CN110105568A - A method of utilizing aromatic nitration by-product production PBI functional material - Google Patents
A method of utilizing aromatic nitration by-product production PBI functional material Download PDFInfo
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- CN110105568A CN110105568A CN201910339731.1A CN201910339731A CN110105568A CN 110105568 A CN110105568 A CN 110105568A CN 201910339731 A CN201910339731 A CN 201910339731A CN 110105568 A CN110105568 A CN 110105568A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0677—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
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Abstract
The invention discloses a kind of methods using aromatic nitration by-product production PBI functional material.By the nitration by-products of 2,4- dinitrochlorobenzene manufacturing enterprise, that is, contain 2, the mixture of 6- dinitrochlorobenzene (I), the mode through fractional crystallization obtain 2,4- dinitrochlorobenzene, 2,6- dinitrochlorobenzene (I) and a small amount of residue.Wherein 2,4- dinitrochlorobenzene as product it is directly outer sell, a small amount of residue makees waste processing, and the simple compound of 2,6- dinitrochlorobenzenes (I) then reacted PBI (X) resin being had excellent performance.This method efficiently solves 2, the generally existing difficulty of 4- dinitrochlorobenzene manufacturing enterprise increases business economic income while reducing enterprise's dangerous waste amount, promote enterprise security, strong support is provided for the steady sustainable production of 2,4- dinitrochlorobenzene manufacturing enterprise.
Description
Technical field
The invention belongs to chemical field more particularly to a kind of sides using aromatic nitration by-product production PBI functional material
Method
Background technique
Substituent group has direct relation for electrophilic characteristic on aromatic nitration product and its substrate aromatic ring, such as with a chlorine
Change benzene or ortho-nitrochlorobenzene is raw material, through nitration reaction, during producing 2,4- dinitrochlorobenzene, due to substrate virtue
The donor properties of chlorine atom on ring determine in the conversion process, are generating principal product 2, the mistake of 4- dinitrochlorobenzene
The generation of 2,6- dinitrochlorobenzene (I) is necessarily accompanied in journey.
The above process can indicate with following equation,
This theoretical estimation result also produces 2,4- bis- through nitration reaction with chlorobenzene or ortho-nitrochlorobenzene by any
The actual result of the enterprise of nitro chlorobenzene is verified.
In the past to the industry stubborn problem, a small number of enterprises by its aromatic nitration by-product, 2,4- dinitrochlorobenzenes with
The mixture of 2,6- dinitrochlorobenzenes (I) is used as production black sulfide dye, the black sulfide dye that this this method obtains not only product
Matter is low, using difficulty, and high production cost, deficiency in economic performance.Therefore, most of enterprise is in order to reduce by 2,4- dinitro chlorination
Benzene cost increases economic benefit, and the processing mode adopted is not scientific.
Polybenzimidazoles, full name are poly- 2,2 ' -5,5 '-bisbenzimidazole fibers of penylene -, also abbreviation Torquay synthetic fibre
(Togylen), English name Polybenzimidazoles, english abbreviation PBI are the engineering plastics of current highest level
Material, advantage major embodiment are as follows: (1) 310 DEG C of high temperature resistant long-term operating temperature, instantaneous tolerable temperature is up to 760 DEG C；(2) corrosion resistant
Erosion still keeps stability characteristic (quality) in acid or alkali environment；(3) its high-intensitive intensity is twice of Vespel product, existing engineering plastics
The middle highest product of intensity；(4) high rigidity, hardness are the half of glass；(5) high-purity ash content can be controlled in 2ppm
Below.It is succeeded in developing by HoechstCelanse company, the U.S. in middle 1960s, is used primarily for U.S. NASA plan
Middle space flight plane parachute and fire-retardant aerospace protective garment；From after nineteen eighty-three, and develop high-temperature protective clothes etc. comfortable and easy to wear
The product for civilian use；Nearly ten years using increasingly extensively.Current PBI, which is mainly used for high temperature filtration fabric, heat-protective clothing and asbestos, to be replaced
For material；Meanwhile this polymer is in the fields such as film, foamed material and adhesive, semicon industry, special glass industry
Also show its good development prospect.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, and provide a kind of utilization aromatic nitration by-product production
The method of PBI functional material.
Specific technical solution of the present invention is as follows:
A method of using aromatic nitration by-product production PBI functional material, include the following steps:
1) it using aromatic nitration by-product as raw material, separated, collected using Steppecd crystallization and obtained 2,6- dinitro
Benzene Chloride (I), 2,4- dinitrochlorobenzene and residue；
2) the simple compound of 2,6- dinitrochlorobenzene (I) is mixed with the ammonium hydroxide that mass concentration is 18~20%, is heated
40~60 DEG C and stirring extremely reaction completion, obtain 2,6- dinitroaniline (II)；
3) 2,6- dinitroaniline (II), vulcanized sodium are mixed and is added to the water, 95~105 DEG C of heating is simultaneously stirred to reaction
It completes, obtains 3- nitro-o-phenylenediamine (III)；
4) 3- nitro-o-phenylenediamine (III) is reacted to terminal under the conditions of 60~90 DEG C with cyclization reagent, obtains 4- nitre
Base -2- benzimidazolone (IV)；The cyclization reagent is the combination of urea and sulfuric acid or the combination of solid light and triethylamine；
5) a 4- nitro -2- benzimidazolone (IV) successively obtains compound (VIII) through coupling, ammonification, deamination；
Or
B 4- nitro -2- benzimidazolone (IV) successively obtains compound (VIII) through ammonification, coupling, deamination；
Or
C 4- nitro -2- benzimidazolone (IV) successively obtains compound (VIII) through ammonification, deamination, coupling；
6) compound (VIII) is added to the water by a with hydrolysing agent, is lauched in 95~105 DEG C, 0.0~0.2MPa condition
Solution reaction to terminal, obtains 3,3 ', 4,4 '-benzidine (IX)；
Or
Compound (VIII) is added to the water by b with hydrolysing agent, hydrolyzes under the conditions of 95~105 DEG C, 0.0~0.2MPa
Reaction to terminal, obtains 3,3 ', 4,4 '-benzidine (IX)；Then it is further reacted with hydrochloric acid and generates 3,3 ', 4,4 '-benzidine
(IX) hydrochloride；
Wherein hydrolysing agent is one of liquid alkaline, ammonium hydroxide or disodium hydrogen phosphate.
