CN116063679A - Method for synthesizing high molecular weight polybenzimidazole compound by utilizing microwave assistance - Google Patents
Method for synthesizing high molecular weight polybenzimidazole compound by utilizing microwave assistance Download PDFInfo
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- 239000004693 Polybenzimidazole Substances 0.000 title claims abstract description 40
- 229920002480 polybenzimidazole Polymers 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 39
- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 87
- 238000010438 heat treatment Methods 0.000 claims abstract description 68
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims abstract description 40
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 40
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 11
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 18
- 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 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 7
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 3
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 claims description 2
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 10
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 9
- 239000011259 mixed solution Substances 0.000 abstract description 8
- 229920000137 polyphosphoric acid Polymers 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 3
- SXEHKFHPFVVDIR-UHFFFAOYSA-N [4-(4-hydrazinylphenyl)phenyl]hydrazine Chemical compound C1=CC(NN)=CC=C1C1=CC=C(NN)C=C1 SXEHKFHPFVVDIR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 16
- 239000000178 monomer Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000000227 grinding Methods 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 229940098779 methanesulfonic acid Drugs 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- WJJMNDUMQPNECX-UHFFFAOYSA-N Dipicolinic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000006257 total synthesis reaction Methods 0.000 description 1
- 239000002699 waste material 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
- C08G73/18—Polybenzimidazoles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a method for synthesizing a high molecular weight polybenzimidazole compound by utilizing microwave assistance. The preparation method of the invention comprises the following steps: the mixed solution of phosphorus pentoxide and organic sulfonic acid is used as a reaction solvent, and dicarboxylic acid and diaminobenzidine with equal molar weights are used as main reaction raw materials, and the raw materials are synthesized by microwave heating under the protection of nitrogen. The traditional solution polymerization uses polyphosphoric acid as a reaction solvent, has the defects of high viscosity, poor mass and heat transfer, troublesome post-treatment and the like, adopts a common heating mode, and has long reaction time and low efficiency of a synthesized product. The invention combines the advantages of high microwave heating efficiency, low viscosity, good mass and heat transfer and simple post treatment by taking the mixed solution of phosphorus pentoxide and organic sulfonic acid as the reaction solvent, and can rapidly synthesize polybenzimidazole compounds with higher molecular weight in a shorter time.
Description
Technical Field
The invention relates to the technical field of proton exchange membrane preparation, in particular to a method for synthesizing a high molecular weight polybenzimidazole compound by taking a mixed solution consisting of phosphorus pentoxide and organic sulfonic acid as a solvent and utilizing microwaves.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have the advantages of high efficiency, no pollution, no electrolyte loss and the like, and Proton Exchange Membranes (PEM) are core components of proton exchange membrane fuel cells, and the electrochemical activity of a fuel cell system can be increased by increasing the operation temperature of the fuel cells, so that development of high-temperature-resistant proton exchange membrane materials has become an important point of research in recent years. At present, a phosphoric acid doped Polybenzimidazole (PBI) membrane is the most successful high-temperature proton exchange membrane, but PBI as a core material has a plurality of problems in synthesis. The PBI and the derivative thereof are mainly synthesized by a melt polycondensation method and a solution polycondensation method at present, wherein the melt polycondensation method has high requirements on the purity of monomers, and meanwhile, the reaction temperature is high (more than 350 ℃), so that the requirements on the high temperature resistance of equipment are severe; the solution polycondensation method generally adopts polyphosphoric acid as a solvent for polycondensation, and the defects of the melt polycondensation method are overcome to a certain extent, but the solution polycondensation method has the defects of high viscosity of a synthetic solvent, low success rate of synthesis, long reaction period, difficult removal of polyphosphoric acid, troublesome treatment and the like; in addition, the synthesis process needs to be performed under heating conditions, and the conventional heating efficiency is low.
For the above reasons, the present application is presented.
Disclosure of Invention
In order to overcome the defects of the existing PBI synthesis method, the invention combines the advantages of high microwave heating efficiency, low viscosity, good mass and heat transfer and simple treatment by taking the mixed solution consisting of phosphorus pentoxide and organic sulfonic acid as a reaction solvent, and provides the method and the application of the method which have simple post-synthesis treatment, high success rate and can rapidly synthesize the high molecular weight polybenzimidazole compound in a short time.
