CN115490859A - Polybenzimidazole and preparation method and application thereof - Google Patents
Polybenzimidazole and preparation method and application thereof Download PDFInfo
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- 239000004693 Polybenzimidazole Substances 0.000 title claims abstract description 60
- 229920002480 polybenzimidazole Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 150000008282 halocarbons Chemical class 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical class [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims 8
- 239000007864 aqueous solution Substances 0.000 claims 3
- MYTMXVHNEWBFAL-UHFFFAOYSA-L dipotassium;carbonate;hydrate Chemical class O.[K+].[K+].[O-]C([O-])=O MYTMXVHNEWBFAL-UHFFFAOYSA-L 0.000 claims 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical class O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 150000005826 halohydrocarbons Chemical class 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 3
- 238000007385 chemical modification Methods 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000006011 modification reaction Methods 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 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 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-ZSJDYOACSA-N Sulfuric acid-d2 Chemical compound [2H]OS(=O)(=O)O[2H] QAOWNCQODCNURD-ZSJDYOACSA-N 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to polybenzimidazole, which comprises a repeating unit structure shown as a formula I:
the polybenzimidazole contains an allyl structure capable of further modification reaction, is easy to dissolve, and can be used for subsequent chemical modification reaction and introducing other functional groups, so that the application range of the polybenzimidazole is expanded.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to polybenzimidazole and a preparation method and application thereof.
Background
Polybenzimidazole (PBI) is an aromatic heterocyclic polymer with a main chain containing a benzimidazole ring repeating structural unit, is mainly prepared by condensing aromatic dicarboxylic acid and a tetramine monomer, is firstly reported in 1961 and synthesized by Vogel, marvel and the like, and wholly aromatic polybenzimidazole resin has good heat resistance and excellent mechanical property, is special engineering plastic with excellent performance, and is widely applied to high-precision fields such as aerospace, semiconductors, fireproof heat-resistant materials, fuel cells and the like. The commercial polybenzimidazole resin (poly [2,2'- (m-phenylene) -5,5' -dibenzoimidazole ], mPBI) has high heat-resistant temperature, can instantaneously resist heat above 700 ℃, has high strength and can be used in various extremely high-temperature occasions. However, the poly [2,2'- (m-phenylene) -5,5' -dibenzoimidazole ] resin has the defects of high preparation temperature (above 200 ℃), difficult melting and difficult processing, the requirement of a film forming process on an experimental device is high, the operation conditions are harsh, the prepared polybenzimidazole film material is difficult to modify, and difficulty is brought to further application of the polybenzimidazole film material.
Therefore, there is a need to develop a polybenzimidazole which is easy to dissolve and process, and is beneficial to expanding the application range of the polybenzimidazole.
Disclosure of Invention
The technical problem to be solved by the invention is to provide polybenzimidazole which is easy to dissolve and process and can be further modified subsequently, aiming at the defects of the prior art, and the polybenzimidazole is beneficial to expanding the application range.
In a first aspect, the present invention provides a polybenzimidazole comprising a repeat unit structure represented by formula i:
wherein R is selected from any one of a formula II or a formula III:
x is selected from any one of formula (1) to formula (7):
R 2 all or part of any one of the formulas IV-i:
r and R 2 The same or different along the molecular chain.
In one embodiment of the present invention, the polybenzimidazole has a number average molecular weight of 2000g/mol to 800000g/mol, such as 2000g/mol,5000g/mol,8000g/mol,10000g/mol,50000g/mol,100000g/mol,200000g/mol,300000g/mol,400000g/mol,500000g/mol,600000g/mol,700000g/mol,800000g/mol and any combination thereof.
The raw materials in the present invention may be obtained by themselves or commercially, unless otherwise specified, and the present invention is not limited thereto.
The polybenzimidazole contains an allyl structure capable of being further modified, and is easy to dissolve, and the allyl structure can be subjected to subsequent chemical modification reaction, and other functional groups are introduced, so that the application range of the polybenzimidazole is expanded.