7) by 3,3 ', 4,4 '-benzidine (IX) or 3,3 ', 4,4 '-benzidine (IX) hydrochloride, M-phthalic acid or
Phthalic acid methyl ester, polyphosphoric acids mixing, under 150~230 DEG C, oxygen free condition, reaction obtains PBI (X)；
It is expressed as follows with chemical equation,
Preferably, the step 5) a includes the following steps:
4- nitro -2- benzimidazolone (IV), halogen source and hydrogen peroxide are added in halogenated solvent, reaction to terminal, obtains
To the halogenated -4- nitro -2- benzimidazolone (V) of 6-；The halogen source is bromine, iodine, hydrochloric acid, one in sodium iodide-sulfuric acid
Kind；The halogenated solvent is one of methanol, ethyl alcohol；Halogen source, hydrogen peroxide and 4- nitro -2- benzimidazolone (IV) rub
You are than being 1.04:1.02:1.0；The mass ratio of the halogenated solvent and 4- nitro -2- benzimidazolone (IV) is (2~3): 1；
In the sodium iodide-sulfuric acid, the mass ratio of sodium iodide and sulfuric acid is (0.85~0.87): (1.8~2.1)；
Halogenated -4- nitro -2- the benzimidazolone (V) of 6- is mixed with coupling solvent, acid binding agent, coupling catalyst, in nothing
Under water oxygen free condition, heating stirring to terminal, obtains compound (VI)；The coupling solvent is toluene, dimethylbenzene, N, N- bis-
One of methylformamide；The coupling catalyst is palladium chloride, palladium dydroxide, palladium acetate, palladium carbon, platinum carbon, triphenyl
One of phosphine palladium；The acid binding agent be triethylamine, N-Methyl pyrrolidone, N- methyl piperidine, N- methyl bicyclic oneself
One of amine, pyridine；The coupling solvent and the mass ratio of the halogenated -4- nitro -2- benzimidazolone (V) of 6- are (3~5):
1；The coupling catalyst and the mass ratio of the halogenated -4- nitro -2- benzimidazolone (V) of 6- are (0.003~0.01): 1；Institute
The molar ratio for stating acid binding agent and the halogenated -4- nitro -2- benzimidazolone (V) of 6- is 1.02:1；
Compound (VI), ammonification solvent, amination catalyst, reducing agent are mixed, under the conditions of 0.5~0.8MPa, heating
Stirring to terminal, obtains compound (VII)；Wherein ammonification solvent is one of water, methanol, ethyl alcohol；Wherein amination catalyst
For Raney's nickel, palladium carbon, one kind of platinum carbon；Wherein reducing agent is one kind of hydrogen, hydrazine hydrate, akali sulphide, stannous chloride, zinc powder；
The mass ratio of the ammonification solvent and compound (VI) are (3~5): 1, the mass ratio of amination catalyst and compound (VI) is
(0.005~0.008): 1,2.0~20:1 of molar ratio of reducing agent and compound (VI)；
Compound (VII) is mixed with deamination based solvent, sodium nitrite, sulfuric acid, under the conditions of catalysis of cupric sulphate, is obtained
Compound (VIII)；Wherein deamination based solvent is that isopropanol, one kind of ethyl acetate or arbitrary proportion mixture, deamination are molten
The mass ratio of agent and compound (VII) are (5~8): 1；The mass ratio of copper sulphate and compound (VII) be (0.005~
0.01):1；Sulfuric acid and 4- amino-benzoxazoles class compound (XII) mass ratio are (2~3): 1；Sodium nitrite and 4- ammonia
Base-benzoxazoles class compound (XII) molar ratio is (1.02~1.05): 1；
It is expressed as follows with chemical equation,
Preferably, the step 5) b includes the following steps:
4- nitro -2- benzimidazolone (IV), halogen source and hydrogen peroxide are added in halogenated solvent, reaction to terminal, obtains
To the halogenated -4- nitro -2- benzimidazolone (V) of 6-；The halogen source is bromine, iodine, hydrochloric acid, one in sodium iodide-sulfuric acid
Kind；The halogenated solvent is one of methanol, ethyl alcohol；Mole of halogen source, hydrogen peroxide and 4- nitro -2- benzimidazolone (IV)
Than for 1.04:1.02:1.0；The mass ratio of the halogenated solvent and 4- nitro -2- benzimidazolone (IV) is (2~3): 1；Institute
It states in sodium iodide-sulfuric acid, the mass ratio of sodium iodide and sulfuric acid is (0.85~0.87): (1.8~2.1)；
Halogenated -4- nitro -2- the benzimidazolone (V) of 6-, ammonification solvent, amination catalyst, reducing agent are mixed, 0.5
Under the conditions of~0.8MPa, heating stirring to terminal, obtains compound (XI)；Wherein ammonification solvent is water, in methanol, ethyl alcohol
It is a kind of；Wherein amination catalyst is Raney's nickel, palladium carbon, one kind of platinum carbon；Wherein reducing agent be hydrogen, hydrazine hydrate, akali sulphide,
One kind of stannous chloride, zinc powder；The ammonification solvent and the mass ratio of the halogenated -4- nitro -2- benzimidazolone (V) of 6- are (3
~5): 1, the mass ratio of amination catalyst and the halogenated -4- nitro -2- benzimidazolone (V) of 6- is (0.005~0.008): 1,
The molar ratio (2.0~20) of reducing agent and the halogenated -4- nitro -2- benzimidazolone (V) of 6-: 1；
Compound (XI) is mixed with coupling solvent, acid binding agent, coupling catalyst again, under the conditions of anhydrous and oxygen-free, heating
Stirring to terminal, obtains compound (VII)；The coupling solvent is toluene, dimethylbenzene, N, one in N- dimethylformamide
Kind；The coupling catalyst is one of palladium chloride, palladium dydroxide, palladium acetate, palladium carbon, platinum carbon, triphenylphosphine palladium；