In order to achieve the first object of the present invention, the present invention adopts the following technical scheme:
the method for synthesizing the high molecular weight polybenzimidazole compound by utilizing the microwave assistance comprises the following steps:
(1) Under the protection of inert gas, heating, stirring and dissolving the pre-prepared mixed solvent uniformly, then adding dicarboxylic acid and 3,3' -diaminobenzidine with equal molar weight, and uniformly mixing to obtain a reaction precursor; wherein: the mixed solvent consists of phosphorus pentoxide and organic sulfonic acid;
(2) Transferring the reaction precursor in the step (1) into a microwave synthesizer, heating under microwaves with certain power, setting relevant programming parameters, and heating to react, wherein the reaction is carried out in two stages: firstly, reacting for 10-60min at 100-120 ℃, and then continuously heating to 140-160 ℃ for reacting for 10-120min;
(3) After the reaction is finished, slowly pouring the product into a glass beaker containing deionized water when the temperature of the obtained product is reduced to 50-80 ℃, washing the precipitated polymer to be nearly neutral, then adding saturated sodium bicarbonate solution for neutralization, carrying out vacuum filtration, washing the product obtained by the vacuum filtration, and carrying out vacuum drying to obtain the high molecular weight polybenzimidazole compound.
Further, in the above technical solution, in step (1), the inert gas is N 2 Or argon.
Further, according to the technical scheme, in the step (1), the temperature of heating, stirring and dissolving is 30-50 ℃.
Further, in the above technical solution, in step (1), the dicarboxylic acid is: isophthalic acid, terephthalic acid, 4 '-diphenyldicarboxylic acid, 4' -dicarboxydiphenyl ether, 2, 5-dipicolinic acid, 2, 6-naphthalenedicarboxylic acid, and the like.
Further, in the above technical scheme, in the step (1), the addition amounts of the dicarboxylic acid and the 3,3' -diaminobenzidine are 1-10mmol.
Further, in the above technical solution, in step (1), the organic sulfonic acid is any one of methylsulfonic acid, ethylsulfonic acid, propylsulfonic acid, butylsulfonic acid, and the like.
Further, in the above technical scheme, in step (1), the specific preparation method of the mixed solvent is as follows: 1.00g-10.00g phosphorus pentoxide is added into 25mL organic sulfonic acid, and the mixture is magnetically stirred and heated for 1-12h at 60-150 ℃, and cooled to room temperature after being dissolved.
Further, in the above technical scheme, in the step (1), the dosage ratio of the dicarboxylic acid to the mixed solvent is (1-10) mmol: (10-100) mL.
Further, in the above technical solution, in step (2), the power of the microwave is 200-2000W, and more preferably 300-600W.
Specifically, according to the technical scheme, the deionized water in the step (3) has the following functions: excess solvent and possibly unreacted monomers in the synthesis product are removed, while the synthesis crude product (polymer) is precipitated. Deionized water cannot be replaced with other solvents in this step.
Specifically, according to the technical scheme, the saturated sodium bicarbonate in the step (3) has the following functions: in order to further neutralize the organic sulfonic acid which is a reaction solvent, the effect of further purification is achieved. Other types of alkaline solutions may be neutralized, but the purification effect is poor.
Further, in the above technical scheme, in step (3), the solvent used for washing is deionized water, methanol or ethanol.
Further, in the above technical solution, in step (3), the process conditions adopted in the vacuum drying are as follows: vacuum drying at 100-150deg.C for 12-48h, preferably 120 deg.C for 24h.
Further, in the technical scheme, in the step (3), the molecular weight of the obtained high molecular weight polybenzimidazole compound ranges from 20000 g/mol to 200000g/mol.
The second object of the present invention is to provide a high molecular weight polybenzimidazole compound prepared by the above method.
