber and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116970136A (en) * | 2023-09-20 | 2023-10-31 | 山西大学 | Benzimidazolyl covalent organic framework, preparation method and application thereof, proton conductor, and preparation method and application thereof |
| CN116970136B (en) * | 2023-09-20 | 2024-02-09 | 山西大学 | Benzimidazolyl covalent organic framework, preparation method and application thereof, proton conductor, and preparation method and application thereof |
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