The acid binding agent is one of triethylamine, N-Methyl pyrrolidone, N- methyl piperidine, N- methyldicyclohexylamine, pyridine；
The mass ratio of the coupling solvent and compound (XI) are (3~5): 1；The quality of the coupling catalyst and compound (XI)
Than for (0.003~0.01): 1；The molar ratio of the acid binding agent and compound (XI) are 1.02:1；
Compound (VII) is mixed with deamination solvent, sodium nitrite, sulfuric acid, under the conditions of catalysis of cupric sulphate, is changed
It closes object (VIII)；Wherein deamination solvent be isopropanol, one kind of ethyl acetate or arbitrary proportion mixture, deamination solvent and change
The mass ratio for closing object (VII) is (5~8): 1；The mass ratio of copper sulphate and compound (VII) are (0.005~0.01): 1；Sulphur
Acid is (2~3) with 4- amino-benzoxazoles class compound (XII) mass ratio: 1；Sodium nitrite and 4- amino-benzoxazoles
The molar ratio of class compound (XII) is (1.02~1.05): 1；
It is expressed as follows with chemical equation,
Preferably, the step 5) c includes the following steps:
Compound (IV), ammonification solvent, amination catalyst, reducing agent are mixed, under the conditions of 0.5~0.8MPa, heating
Stirring to terminal, obtains compound (XII)；Wherein ammonification solvent is one of water, methanol, ethyl alcohol；Wherein amination catalyst
For Raney's nickel, palladium carbon, one kind of platinum carbon；Wherein reducing agent is one kind of hydrogen, hydrazine hydrate, akali sulphide, stannous chloride, zinc powder；
The mass ratio of ammonification solvent and compound (IV) are (3~5): 1, the mass ratio of amination catalyst and compound (IV) is
(0.005~0.008): 1,2.0~20:1 of molar ratio of reducing agent and compound (IV)；
Compound (XII) is mixed with deamination based solvent, sodium nitrite, sulfuric acid, under the conditions of catalysis of cupric sulphate, is obtained
Compound (XIII)；Wherein deamination based solvent is that isopropanol, one kind of ethyl acetate or arbitrary proportion mixture, deamination are molten
The mass ratio of agent and compound (XII) are (5~8): 1；The mass ratio of copper sulphate and compound (XII) be (0.005~
0.01):1；Sulfuric acid and 4- amino-benzoxazoles class compound (XII) mass ratio are 2~3:1；Sodium nitrite and 4- amino-
The molar ratio of benzoxazoles class compound (XII) is (1.02~1.05): 1；
Compound (XIII), halogen source and hydrogen peroxide are added in halogenated solvent, reaction to terminal, obtains compound
(XIV)；The halogen source is one of bromine, iodine, hydrochloric acid, sodium iodide-sulfuric acid；The halogenated solvent is methanol, ethyl alcohol
One of；The molar ratio of the halogen source, hydrogen peroxide and compound (XIII) is 1.04:1.02:1.0；The halogenated solvent with
The mass ratio of compound (XIII) is (2~3): 1；In the sodium iodide-sulfuric acid, the mass ratio of sodium iodide and sulfuric acid is (0.85
~0.87): (1.8~2.1)；
Compound (XIV) is mixed with coupling solvent, acid binding agent, coupling catalyst, under the conditions of anhydrous and oxygen-free, heating
Stirring to terminal, obtains compound (VIII)；The coupling solvent is toluene, dimethylbenzene, N, one in N- dimethylformamide
Kind；The coupling catalyst is one of palladium chloride, palladium dydroxide, palladium acetate, palladium carbon, platinum carbon, triphenylphosphine palladium；
The acid binding agent is one of triethylamine, N-Methyl pyrrolidone, N- methyl piperidine, N- methyldicyclohexylamine, pyridine；
The mass ratio of the coupling solvent and compound (XIV) are (3~5): 1；The matter of the coupling catalyst and compound (XIV)
Amount is than being (0.003~0.01): 1；The molar ratio of the acid binding agent and compound (XIV) are 1.02:1.
It is expressed as follows with chemical equation,
Preferably, in the step 2), ammonia and 2 in ammonium hydroxide, the molar ratio of 6- dinitrochlorobenzene (I) be (2.5~
3):1。
Preferably, in the step 3), wherein the molar ratio of 2,6- dinitroanilines (II) and vulcanized sodium is 1:1.5,
The mass ratio of water and 2,6- dinitroaniline (II) are (2~3): 1.
Preferably, in the step 4), when the cyclization reagent is the combination of urea and sulfuric acid, urea and 3- nitre
The molar ratio of base o-phenylenediamine (III) is (1.05~1.1): the matter of 1,68~70% sulfuric acid and 3- nitro-o-phenylenediamine (III)
Amount is than being (1.3~1.5): 1；When the cyclization reagent is the combination of solid light and triethylamine, organic solvent is toluene, diformazan
The one or more combination of benzene, methylene chloride, dichloroethanes, chloroform, wherein organic solvent and 3- nitro-o-phenylenediamine (III)
(3) mass ratio is (2~3): 1, the molar ratio of solid light and 3- nitro-o-phenylenediamine (III) are (0.33~0.34): 1, three second
The molar ratio of amine and solid light is (3.05~3.1): 1；
Preferably, the mass ratio of water and compound (VIII) are 3~5:1 in the step 6), wherein hydrogen in liquid alkaline
The molar ratio of ketone carbonyl is 1.5~2.5:1 in sodium oxide molybdena and hydrolyzed substrate structure；Ammonia and hydrolyzed substrate structure in ammonium hydroxide
The molar ratio of middle ketone carbonyl is 2.5~3.0:1；Disodium hydrogen phosphate hydrolysis reaction system pH is 8.0~8.5.