The mechanism involved in the invention is as follows:
the invention relates to a method for synthesizing high molecular weight polybenzimidazole compound by microwave, which takes mixed solution composed of phosphorus pentoxide and organic sulfonic acid as solvent, and performs polycondensation of dicarboxylic acid and 3,3' -diaminobenzidine under the assistance of microwave, wherein the reaction formula is shown in the following formula one
In the two-stage reaction related to the microwave synthesis, the first stage heating is an initial reaction (slow reaction process), so that the reaction degree is stably carried out, and the narrow molecular weight distribution of a synthesized product is facilitated; the second stage of heating is further polymerization to raise molecular weight.
Compared with the prior art, the method for synthesizing the high molecular weight polybenzimidazole compound by microwaves has the following advantages:
(1) The invention adopts microwave heating synthesis, has uniform heating, accurate temperature control and high efficiency, and can shorten the reaction time;
(2) The invention uses the mixed solution composed of phosphorus pentoxide and organic sulfonic acid as the solvent, has small viscosity, high mass transfer efficiency, low required reaction temperature, simple post-reaction treatment and less waste acid.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance spectrum of the product prepared in example 4 of the present invention.
Detailed Description
The invention is described in further detail below by way of examples.
The invention discloses a method for synthesizing a high molecular weight polybenzimidazole compound by utilizing microwave assistance. The preparation method of the invention comprises the following steps: the mixed solution of phosphorus pentoxide and organic sulfonic acid is used as a reaction solvent, and dicarboxylic acid and diaminobenzidine with equal molar weights are used as main reaction raw materials, and the raw materials are synthesized by microwave heating under the protection of nitrogen. The traditional solution polymerization uses polyphosphoric acid as a reaction solvent, has the defects of high viscosity, poor mass and heat transfer, troublesome post-treatment and the like, adopts a common heating mode, and has long reaction time and low efficiency of a synthesized product. The invention combines the advantages of high microwave heating efficiency, low viscosity, good mass and heat transfer and simple post treatment by taking the mixed solution of phosphorus pentoxide and organic sulfonic acid as the reaction solvent, and can rapidly synthesize polybenzimidazole compounds with higher molecular weight in a shorter time.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein. It is to be understood that the scope of the invention is not limited to the defined processes, properties or components, as these embodiments, as well as other descriptions, are merely illustrative of specific aspects of the invention.
For a better understanding of the present invention, and not to limit its scope, all numbers expressing quantities, percentages, and other values used in the present application are to be understood as being modified in all instances by the term "about". Accordingly, unless specifically indicated otherwise, the numerical parameters set forth in the specification are approximations that may vary depending upon the desired properties sought to be obtained. Each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The equipment and materials used in the present invention are commercially available or are commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
The method for synthesizing the high molecular weight polybenzimidazole compound by utilizing the microwave assistance in the embodiment specifically comprises the following steps:
(1) 4.00g of phosphorus pentoxide is added to 25mL of ethanesulfonic acid (also called ethanesulfonic acid; CAS: 594-45-6), and the mixture is heated by magnetic stirring at 120 ℃ for 5 hours, and cooled to room temperature after dissolving, so as to obtain a phosphorus pentoxide/ethanesulfonic acid solution;
adding 20mL of a pre-prepared phosphorus pentoxide/ethylsulfonic acid solution into a 100mL round-bottom flask, and heating, stirring and heating to 40 ℃ under the protection of nitrogen; accurately weighing 5mmol of 4,4 '-biphenyl dicarboxylic acid and 5mmol of 3,3' -diaminobenzidine respectively (the corresponding mass of the two monomers is calculated after the two monomers are folded, and then adding the two monomers into the phosphorus pentoxide/ethyl sulfonic acid solution); stirring and mixing completely to obtain a reaction precursor;
(2) Transferring the reaction precursor into a microwave synthesizer, heating under microwave with certain power, setting relevant programming parameters, and heating to react, wherein the reaction is carried out in two stages: firstly, heating to 120 ℃ for reaction for 15min, and then continuing heating to 150 ℃ for reaction for 30min, wherein the microwave power is 400W;
(3) After the reaction is finished, slowly pouring the reaction solution into a glass beaker filled with deionized water when the temperature of the reaction solution is reduced to about 80 ℃, washing the precipitated polymer to be nearly neutral, adding saturated sodium bicarbonate solution for neutralization, performing vacuum suction filtration, washing with water for multiple times, washing with ethanol for multiple times, vacuum drying the obtained polymer at 120 ℃ for 24 hours, and grinding the polymer into powder to obtain the high molecular weight polybenzimidazole compound with the weight average molecular weight ranging from 40000 g/mol to 50000g/mol.