In a second aspect, the present invention provides a method for preparing the polybenzimidazole, comprising the following steps:
dissolving a compound containing a tetraamino group and a compound containing a diacid group in a molar ratio of (0.8.
As a specific embodiment of the present invention, the sum of the mass of the tetraamino-group containing compound and the diacid-group containing compound is in the range of 1% to 20%, such as 1%,5%,15%,20% and any combination thereof, of the clear solution.
As a specific embodiment of the present invention, the molar ratio of the tetraamino-group-containing compound to the diacid-group-containing compound is preferably in the range of (1.02.
In a specific embodiment of the present invention, the clarified solution containing polyphosphoric acid further comprises phosphorus pentoxide, and the mass ratio of the phosphorus pentoxide to the polyphosphoric acid is preferably 1 (6-15), more preferably 1 (8-13), for example, the range of 1.
As a specific embodiment of the present invention, the tetraamino group-containing compound is selected from any one of formula ii 'or formula iii':
wherein X is selected from any one of formula (1) to formula (7):
as a specific embodiment of the invention, the diacid group containing compound is selected from any one of the formulas IV 'to i' in whole or in part:
as a specific embodiment of the invention, the diacid group-containing compound is prepared by dissolving the hydroxyl diacid group-containing compound and halogenated hydrocarbon in a solvent and refluxing for 2 to 24 hours, such as 2h,8h, 169, 24h and any combination thereof.
As a specific embodiment of the invention, the compound containing a hydroxy diacid group is selected from any one of formulas IV 'to VIII':
as a particular embodiment of the present invention, the halogenated hydrocarbon has the formula
The structure is shown in the specification, wherein Z is selected from any one of F, cl, br and I.
As a specific embodiment of the present invention, the solvent is selected from one or more of tetrahydrofuran, acetone, ethanol, acetonitrile, N-methylpyrrolidone, dimethylsulfoxide, N' N-dimethylformamide and N, N-dimethylacetamide.
In a specific embodiment of the present invention, the mass ratio of the phosphorus pentoxide to the polyphosphoric acid is 1 (6-15), preferably 1 (8-13).
As a specific embodiment of the present invention, a washing operation is performed using a saturated aqueous sodium bicarbonate solution, a saturated aqueous potassium carbonate solution, a saturated aqueous sodium carbonate solution, or ammonia water.
As a specific embodiment of the present invention, the drying is mainly intended to remove the solvent, and the drying manner may be a method that is conventional in the art, and the present invention is not particularly limited thereto. The drying temperature may range from 80 ℃ to 100 ℃, such as 80 ℃,90 ℃,100 ℃ and any combination thereof, and may be adjusted depending on the drying time.
As a specific embodiment of the present invention, the protective gas is nitrogen.
In a third aspect, the present invention provides another method for preparing polybenzimidazole.
The preparation method of the polybenzimidazole comprises the following steps:
s101: under the condition of protective gas, dissolving a compound containing a tetraamino group and a compound containing a hydroxy diacid group in a molar ratio of (0.8;
s102: and dissolving the polybenzimidazole intermediate and halogenated hydrocarbon in a solvent, and refluxing for 2-24 h to obtain the polybenzimidazole intermediate.
In a specific embodiment of the present invention, the clarified solution containing polyphosphoric acid further comprises phosphorus pentoxide, and the mass ratio of the phosphorus pentoxide to the polyphosphoric acid is preferably 1 (6-15), more preferably 1 (8-13), for example, the range of 1.
In a specific embodiment of the present invention, the sum of the mass of the tetraamino group-containing compound and the mass of the hydroxy diacid group-containing compound accounts for 1% to 20% of the clear solution.
As a specific embodiment of the present invention, the molar ratio of the tetraamino group-containing compound to the hydroxydiacid group-containing compound may be in the range of (1.02.