Preferably, in the step 7), 3,3 ', 4,4 '-benzidine (IX) or 3,3 ', 4,4 '-benzidine (IX) salt
Hydrochlorate is 1:1, polyphosphoric acids and 3,3 ', 4,4 '-benzidine with the molar ratio of M-phthalic acid or M-phthalic acid methyl esters
(IX) or 3,3 ', 4,4 '-benzidine (IX) hydrochloride mass ratio is (0.01~0.015): 1.
Further experiment is studies have shown that directly using aromatic nitration by-product as raw material, through above-mentioned similar synthesis process
Available target compound PBI (X), but synthesis technology is extremely complex and production arylamine class tar content is big, waste is more, mainly
The reason is that need to refine coupling, aminating reaction product repeatedly in the process, be otherwise difficult to meet preparation 3,3 ', 4,
4 '-benzidine compounds (IX) to the quality requirement of its synthesis material, and PBI (X) the plexiglas temperature synthesized it is low,
Hardness is insufficient.Therefore, the method for the present invention is separated using Steppecd crystallization, is received preferably using aromatic nitration by-product as raw material
Collect and obtain 2,6- dinitrochlorobenzene (I) simple compound, is then with the simple compound of 2,6- dinitrochlorobenzene (I)
Material synthesis compound PBI (X).
The present invention in terms of existing technologies, has the advantages that
The present invention discloses a kind of method using aromatic nitration by-product production PBI functional material, and the disclosure method will be difficult
It is converted into the special type function material with Important Economic value with the chemical industry by-product of disposition, enterprise's dangerous waste discharge amount is reduced, is promoted
While enterprise security, business economic income is increased.
The method of the present invention comprehensively consider economic technology it is feasible it is high, environment compatibility is good under the premise of, take reasonable turn
Change process is separated using Steppecd crystallization, is collected and obtained 2,6- dinitro-chlorine using aromatic nitration by-product as raw material
Change benzene (I), 2,4- dinitrochlorobenzene and residue, wherein 2,4- dinitrochlorobenzenes are as commodity direct marketing, residual
The main component of object is the substance of unknown structure, makees waste processing, and 2,6- dinitrochlorobenzenes (I) are then set for PBI (X)
The synthesis of rouge.The present invention is directed to aromatic nitration by-product, i.e. 2,4- dinitrochlorobenzene produces the purification of by-product, discloses one
Kind Steppecd crystallization, primary operational process are that 2, the 4- dinitrochlorobenzene of molten state is produced to by-product to enter substep knot
In brilliant device, according to the difference of 2,4- dinitrochlorobenzene, the fusing point of 2,6- dinitrochlorobenzene, the mode for taking substep to cool down,
2,4- dinitrochlorobenzene, 2,6- dinitrochlorobenzene is precipitated in different temperature stages, cooperation centrifuge is separated by solid-liquid separation, by
Step obtains 2,4- dinitrochlorobenzene or the simple compound of 2,6- dinitrochlorobenzene.This method analysis efficiency is high, can be primary
Property obtain crystallinity very well, 2, the 4- dinitrochlorobenzene or 2 of 99% or more purity, the simple compound of 6- dinitrochlorobenzene,
Meet requirement of the downstream production to 2,4- dinitrochlorobenzene or the simple chemicals matter of 2,6- dinitrochlorobenzene.
Further research, by 3,3 ', 4,4 '-biphenyl of PBI (X) resin obtained through this method and its crucial synthetic intermediate
Amine (IX) delivers PBI (X) production of resins and resin property testing agency carries out all-round property testing, as a result unanimously shows through this
PBI (X) resin and its 3,3 ', 4,4 '-benzidine (IX) of crucial synthetic intermediate that published method obtains are best in quality, and this
PBI (X) is consistent with the comprehensive performance of presently commercially available PBI resin.
Specific embodiment
The present invention is further elaborated and is illustrated With reference to embodiment.Each embodiment in the present invention
Technical characteristic under the premise of not conflicting with each other, can carry out the corresponding combination.
The purification of embodiment 1.2,6- dinitrochlorobenzene (I)
The purification process of 2,6- dinitrochlorobenzene (I) can be summarized as follows:
By the aromatic nitration by-product of 2,4- dinitrochlorobenzene manufacturing enterprise, i.e. 5000kg aromatic nitration by-product is thrown
Enter in fractional crystallization separator, through fractional crystallization process, obtains 2, the 4- dinitrochlorobenzene that 815.5kg purity is 99.3%
The simple compound of simple compound, the 2,6- dinitrochlorobenzene (I) that 4112kg purity is 99.5% and 72.5kg residue.
Wherein, it is obtained through process set forth above:
The simple compound of 2,4- dinitrochlorobenzene that 815.5kg purity is 99.3% produces major product pin as enterprise
It sells；
The simple compound of the 2,6- dinitrochlorobenzene (I) that 4112kg purity is 99.5% is then used as compound PBI (X)
Raw materials for production；
72.5kg residue makees waste processing.
The synthesis of 2. compound PBI (X) of embodiment
1) synthesis of 2,6- dinitroaniline (II)
By 1800kg 2,6- dinitrochlorobenzene (I) is mixed with the ammonium hydroxide of 2200kg 20%, stir, be warming up to 80~
105 DEG C, reaction to terminal, obtains 2, the 6- dinitroaniline (II) of 1619.3kg purity 99%, yield 98.5%.
2) synthesis of 3- nitro-o-phenylenediamine (III)
2, the 6- dinitroaniline (II) of 1619.3kg purity 99% is mixed with 4050kg water, 1366.6kg vulcanized sodium,
Stirring, is heated to 85~95 DEG C, until fully reacting, obtains the 3- nitro-o-phenylenediamine (III) of 1319.6kg purity 99.4%,
Yield 97.8%.
3) synthesis of 4- nitro -2- benzimidazolone (IV)
By the 3- nitro-o-phenylenediamine (III) of 1319.6kg purity 99.4% and 565.4kg urea, 1847.4kg 69%
Sulfuric acid mixing, stirring heat 108~110 DEG C, until fully reacting, obtains the 4- nitro -2- benzene of 1521.9kg purity 98.8%
And imidazolone (IV), yield 98.0%.