The reaction formula involved in the synthesis reaction of this example is shown in the following formula two:
example 2
The method for synthesizing the high molecular weight polybenzimidazole compound by utilizing the microwave assistance in the embodiment specifically comprises the following steps:
(1) 3.85g of phosphorus pentoxide is added into 25mL of propylsulfonic acid (also called 1-propylsulfonic acid, CAS number: 5284-66-2), and the mixture is magnetically stirred and heated for 5 hours at 120 ℃, and cooled to room temperature after being dissolved, so as to obtain a phosphorus pentoxide/propylsulfonic acid solution;
adding 20mL of pre-prepared phosphorus pentoxide/propyl sulfonic acid solution into a 100mL round-bottom flask, and heating, stirring and heating to 40 ℃ under the protection of nitrogen; accurately weighing 5mmol (corresponding mass calculated after both monomers are folded) of terephthalic acid and 3,3 '-diaminobenzidine respectively, and adding the terephthalic acid and the 3,3' -diaminobenzidine into the phosphorus pentoxide/propylsulfonic acid solution; stirring and mixing completely to obtain a reaction precursor;
(2) Transferring the reaction precursor into a microwave synthesizer, heating under microwave with certain power, setting relevant programming parameters, and heating to react, wherein the reaction is carried out in two stages: firstly, heating to 120 ℃ for reaction for 15min, then heating to 150 ℃ for reaction for 30min, wherein the microwave power is 300W;
(3) After the reaction is finished, slowly pouring the reaction solution into a glass beaker filled with deionized water when the temperature of the reaction solution is reduced to about 80 ℃, washing the precipitated polymer to be nearly neutral, adding saturated sodium bicarbonate solution for neutralization, performing vacuum suction filtration, washing with water for multiple times, washing with ethanol for multiple times, vacuum drying the obtained polymer at 120 ℃ for 24 hours, and grinding the polymer into powder to obtain the high molecular weight polybenzimidazole compound with the weight average molecular weight ranging from 20000 g/mol to 30000g/mol.
The reaction formula involved in the synthesis reaction of this example is shown in the following formula three:
example 3
The method for synthesizing the high molecular weight polybenzimidazole compound by utilizing the microwave assistance in the embodiment specifically comprises the following steps:
(1) 3.85g of phosphorus pentoxide is added into 25mL of methanesulfonic acid (CAS number: 75-75-2), and the mixture is magnetically stirred and heated for 5 hours at 120 ℃, and cooled to room temperature after being dissolved, so as to obtain a phosphorus pentoxide/methanesulfonic acid solution;
adding 20mL of a pre-prepared phosphorus pentoxide/methanesulfonic acid solution into a 100mL round-bottom flask, and heating, stirring and heating to 40 ℃ under the protection of nitrogen; accurately weighing 5mmol (corresponding mass calculated after both monomers are folded) of isophthalic acid and 3,3 '-diaminobenzidine respectively, and adding the isophthalic acid and the 3,3' -diaminobenzidine into the phosphorus pentoxide/methylsulfonic acid solution; stirring and mixing completely to obtain a reaction precursor;
(2) Transferring the reaction precursor into a microwave synthesizer, heating under microwave with certain power, setting relevant programming parameters, and heating to react, wherein the reaction is carried out in two stages: firstly, heating to 120 ℃ for reaction for 20min, then heating to 160 ℃ for reaction for 40min, wherein the microwave power is 300W;
(3) After the reaction is finished, slowly pouring the reaction solution into a glass beaker filled with deionized water when the temperature of the reaction solution is reduced to about 80 ℃, washing the precipitated polymer to be nearly neutral, adding saturated sodium bicarbonate solution for neutralization, performing vacuum suction filtration, washing with water for multiple times, washing with ethanol for multiple times, vacuum drying the obtained polymer at 120 ℃ for 24 hours, and grinding the polymer into powder to obtain the high molecular weight polybenzimidazole compound with the weight average molecular weight of 60000-80000 g/mol.