As a specific embodiment of the present invention, the tetraamino group-containing compound is selected from any one of formula ii 'or formula iii':
wherein X is selected from any one of formula (1) to formula (7):
as a specific embodiment of the invention, all or part of the compounds containing hydroxyl diacid groups are selected from any one of formulas IV 'to VIII':
as a particular embodiment of the present invention, the halogenated hydrocarbon has the formula
The structure is shown in the specification, wherein Z is selected from any one of F, cl, br and I.
As a specific embodiment of the present invention, the solvent is selected from one or more of tetrahydrofuran, acetone, ethanol, N' N-dimethylformamide, and N, N-dimethylacetamide.
In a specific embodiment of the present invention, the mass ratio of the phosphorus pentoxide to the polyphosphoric acid is 1 (6-15), preferably 1 (8-13).
As a specific embodiment of the present invention, in the step S101, a washing operation is performed using a saturated aqueous sodium bicarbonate solution, a saturated aqueous potassium carbonate solution, a saturated aqueous sodium carbonate solution, or ammonia water.
As a specific embodiment of the present invention, in the step S101, the drying is mainly performed to remove the solvent, and the drying manner may be a method that is conventional in the art, and the present invention is not particularly limited thereto. The drying temperature may range from 80 ℃ to 100 ℃, such as 80 ℃,90 ℃,100 ℃ and any combination thereof, and may be adjusted depending on the drying time.
As a specific embodiment of the present invention, in the step S101, the protective gas is nitrogen.
In a fourth aspect, the invention provides the application of the polybenzimidazole and/or the preparation method of the polybenzimidazole in the fields of aerospace materials, semiconductor materials, fireproof heat-resistant materials and fuel cells.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings.
FIG. 1 is a hydrogen nuclear magnetic spectrum of a polybenzimidazole intermediate of example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of Vinyl-O-PBI;
FIG. 3 is a nuclear magnetic spectrum of co-OH-PBI;
FIG. 4 is a nuclear magnetic hydrogen spectrum of Vinyl-co-PBI-2.
Detailed Description
In order that the invention may be more readily understood, the following detailed description of the invention is given, with reference to the accompanying examples and drawings, which are given by way of illustration only and are not intended to limit the scope of the invention.
The test methods or standards used in the following examples and comparative examples are as follows:
hydrogen nuclear magnetic resonance spectroscopy: agilent technologies, inc. U.S. 400-MR DD2,1H has a resonant frequency of 399.87MHz. The solvent was deuterated sulfuric acid and the test temperature was 50 ℃. The hydrogen spectrum uses a 45 ° pulse, the cycle delay time is 5s, and the sampling time is 2s.
The following examples are from the following sources:
[ example 1 ]
Phosphorus pentoxide (6 g) was weighed and dissolved in polyphosphoric acid (60 g) to form a clear solution, 2,5-dihydroxyterephthalic acid (10 mmol) and 3,3-diaminobenzidine (10 mmol) were added under nitrogen and the temperature was raised to 200 ℃ with stirring for reaction for 3 hours. The reaction solution was washed to neutrality by pouring into saturated sodium bicarbonate, filtered, and the polybenzimidazole intermediate (OH-PBI) was placed in a vacuum oven at 80 ℃ for a whole day and night.
OH-PBI：
The hydrogen nuclear magnetic spectrum diagram is shown in figure 1.
Polybenzimidazole intermediate (OH-PBI, 10 mmol), allyl bromide (40 mol), potassium carbonate (2 mmol) and tetrabutylammonium bromide (2 mmol) are weighed into 50ml acetonitrile, stirred for 1 day and night at 80 ℃, filtered and the solvent is removed by rotary evaporation to obtain Vinyl-O-PBI.
Vinyl-O-PBI：
The nuclear magnetic hydrogen spectrum is shown in figure 2:
H 1 NMR(Vinyl-O-PBI,400MHz,d 2 -H 2 SO 4 ):δ7.69(m,6H),7.44(d,2H),4.16(s,2H),3.02(d,3H),2.13(s,2H).