4) synthesis of the iodo- 4- nitro -2- benzimidazolone (V) of 6-
4- nitro -2- the benzimidazolone (IV) of 1521.9kg purity 98.8% is mixed with 4500kg methanol, is added
1295.7kg sodium iodide, the mixing of 3000kg sulfuric acid, stirring are warming up between 34-38 degree, and 960.9kg mass fraction 30% is added dropwise
Hydrogen peroxide, be added dropwise, stir to fully reacting, obtain the iodo- 4- nitro -2- benzo of 6- of 2545.6kg purity 99.6%
Imidazolone (V), yield 99.0%.The hydrogen nuclear magnetic resonance modal data of the compound (V): 1HNMR (500MHz, DMSO-
D6): δ 5.87 (br., 1H), 6.10 (br., 1H), 8.10 (s, 1H), 8.41 (s, 1H).
5) synthesis of compound (VI)
By the iodo- 4- nitro -2- benzimidazolone (V) of the 6- of 2545.6kg 99.6%, 10000kg dimethylbenzene, 12.5kg
Palladium chloride, the mixing of 856.3kg triethylamine, under the conditions of anhydrous and oxygen-free, heating stirring to terminal, obtains 1249.04kg purity
99.3% compound (VI), yield 97.5%.The hydrogen nuclear magnetic resonance modal data of the compound (VI): 1HNMR
(500MHz, DMSO-d6): δ 5.70 (br., 2H), 6.11 (br., 2H), 7.75~7.76 (d, 2H), 8.23~8.24 (d,
2H)。
6) synthesis of compound (VII)
The compound (VI), 5000kg methanol, 9.9kg Raney's nickel of 1249.04kg purity 99.3% are mixed, stirring adds
Heat is passed through hydrogen, and under the conditions of 0.5~0.8MPa, reaction to terminal, obtains the compound of 995.2kg purity 99.1%
(VII), yield 95.6%.The hydrogen nuclear magnetic resonance modal data of the compound (VII): 1HNMR (500MHz, DMSO-d6): δ
5.58 (br., 2H), 5.91 (br., 2H), 6.25 (br., 4H), 7.25~7.26 (d, 2H), 8.13~7.14 (d, 2H).
7) synthesis of compound (VIII)
By the compound (VII) of 995.2kg purity 99.1% and 201.9kg isopropanol, 5769.3kg ethyl acetate,
2000kg sulfuric acid, 234.2kg sodium nitrite, the mixing of 7.5kg copper sulphate, are stirred, and heating until reaction terminates, obtains 840.5kg
The compound (VIII) of purity 98.5%, yield 93.4%.The hydrogen nuclear magnetic resonance modal data of the compound (VIII):
1HNMR (500MHz, DMSO-d6): δ 5.9~6.1 (br., 4H), 7.51 (d, 2H), 7.85 (d, 2H), 8.05 (s, 2H).
8) synthesis of 3,3', 4,4'- tetra-amino-biphenyl (IX)
The compound (VIII) of 840.5kg purity 98.5% is mixed with 3437.2kg water, disodium hydrogen phosphate is added to body
It is pH=8.3~8.5, stirring, hydrolysis to terminal, it is pure to obtain 643.8kg under the conditions of 95~105 DEG C, 0~0.2MPa
The 3,3' of degree 99.5%, 4,4'- tetra-amino-biphenyl (IX).
9) synthesis of compound PBI (X)
By the 3,3' of 643.8kg purity 99.5%, 4,4'- tetra-amino-biphenyl (IX) and 496.5kg M-phthalic acid are mixed
It closes, 6.5kg polyphosphoric acids is added, air in exclusion system is warming up to 150~230 DEG C, until reaction is completed, obtains
916.5kgPBI (X) resin.
The synthesis of 3. compound PBI (X) of embodiment
1) with the 3,3' of the 643.8kg purity 99.5% obtained through process described in embodiment 2,4,4'- tetra-amino-biphenyl
(IX) it is raw material, is mixed with 1500kg ethyl alcohol, 500kg water, under the conditions of 25~50 DEG C, 422.9 concentration 30~31% is added
Hydrochloric acid, reaction terminate, and obtain the hydrochloride for 3,3', 4, the 4'- tetra-amino-biphenyls (IX) that 818.2kg purity is 99.7%, yield
94.8%；It was post-processed at salt and claims mother liquid obtained to be applied to lower batch salification process；
2) 3,3' for being 99.7% by 818.2kg purity, between the hydrochloride and 553.9kg of 4,4'- tetra-amino-biphenyl (IX)
12.3kg polyphosphoric acids is added in rutgers mixing, and air in exclusion system is warming up to 150~230 DEG C, until reaction
It completes, obtains 866.6.5kgPBI (X) resin.
Embodiment 4. compound PBI (X) performance detection
By PBI (X) resin obtained by embodiment 2,3 processes and commercially available PBI (X) resin, plastotype is under the same conditions
The cylindrical rod of same size carries out performance test as shown in the table to three.
Its key data:
Thus table data it is found that PBI (X) resin and commercially available PBI (X) resin obtained by embodiment 2,3 processes identical
Under the conditions of plastotype be same size cylindrical rod have similar performance.
The synthesis of 5. compound of embodiment (XIII)
1) synthesis of compound (XII)
By in embodiment 2 step 3) synthesize 181.3kg purity 98.8% 4- nitro -2- benzimidazolone (IV) with
537.3kg ethyl alcohol, the mixing of 0.9kg platinum carbon, stirring, heating are passed through hydrogen, under the conditions of 0.5~0.8MPa, react to terminal,
Obtain the compound (XII) of 147.9kg purity 99.1%, yield 98.3%.