The reaction formula involved in the synthesis reaction of this example is shown in the following formula four:
example 4
The method for synthesizing the high molecular weight polybenzimidazole compound by utilizing the microwave assistance in the embodiment specifically comprises the following steps:
(1) 3.90g of phosphorus pentoxide is added to 25mL of methanesulfonic acid (CAS number: 75-75-2), and the mixture is magnetically stirred and heated at 120 ℃ for 5 hours, and cooled to room temperature after being dissolved, so as to obtain a phosphorus pentoxide/methanesulfonic acid solution;
adding 20mL of a pre-prepared phosphorus pentoxide/methanesulfonic acid solution into a 100mL round-bottom flask, and heating, stirring and heating to 40 ℃ under the protection of nitrogen; accurately weighing 5mmol of 4,4 '-dicarboxydiphenyl ether and 3,3' -diaminobenzidine respectively (the corresponding mass of the two monomers is calculated after the two monomers are folded and purified), and adding the two monomers into the phosphorus pentoxide/methanesulfonic acid solution; stirring and mixing completely to obtain a reaction precursor;
(2) Transferring the reaction precursor into a microwave synthesizer, heating under microwave with certain power, setting relevant programming parameters, and heating to react, wherein the reaction is carried out in two stages: firstly, heating to 120 ℃ for reaction for 30min, then heating to 150 ℃ for reaction for 20min, wherein the microwave power is 500W;
(3) After the reaction is finished, slowly pouring the reaction solution into a glass beaker filled with deionized water when the temperature of the reaction solution is reduced to about 80 ℃, washing the precipitated polymer to be nearly neutral, adding saturated sodium bicarbonate solution for neutralization, performing vacuum suction filtration, washing with water for multiple times, washing with ethanol for multiple times, vacuum drying the obtained polymer at 120 ℃ for 24 hours, and grinding the polymer into powder to obtain the high molecular weight polybenzimidazole compound with the weight average molecular weight of 150000 ～ 160000g/mol.
The reaction formula involved in the synthesis reaction of this example is shown in the following formula five:
example 5
The method for synthesizing the high molecular weight polybenzimidazole compound by utilizing the microwave assistance in the embodiment specifically comprises the following steps:
(1) 3.85g of phosphorus pentoxide is added into 25mL of methanesulfonic acid (CAS number: 75-75-2), and the mixture is magnetically stirred and heated for 5 hours at 120 ℃, and cooled to room temperature after being dissolved, so as to obtain a phosphorus pentoxide/methanesulfonic acid solution;
adding 20mL of a pre-prepared phosphorus pentoxide/methanesulfonic acid solution into a 100mL round-bottom flask, and heating, stirring and heating to 40 ℃ under the protection of nitrogen; accurately weighing 5mmol (corresponding mass calculated after the two monomers are folded to purity) of each of 2, 6-pyridine dicarboxylic acid and 3,3' -diaminobenzidine, and adding the two monomers into the phosphorus pentoxide/methanesulfonic acid solution; stirring and mixing completely to obtain a reaction precursor;
(2) Transferring the reaction precursor into a microwave synthesizer, heating under microwave with certain power, setting relevant programming parameters, and heating to react, wherein the reaction is carried out in two stages: firstly, heating to 120 ℃ for reaction for 20min, then heating to 140 ℃ for reaction for 30min, wherein the microwave power is 500W;
(3) After the reaction is finished, slowly pouring the reaction solution into a glass beaker filled with deionized water when the temperature of the reaction solution is reduced to about 80 ℃, washing the precipitated polymer to be nearly neutral, adding saturated sodium bicarbonate solution for neutralization, performing vacuum suction filtration, washing with water for multiple times, washing with ethanol for multiple times, vacuum drying the obtained polymer at 120 ℃ for 24 hours, and grinding the polymer into powder to obtain the high molecular weight polybenzimidazole compound with the weight average molecular weight ranging from 80000g/mol to 100000g/mol.
