CN115490859A - Polybenzimidazole and preparation method and application thereof - Google Patents

Polybenzimidazole and preparation method and application thereof Download PDF

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CN115490859A
CN115490859A CN202110680243.4A CN202110680243A CN115490859A CN 115490859 A CN115490859 A CN 115490859A CN 202110680243 A CN202110680243 A CN 202110680243A CN 115490859 A CN115490859 A CN 115490859A
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polybenzimidazole
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diacid
compound
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王蔼廉
武佳宁
张韬毅
张龙贵
计文希
陈婧
宋建会
苏萃
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/18Polybenzimidazoles
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Abstract

The invention relates to polybenzimidazole, which comprises a repeating unit structure shown as a formula I:
Figure DDA0003122551290000011
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

Polybenzimidazole and preparation method and application thereof
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:
Figure BDA0003122551270000011
wherein R is selected from any one of a formula II or a formula III:
Figure BDA0003122551270000021
x is selected from any one of formula (1) to formula (7):
Figure BDA0003122551270000022
R 2 all or part of any one of the formulas IV-i:
Figure BDA0003122551270000023
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':
Figure BDA0003122551270000031
wherein X is selected from any one of formula (1) to formula (7):
Figure BDA0003122551270000032
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:
Figure BDA0003122551270000041
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':
Figure BDA0003122551270000042
as a particular embodiment of the present invention, the halogenated hydrocarbon has the formula
Figure BDA0003122551270000051
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':
Figure BDA0003122551270000061
wherein X is selected from any one of formula (1) to formula (7):
Figure BDA0003122551270000062
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':
Figure BDA0003122551270000063
as a particular embodiment of the present invention, the halogenated hydrocarbon has the formula
Figure BDA0003122551270000064
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:
Figure BDA0003122551270000071
Figure BDA0003122551270000081
[ 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:
Figure BDA0003122551270000082
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:
Figure BDA0003122551270000083
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):
Figure BDA0003122551270000091
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:
Figure BDA0003122551270000092
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:
Figure BDA0003122551270000101
[ 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:
Figure BDA0003122551270000102
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:
Figure BDA0003122551270000103
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:
Figure FDA0003122551260000011
wherein R is selected from any one of a formula II or a formula III:
Figure FDA0003122551260000012
x is selected from any one of formula (1) to formula (7):
Figure FDA0003122551260000013
R 2 part or all of the formula IV to formula i is selected from any one of the following formulas:
Figure FDA0003122551260000014
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':
Figure FDA0003122551260000021
wherein X is selected from any one of formula (1) to formula (7):
Figure FDA0003122551260000022
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:
Figure FDA0003122551260000031
and/or the compound containing the hydroxyl diacid group is selected from any one of the formulas IV 'to VIII':
Figure FDA0003122551260000032
and/or the halogenated hydrocarbon has the formula
Figure FDA0003122551260000033
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':
Figure FDA0003122551260000041
wherein X is selected from any one of formula (1) to formula (7):
Figure FDA0003122551260000042
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:
Figure FDA0003122551260000051
and/or the halogenated hydrocarbon has the formula
Figure FDA0003122551260000052
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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