2) synthesis of compound (XIII)
By the compound (XII) of 147.9kg purity 99.1% and 739.5kg ethyl acetate, 850.3kg sulfuric acid, 71.2kg
Sodium nitrite, the mixing of 0.75kg copper sulphate, are stirred, and heating until reaction terminates, obtains the compound of 124.6kg purity 99.2%
(XIII), yield 93.8%.
The synthesis of 5. compound of embodiment (VI)
The iodo- 4- nitro -2- benzimidazolone of the 6- for the 2545.6kg 99.6% that will be obtained through step 4) in embodiment 2
(V), 7636.8kgN, dinethylformamide, 12.5kg palladium carbon, the mixing of 1639.6kg N- methyldicyclohexylamine triethylamine,
Under the conditions of anhydrous and oxygen-free, heating stirring to terminal, obtains the compound (VI) of 1245.7kg purity 99.3%, yield 97.2%.
The synthesis of 6. compound of embodiment (XI)
1) synthesis of compound (V)
4- nitro -2- the benzimidazolone (IV) of the 1521.9kg purity 98.8% obtained through step 3) in embodiment 2 with
The mixing of 4500kg methanol, is added 1381.3kg bromine, the mixing of 2850kg sulfuric acid, and stirring is warming up between 40-45 degree, is added dropwise
The hydrogen peroxide of 960.9kg mass fraction 30%, is added dropwise, and stirs to fully reacting, obtains 2149.0kg purity 99.5%
The bromo- 4- nitro -2- benzimidazolone (V) of 6-, yield 98.7%.
2) synthesis of compound (XI)
The bromo- 4- nitro -2- benzimidazolone (V) of the 6- of 2149.0kg purity 99.5% is mixed with 8596kg water, is added
3927.9kg stannous chloride, heating, stirring terminate to reaction, obtain the bromo- 4- amino -2- of 6- of 1827.1kg purity 99.7%
Benzimidazolone (XI), yield 96.4%.The hydrogen nuclear magnetic resonance modal data of the compound (XI): 1HNMR (500MHz,
DMSO-d6): δ 5.91 (br., 1H), 6.11 (br., 1H), 6.23 (br., 2H), 6.51 (s, 1H), 7.22 (s, 1H).
The synthesis of 7. compound of embodiment (XII)
4- nitro -2- the benzimidazolone (IV) for the 181.3kg purity 98.8% that will be synthesized through step 3) in embodiment 2
It mixes, stirs with 895.5kg methanol, 0.9kg palladium carbon, the hydrazine hydrate of 125kg mass fraction 80%, reaction knot is added in heating
Beam obtains the compound (VII) of 146.4kg purity 99.5%, yield 97.7%.
Above-mentioned embodiment is only a preferred solution of the present invention, so it is not intended to limiting the invention.Have
The those of ordinary skill for closing technical field can also make various changes without departing from the spirit and scope of the present invention
Change and modification.Therefore all mode technical solutions obtained for taking equivalent substitution or equivalent transformation, all fall within guarantor of the invention
It protects in range.
Claims (9)
1. a kind of method using aromatic nitration by-product production PBI functional material, which comprises the steps of:
1) it using aromatic nitration by-product as raw material, separated, collected using Steppecd crystallization and obtained 2,6- dinitro chlorination
Benzene (I), 2,4- dinitrochlorobenzene and residue.
Step 2: 2,6- dinitrochlorobenzene (I) being mixed with the ammonium hydroxide that mass concentration is 18~20%, 40~60 DEG C of heating is simultaneously
Stirring to reaction is completed, and 2,6- dinitroaniline (II) is obtained；
Step 3: 2,6- dinitroaniline (II), vulcanized sodium being mixed and are added to the water, 95~105 DEG C of heating is simultaneously stirred to having reacted
At obtaining 3- nitro-o-phenylenediamine (III).
Step 4: 3- nitro-o-phenylenediamine (III) being reacted to terminal under the conditions of 60~90 DEG C with cyclization reagent, obtains 4- nitre
Base -2- benzimidazolone (IV)；The cyclization reagent is the combination of urea and sulfuric acid or the combination of solid light and triethylamine；
Step 5:
5a) 4- nitro -2- benzimidazolone (IV) successively obtains compound (VIII) through coupling, ammonification, deamination；
Or
5b) 4- nitro -2- benzimidazolone (IV) successively obtains compound (VIII) through ammonification, coupling, deamination；
Or
5c) 4- nitro -2- benzimidazolone (IV) successively obtains compound (VIII) through ammonification, deamination, coupling；
Step 6:
6a) compound (VIII) is added to the water with hydrolysing agent, hydrolysis under the conditions of 95~105 DEG C, 0.0~0.2MPa
To terminal, 3,3 ', 4,4 '-benzidine (IX) are obtained；
Or
6b) compound (VIII) is added to the water with hydrolysing agent, hydrolysis under the conditions of 95~105 DEG C, 0.0~0.2MPa
To terminal, 3,3 ', 4,4 '-benzidine (IX) are obtained；Then it is further reacted with hydrochloric acid and generates 3,3 ', 4,4 '-benzidine (IX)
Hydrochloride；
Wherein hydrolysing agent is one of liquid alkaline, ammonium hydroxide or disodium hydrogen phosphate；
Step 7: by 3,3 ', 4,4 '-benzidine (IX) or 3,3 ', 4,4 '-benzidine (IX) hydrochloride, M-phthalic acid or isophthalic
Dicarboxylic acid methyl ester, polyphosphoric acids mixing, under 150~230 DEG C, oxygen free condition, reaction obtains PBI (X).