The reaction formula involved in the synthesis reaction of this example is shown in the following formula six:
example 6
The method for synthesizing the high molecular weight polybenzimidazole compound by utilizing the microwave assistance in the embodiment specifically comprises the following steps:
(1) Adding 4.00g of phosphorus pentoxide into 25mL of methanesulfonic acid (CAS number: 75-75-2), magnetically stirring and heating at 120 ℃ for 5 hours, and cooling to room temperature after dissolving to obtain the phosphorus pentoxide/methanesulfonic acid solution;
adding 20mL of a pre-prepared phosphorus pentoxide/methanesulfonic acid solution into a 100mL round-bottom flask, and heating, stirring and heating to 40 ℃ under the protection of nitrogen; accurately weighing 5mmol (corresponding mass calculated after the two monomers are folded and pure) of each of 2, 6-naphthalene dicarboxylic acid and 3,3' -diaminobenzidine, and adding the two monomers into the phosphorus pentoxide/methanesulfonic acid solution; stirring and mixing completely to obtain a reaction precursor;
(2) Transferring the reaction precursor into a microwave synthesizer, heating under microwave with certain power, setting relevant programming parameters, and heating to react, wherein the reaction is carried out in two stages: firstly, heating to 110 ℃ for reaction for 30min, then heating to 160 ℃ for reaction for 30min, wherein the microwave power is 400W;
(3) After the reaction is finished, slowly pouring the reaction solution into a glass beaker filled with deionized water when the temperature of the reaction solution is reduced to about 80 ℃, washing the precipitated polymer to be nearly neutral, adding saturated sodium bicarbonate solution for neutralization, performing vacuum suction filtration, washing with water for multiple times, washing with ethanol for multiple times, vacuum drying the obtained polymer at 120 ℃ for 24 hours, and grinding the polymer into powder to obtain the high molecular weight polybenzimidazole compound with the weight average molecular weight ranging from 50000g/mol to 60000g/mol.
The reaction formula involved in the synthesis reaction of this example is shown in the following formula seven:
comparative example 1
The method of the polybenzimidazole compound of the comparative example specifically comprises the following steps:
sequentially adding 25mL of methanesulfonic acid (CAS number: 75-75-2) and 3.90g of phosphorus pentoxide into a 100mL round bottom flask, heating in an oil bath under the protection of nitrogen, stirring and heating to 120 ℃ under magnetic stirring for 5h, and cooling to room temperature after dissolving to obtain a phosphorus pentoxide/methanesulfonic acid solution;
accurately weighing 5mmol of 4,4 '-dicarboxydiphenyl ether and 3,3' -diaminobenzidine respectively, and adding into the phosphorus pentoxide/methanesulfonic acid solution; after stirring and mixing are completed, heating in an oil bath to 170 ℃ for reaction for 5 hours; then the reaction temperature is increased to 220 ℃ and the reaction is continued for about 19 hours;
after the reaction is finished, slowly pouring the reaction solution into a glass beaker filled with deionized water when the temperature of the reaction solution is reduced to about 80 ℃, washing the precipitated polymer to be nearly neutral, adding saturated sodium bicarbonate solution for neutralization, performing vacuum suction filtration, washing with water for multiple times, washing with ethanol for multiple times, vacuum drying the obtained polymer at 100 ℃ for 24 hours, and grinding the polymer into powder to obtain the polybenzimidazole compound with the weight average molecular weight ranging from 30000g/mol to 80000g/mol.
As can be seen, the comparative example uses a conventional oil bath heating mode, and has the advantages of long total synthesis time of more than 20h, low synthesis success rate, wide molecular weight distribution of the synthesized product and small molecular weight compared with microwave heating synthesis.