[ example 2 ]
2,5-dihydroxyterephthalic acid (20 mmol), allyl bromide (40 mol), potassium carbonate (2 mmol) and tetrabutylammonium bromide (2 mmol) were weighed into 10ml tetrahydrofuran, stirred at room temperature for 1 day and night, filtered, and the solvent was removed by rotary evaporation to give VDA (whose structure is shown below):
phosphorus pentoxide (6 g) was weighed out and dissolved in polyphosphoric acid (60 g) to form a clear solution, VDA (10 mmol) and 3,3-diaminobenzidine (10 mmol) were added under nitrogen and the temperature was raised to 200 ℃ with stirring for 10 hours. The reaction solution was washed to neutrality by pouring into saturated sodium bicarbonate, filtered, and the product (Vinyl-O-PBI) was placed in a vacuum oven at 80 ℃ for a whole day and night.
Vinyl-O-PBI：
The nuclear magnetic hydrogen spectrum (as shown in figure 2) shows that:
H 1 NMR(Vinyl-O-PBI,400MHz,d 2 -H 2 SO 4 ):δ7.69(m,6H),7.44(d,2H),4.16(s,2H),3.02(d,3H),2.13(s,2H).
[ example 3 ]
VDA was prepared as in example 2.
Phosphorus pentoxide (6 g) was weighed out and dissolved in polyphosphoric acid (60 g) to form a clear solution, VDA (1 mmol), 2,5-dihydroxyterephthalic acid (9 mmol) and 3,3-diaminobenzidine (10 mmol) were added under nitrogen and the temperature was raised to 200 ℃ with stirring for 10 hours. The reaction solution was washed to neutrality by pouring into saturated sodium bicarbonate, filtered, and the product (Vinyl-co-PBI) was placed in a vacuum oven at 80 ℃ for a whole day and night.
Structure of Vinyl-co-PBI:
[ example 4 ] A method for producing a polycarbonate
Polyphosphoric acid (70 g) was weighed, 2,5-dihydroxyterephthalic acid (1 mmol), 4,4-dicarboxydiphenyl ether (9 mmol) and 3,3-diaminobenzidine (10 mmol) were added under nitrogen and the temperature was raised to 190 ℃ with stirring for reaction for 3 hours. The reaction solution was washed to neutrality by pouring into saturated sodium bicarbonate, filtered, and the intermediate (co-OH-PBI) was placed in a vacuum oven at 80 ℃ for a whole day and night.
Structure of co-OH-PBI:
the nuclear magnetic spectrum is shown in figure 3.
Polybenzimidazole intermediate (co-OH-PBI, 10 mmol), allyl bromide (20 mol), potassium carbonate (2 mmol) and tetrabutylammonium bromide (2 mmol) are weighed out in 100ml DMAc, stirred at 80 ℃ for 1 day and night, filtered and the solvent is removed by rotary evaporation to obtain Vinyl-co-PBI-2.
The structure of Vinyl-co-PBI-2 is as follows:
the nuclear magnetic hydrogen spectrum is shown in FIG. 4.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A polybenzimidazole comprising a repeating unit structure represented by formula I:
wherein R is selected from any one of a formula II or a formula III:
x is selected from any one of formula (1) to formula (7):
R 2 part or all of the formula IV to formula i is selected from any one of the following formulas:
r and R 2 The same or different along the molecular chain.
2. The polybenzimidazole according to claim 1, where the polybenzimidazole has a number average molecular weight of 2000 to 800000g/mol.
3. The process for preparing polybenzimidazole according to claim 1 or 2, characterized by comprising the steps of:
under the condition of protective gas, dissolving a compound containing a tetramino group and a compound containing a diacid group in a molar ratio of (0.8; preferably, the sum of the mass of the tetraamino-group-containing compound and the diacid-group-containing compound accounts for 1% to 20% of the clear solution, and/or the molar ratio of the tetraamino-group-containing compound to the diacid-group-containing compound is (1.02.