It is expressed as follows with chemical equation,
2. utilizing the method for aromatic nitration by-product production PBI functional material as described in claim 1, which is characterized in that described
Step 5a) include the following steps:
4- nitro -2- benzimidazolone (IV), halogen source and hydrogen peroxide are added in halogenated solvent, reaction to terminal, obtains 6-
Halogenated -4- nitro -2- benzimidazolone (V)；The halogen source is one of bromine, iodine, hydrochloric acid, sodium iodide-sulfuric acid；Institute
Stating halogenated solvent is one of methanol, ethyl alcohol；The molar ratio of halogen source, hydrogen peroxide and 4- nitro -2- benzimidazolone (IV) is
1.04:1.02:1.0；The mass ratio of the halogenated solvent and 4- nitro -2- benzimidazolone (IV) is (2~3): 1；The iodine
Change in sodium-sulfuric acid, the mass ratio of sodium iodide and sulfuric acid is (0.85~0.87): (1.8~2.1)；
Halogenated -4- nitro -2- the benzimidazolone (V) of 6- is mixed with coupling solvent, acid binding agent, coupling catalyst, in anhydrous nothing
Under the conditions of oxygen, heating stirring to terminal, obtains compound (VI)；The coupling solvent is toluene, dimethylbenzene, N, N- dimethyl methyl
One of amide；The coupling catalyst is palladium chloride, palladium dydroxide, palladium acetate, palladium carbon, platinum carbon, triphenylphosphine palladium
One of；The acid binding agent is triethylamine, in N-Methyl pyrrolidone, N- methyl piperidine, N- methyldicyclohexylamine, pyridine
One kind；The coupling solvent and the mass ratio of the halogenated -4- nitro -2- benzimidazolone (V) of 6- are (3~5): 1；The coupling
Catalyst and the mass ratio of the halogenated -4- nitro -2- benzimidazolone (V) of 6- are (0.003~0.01): 1；The acid binding agent and 6-
The molar ratio of halogenated -4- nitro -2- benzimidazolone (V) is 1.02:1；
Compound (VI), ammonification solvent, amination catalyst, reducing agent are mixed, under the conditions of 0.5~0.8MPa, heating stirring
To terminal, compound (VII) is obtained；Wherein ammonification solvent is one of water, methanol, ethyl alcohol；Wherein amination catalyst is thunder
Buddhist nun's nickel, palladium carbon, one kind of platinum carbon；Wherein reducing agent is one kind of hydrogen, hydrazine hydrate, akali sulphide, stannous chloride, zinc powder；It is described
The mass ratio of ammonification solvent and compound (VI) are (3~5): 1, the mass ratio of amination catalyst and compound (VI) are (0.005
~0.008): 1,2.0~20:1 of molar ratio of reducing agent and compound (VI)；
Compound (VII) is mixed with deamination based solvent, sodium nitrite, sulfuric acid, under the conditions of catalysis of cupric sulphate, obtains compound
(VIII)；Wherein deamination based solvent is isopropanol, one kind of ethyl acetate or arbitrary proportion mixture, deamination based solvent and chemical combination
The mass ratio of object (VII) is (5~8): 1；The mass ratio of copper sulphate and compound (VII) are (0.005~0.01): 1；Sulfuric acid with
4- amino-benzoxazoles class compound (XII) mass ratio is (2~3): 1；Sodium nitrite and 4- amino-benzoxazoles class
The molar ratio for closing object (XII) is (1.02~1.05): 1；
It is expressed as follows with chemical equation,
3. utilizing the method for aromatic nitration by-product production PBI functional material as described in claim 1, which is characterized in that described
Step 5b) include the following steps:
4- nitro -2- benzimidazolone (IV), halogen source and hydrogen peroxide are added in halogenated solvent, reaction to terminal, obtains 6-
Halogenated -4- nitro -2- benzimidazolone (V)；The halogen source is one of bromine, iodine, hydrochloric acid, sodium iodide-sulfuric acid；Institute
Stating halogenated solvent is one of methanol, ethyl alcohol；The molar ratio of halogen source, hydrogen peroxide and 4- nitro -2- benzimidazolone (IV) is
1.04:1.02:1.0；The mass ratio of the halogenated solvent and 4- nitro -2- benzimidazolone (IV) is (2~3): 1；The iodine
Change in sodium-sulfuric acid, the mass ratio of sodium iodide and sulfuric acid is (0.85~0.87): (1.8~2.1)；
Halogenated -4- nitro -2- the benzimidazolone (V) of 6-, ammonification solvent, amination catalyst, reducing agent are mixed, 0.5~
Under the conditions of 0.8MPa, heating stirring to terminal, obtains compound (XI)；Wherein ammonification solvent is water, methanol, one in ethyl alcohol
Kind；Wherein amination catalyst is Raney's nickel, palladium carbon, one kind of platinum carbon；Wherein reducing agent is hydrogen, hydrazine hydrate, akali sulphide, chlorination
Stannous, one kind of zinc powder；The ammonification solvent and the mass ratio of the halogenated -4- nitro -2- benzimidazolone (V) of 6- are (3~5):
1, the mass ratio of amination catalyst and the halogenated -4- nitro -2- benzimidazolone (V) of 6- is (0.005~0.008): 1, reducing agent
With the molar ratio (2.0~20) of the halogenated -4- nitro -2- benzimidazolone (V) of 6-: 1；
Compound (XI) is mixed with coupling solvent, acid binding agent, coupling catalyst again, under the conditions of anhydrous and oxygen-free, heating stirring
To terminal, compound (VII) is obtained；The coupling solvent is one of toluene, dimethylbenzene, N,N-dimethylformamide；Institute
The coupling catalyst stated is one of palladium chloride, palladium dydroxide, palladium acetate, palladium carbon, platinum carbon, triphenylphosphine palladium；Described
Acid binding agent is one of triethylamine, N-Methyl pyrrolidone, N- methyl piperidine, N- methyldicyclohexylamine, pyridine；The coupling
The mass ratio of solvent and compound (XI) are (3~5): 1；The mass ratio of the coupling catalyst and compound (XI) are (0.003
~0.01): 1；The molar ratio of the acid binding agent and compound (XI) are 1.02:1；
Compound (VII) is mixed with deamination solvent, sodium nitrite, sulfuric acid, under the conditions of catalysis of cupric sulphate, obtains compound