Comparative example 2
The synthesis method of the polybenzimidazole compound of the comparative example adopts polyphosphoric acid to replace phosphorus pentoxide/methanesulfonic acid solution. The specific synthetic procedure of this comparative example is as follows:
(1) 50mL of polyphosphoric acid (CAS number: 8017-16-1) was added to a 100mL round bottom flask, and the mixture was heated to 40℃under nitrogen protection; accurately weighing 1mmol of 4,4 '-dicarboxydiphenyl ether and 3,3' -diaminobenzidine respectively, adding into the flask, stirring and mixing completely to obtain reaction precursors;
(2) Transferring the reaction precursor into a microwave synthesizer, heating under microwave with certain power, setting relevant programming parameters, and heating to react, wherein the reaction is carried out in two stages: firstly, heating to 120 ℃ for reaction for 30min, then heating to 150 ℃ for reaction for 20min, wherein the microwave power is 500W;
(3) After the reaction is finished, slowly pouring the reaction solution into a glass beaker filled with deionized water while the reaction solution is hot to prevent the whole viscosity from becoming larger and the fluidity from becoming worse due to the cooling of a solvent, sufficiently stirring at a high speed to wash the precipitated polymer to be close to neutral, then adding saturated sodium bicarbonate solution for neutralization, decompressing and filtering, washing with water for multiple times, washing with ethanol for multiple times, vacuum drying the obtained polymer for 24 hours at 120 ℃, and grinding the polymer into powder to obtain the high molecular weight polybenzimidazole compound, wherein the weight average molecular weight range of the polybenzimidazole compound is 20000-60000 g/mol.
From this, the comparative example uses polyphosphoric acid instead of phosphorus pentoxide/methanesulfonic acid solution, and the existence of the reaction solvent has excessive viscosity, which is unfavorable for the reaction to proceed in the forward direction, resulting in a synthesized product with small molecular weight and wide molecular weight distribution.
Structural test:
FIG. 1 shows the product of example 4 of the present invention 1 H-NMR spectrum. As can be seen from fig. 1, a single peak around chemical shift δ is 13 corresponds to the only hydrogen on the imidazole ring; peaks numbered a, b and c correspond to 3 hydrogens on the benzene ring in the benzimidazole ring; peaks numbered d and e correspond to the hydrogen on the benzene ring in the diacid. 1 H-NMR confirmed that the synthesized polymer had the expected structure.
Claims (8)
1. A method for synthesizing high molecular weight polybenzimidazole compounds by utilizing microwave assistance is characterized in that: the method specifically comprises the following steps:
(1) Under the protection of inert gas, heating, stirring and dissolving the pre-prepared mixed solvent uniformly, then adding dicarboxylic acid and 3,3' -diaminobenzidine with equal molar weight, and uniformly mixing to obtain a reaction precursor; wherein: the mixed solvent consists of phosphorus pentoxide and organic sulfonic acid;
(2) Transferring the reaction precursor in the step (1) into a microwave synthesizer, heating under microwaves with certain power, setting relevant programming parameters, and heating to react, wherein the reaction is carried out in two stages: firstly, reacting for 10-60min at 100-120 ℃, and then continuously heating to 140-160 ℃ for reacting for 10-120min;
(3) After the reaction is finished, slowly pouring the product into a glass beaker containing deionized water when the temperature of the obtained product is reduced to 50-80 ℃, washing the precipitated polymer to be nearly neutral, then adding saturated sodium bicarbonate solution for neutralization, carrying out vacuum filtration, washing the product obtained by the vacuum filtration, and carrying out vacuum drying to obtain the high molecular weight polybenzimidazole compound.
2. The method according to claim 1, characterized in that: in step (1), the dicarboxylic acid is: isophthalic acid, terephthalic acid, 4 '-biphenyl dicarboxylic acid, 4' -dicarboxydiphenyl ether, 2, 5-pyridinedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid.
3. The method according to claim 1, characterized in that: in the step (1), the addition amount of the dicarboxylic acid and the 3,3' -diaminobenzidine is 1-10mmol.
4. The method according to claim 1, characterized in that: in the step (1), the organic sulfonic acid is any one of methyl sulfonic acid, ethyl sulfonic acid, propyl sulfonic acid and butyl sulfonic acid.
5. The method according to claim 1, characterized in that: the dosage ratio of the dicarboxylic acid to the mixed solvent is (1-10) mmol: (10-100) mL.
6. The method according to claim 1, characterized in that: in the step (2), the power of the microwaves is 200-2000W.
7. The method according to claim 1, characterized in that: in the step (3), the molecular weight of the obtained high molecular weight polybenzimidazole compound ranges from 20000 g/mol to 200000g/mol.
8. The high molecular weight polybenzimidazole compound prepared by the method of any one of claims 1 to 7.
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