4. The preparation method of polybenzimidazole according to claim 3, wherein the diacid group containing compound is prepared by dissolving a hydroxyl diacid group containing compound and halohydrocarbon in a solvent and refluxing for 2-24 h; and/or
The clarified solution containing polyphosphoric acid further comprises phosphorus pentoxide, and the mass ratio of the phosphorus pentoxide to the polyphosphoric acid is preferably 1 (6-15), and more preferably 1 (8-13).
5. The method of claim 3 or 4, wherein the compound containing a tetraamino group is selected from any one of the formulae II 'and III':
wherein X is selected from any one of formula (1) to formula (7):
6. the process for preparing polybenzimidazole according to any one of claims 3 to 5, where in the diacid group containing compound is selected from any one of formulae IV 'to i', in whole or in part:
and/or the compound containing the hydroxyl diacid group is selected from any one of the formulas IV 'to VIII':
and/or the halogenated hydrocarbon has the formula
The structure is shown in the specification, wherein Z is selected from any one of F, cl, br and I;
and/or the solvent is selected from one or more of tetrahydrofuran, acetone, ethanol, acetonitrile, N-methylpyrrolidone, dimethyl sulfoxide, N' N-dimethylformamide and N, N-dimethylacetamide; and/or the presence of a gas in the gas,
washing with saturated sodium bicarbonate water solution, saturated potassium carbonate water solution, saturated sodium carbonate water solution or ammonia water; and/or the presence of a gas in the gas,
and/or the drying temperature is 80-100 ℃; and/or the presence of a gas in the gas,
and/or the protective gas is nitrogen.
7. The process for preparing polybenzimidazole according to claim 1 or 2, characterized by comprising the steps of:
s101: under the condition of protective gas, dissolving a compound containing a tetraamino group and a compound containing a hydroxy diacid group in a molar ratio of 0.8/1-1/1.2 in a clear solution containing polyphosphoric acid, heating to 160-220 ℃, reacting for 1-48 h, washing to be neutral, filtering, collecting filter residues, and drying to obtain a polybenzimidazole intermediate; preferably, the sum of the mass of the tetraamino-group-containing compound and the mass of the hydroxy diacid-group-containing compound accounts for 1% to 20% of the clear solution, and/or the molar ratio of the tetraamino-group-containing compound to the hydroxy diacid-group-containing compound is (1.02; and/or the clarified solution containing polyphosphoric acid further comprises phosphorus pentoxide, preferably, the mass ratio of the phosphorus pentoxide to the polyphosphoric acid is 1 (6-15), more preferably 1 (8-13);
s102: and dissolving the polybenzimidazole intermediate and halogenated hydrocarbon in a solvent, and refluxing for 2-24 h to prepare the polybenzimidazole.
8. The method of claim 7, wherein the compound having a tetraamino group is selected from any one of the following formulae II 'and III':
wherein X is selected from any one of formula (1) to formula (7):
9. the method for preparing polybenzimidazole according to claim 7 or 8, where in the compound containing a hydroxy diacid group is selected from any one of formulae IV "to VIII" in whole or in part:
and/or the halogenated hydrocarbon has the formula
The structure is shown in the specification, wherein Z is selected from any one of F, cl, br and I;
and/or the solvent is selected from one or more of tetrahydrofuran, acetone, ethanol, acetonitrile, N-methylpyrrolidone, dimethyl sulfoxide, N' N-dimethylformamide and N, N-dimethylacetamide;
and/or, in the step S101, a saturated sodium bicarbonate aqueous solution, a saturated potassium carbonate aqueous solution, a saturated sodium carbonate aqueous solution or ammonia water is used for washing operation;
and/or, in the step S101, the drying temperature is 80-100 ℃;
and/or, in the step S101, the protective gas is nitrogen.
10. Use of a polybenzimidazole according to claim 1 or 2 and/or a polybenzimidazole according to any one of claims 3 to 9 for the preparation of materials for aerospace, semiconductor, fire and heat protection and fuel cells.
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