(VIII)；Wherein deamination solvent is isopropanol, one kind of ethyl acetate or arbitrary proportion mixture, deamination solvent and compound
(VII) mass ratio is (5~8): 1；The mass ratio of copper sulphate and compound (VII) are (0.005~0.01): 1；Sulfuric acid and 4-
Amino-benzoxazoles class compound (XII) mass ratio is (2~3): 1；Sodium nitrite and 4- amino-benzoxazoles class chemical combination
The molar ratio of object (XII) is (1.02~1.05): 1；
It is expressed as follows with chemical equation,
4. utilizing the method for aromatic nitration by-product production PBI functional material as described in claim 1, which is characterized in that described
Step 5c) include the following steps:
Compound (IV), ammonification solvent, amination catalyst, reducing agent are mixed, under the conditions of 0.5~0.8MPa, heating stirring
To terminal, compound (XII) is obtained；Wherein ammonification solvent is one of water, methanol, ethyl alcohol；Wherein amination catalyst is thunder
Buddhist nun's nickel, palladium carbon, one kind of platinum carbon；Wherein reducing agent is one kind of hydrogen, hydrazine hydrate, akali sulphide, stannous chloride, zinc powder；Ammonification
The mass ratio of solvent and compound (IV) are (3~5): 1, the mass ratio of amination catalyst and compound (IV) be (0.005~
0.008): 1,2.0~20:1 of molar ratio of reducing agent and compound (IV)；
Compound (XII) is mixed with deamination based solvent, sodium nitrite, sulfuric acid, under the conditions of catalysis of cupric sulphate, obtains compound
(XIII)；Wherein deamination based solvent is isopropanol, one kind of ethyl acetate or arbitrary proportion mixture, deamination based solvent and chemical combination
The mass ratio of object (XII) is (5~8): 1；The mass ratio of copper sulphate and compound (XII) are (0.005~0.01): 1；Sulfuric acid with
4- amino-benzoxazoles class compound (XII) mass ratio is 2~3:1；Sodium nitrite and 4- amino-benzoxazoles class chemical combination
The molar ratio of object (XII) is (1.02~1.05): 1；
Compound (XIII), halogen source and hydrogen peroxide are added in halogenated solvent, reaction to terminal, obtains compound (XIV)；Institute
Stating halogen source is one of bromine, iodine, hydrochloric acid, sodium iodide-sulfuric acid；The halogenated solvent is one of methanol, ethyl alcohol；
The molar ratio of the halogen source, hydrogen peroxide and compound (XIII) is 1.04:1.02:1.0；The halogenated solvent and compound
(XIII) mass ratio is (2~3): 1；In the sodium iodide-sulfuric acid, the mass ratio of sodium iodide and sulfuric acid be (0.85~
0.87): (1.8~2.1)；
Compound (XIV) is mixed with coupling solvent, acid binding agent, coupling catalyst, under the conditions of anhydrous and oxygen-free, heating stirring is extremely
Terminal obtains compound (VIII)；The coupling solvent is one of toluene, dimethylbenzene, N,N-dimethylformamide；It is described
Coupling catalyst be one of palladium chloride, palladium dydroxide, palladium acetate, palladium carbon, platinum carbon, triphenylphosphine palladium；Described ties up
Sour agent is one of triethylamine, N-Methyl pyrrolidone, N- methyl piperidine, N- methyldicyclohexylamine, pyridine；The coupling is molten
The mass ratio of agent and compound (XIV) are (3~5): 1；The mass ratio of the coupling catalyst and compound (XIV) are (0.003
~0.01): 1；The molar ratio of the acid binding agent and compound (XIV) are 1.02:1；
It is expressed as follows with chemical equation,
5. utilizing the method for aromatic nitration by-product production PBI functional material as described in claim 1, which is characterized in that described
In step 2), ammonia and 2 in ammonium hydroxide, the molar ratio of 6- dinitrochlorobenzene (I) is (2.5~3): 1.
6. utilizing the method for aromatic nitration by-product production PBI functional material as described in claim 1, which is characterized in that described
In step 3), wherein the molar ratio of 2,6- dinitroanilines (II) and vulcanized sodium is 1:1.5, water and 2,6- dinitroaniline (II)
Mass ratio be (2~3): 1.
7. utilizing the method for aromatic nitration by-product production PBI functional material as described in claim 1, which is characterized in that described
In step 4), when the cyclization reagent is the combination of urea and sulfuric acid, the molar ratio of urea and 3- nitro-o-phenylenediamine (III)
For (1.05~1.1): the mass ratio of 1,68~70% sulfuric acid and 3- nitro-o-phenylenediamine (III) are (1.3~1.5): 1；Work as institute
When stating the combination that cyclization reagent is solid light and triethylamine, organic solvent is toluene, dimethylbenzene, methylene chloride, dichloroethanes, chloroform
One or more combination, wherein the mass ratio of organic solvent and 3- nitro-o-phenylenediamine (III) (3) is (2~3): 1, solid light
Molar ratio with 3- nitro-o-phenylenediamine (III) is (0.33~0.34): 1, the molar ratio of triethylamine and solid light be (3.05~
3.1):1。
8. utilizing the method for aromatic nitration by-product production PBI functional material as described in claim 1, which is characterized in that described
Step 6 in the mass ratio of water and compound (VIII) be 3~5:1, wherein sodium hydroxide and hydrolyzed substrate structure in liquid alkaline
The molar ratio of middle ketone carbonyl is 1.5~2.5:1；In ammonium hydroxide in ammonia and hydrolyzed substrate structure the molar ratio of ketone carbonyl be 2.5~
3.0:1；Disodium hydrogen phosphate hydrolysis reaction system pH is 8.0~8.5.
9. utilizing the method for aromatic nitration by-product production PBI functional material as described in claim 1, which is characterized in that described
Step 7) in, 3,3 ', 4,4 '-benzidine (IX) or 3,3 ', 4,4 '-benzidine (IX) hydrochlorides, with M-phthalic acid or
The molar ratio of phthalic acid methyl ester is 1:1, polyphosphoric acids and 3,3 ', 4,4 '-benzidine (IX) or 3,3 ', 4,4 '-benzidine
(IX) hydrochloride mass ratio is (0.01~0.015): 1.
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