CN108191669A - A kind of synthetic method of 1,2,4,5- tetraminos benzene and application - Google Patents

A kind of synthetic method of 1,2,4,5- tetraminos benzene and application Download PDF

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CN108191669A
CN108191669A CN201711479561.4A CN201711479561A CN108191669A CN 108191669 A CN108191669 A CN 108191669A CN 201711479561 A CN201711479561 A CN 201711479561A CN 108191669 A CN108191669 A CN 108191669A
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benzene
tetramino
synthetic method
acid solution
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葛裕华
胡慧书
许航
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Southeast University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • 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
    • C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/18—Polybenzimidazoles

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Abstract

Synthetic method and application, synthetic method the invention discloses a kind of 1,2,4,5 tetramino benzene include the following steps：With 1,2,3 trichloro-benzenes of Benzene Chloride by-product for raw material, 4,6 dinitro, 1,2,3 trichloro-benzenes is obtained through nitrification；Further ammonolysis obtains 4,6 dinitro, 2 chlorine, 1,3 phenylenediamine in organic solvent A；Then, ammonia products are dissolved in organic solvent B, catalytic hydrogenolysis obtains 1,2,4,5 tetramino benzene.Compared with prior art, 1,2,3 trichloro-benzenes of by-product of Benzene Chloride is utilized in one aspect of the present invention well, and another aspect hydrogenolysis process collects nitro reduction and halogen hydrogenolysis in a step, and industrialized production preferably provides raw material support to develop product downstream.Its application is for raw material and 2 with 1,2,4,5 tetramino benzene, and PDBI resins are made in 5 dihydric para-phthalic acids polymerization, is a kind of technical fiber material with good spinnability and high-modulus.

Description

A kind of synthetic method of 1,2,4,5- tetraminos benzene and application
Technical field
The invention belongs to technical field of compound preparation, and in particular to a kind of synthetic method of 1,2,4,5- tetramino benzene and Using.
Background technology
1,2,4,5- tetramino benzene, abbreviation TAB are aromatic series quaternary amines relatively simple for structure, utilize 1,2,4,5- tetra- The application of aminobenzene and its hydrochloride on new material research has been reported that more, such as can be with 2,5-Dihydroxyterephthalic acid (DHTA) preparing improves the fiber of durability, but the synthesis of 1,2,4,5- tetramino benzene is but rarely reported, and it is a kind of suitable to design Process route synthesize 1,2,4,5- tetramino benzene, realize 1,2,4,5- tetramino benzene industrialized production, promote new material gather Ester, the application of poly- fiber are particularly important.
Golden rather people is waited with 4,6- dichloros m-dinitrobenzene as raw material, using ammonium hydroxide as the double ammonolysis reactions of ammonolysis agent progress, then Continue catalytic hydrogenating reduction in methanol solution, report the synthesis of 1,2,4,5- tetramino benzene and its hydrochloride for the first time at home (Journal of Chemical Industry and Engineering, 2012,63 (7)：2092-2099), 1 finally synthesized, the total recovery of 2,3,5- tetramino hydrochlorides are 79.7%, total recovery is relatively low, and synthesis cost is higher.
Chinese patent application application No. is CN2013107227365 discloses a kind of 1,2,3,5- tetraminos hydrochloride Synthetic method, first with m-dichlorobenzene the concentrated sulfuric acid, fuming nitric aicd nitration mixture in digestion prepare 1,3-, bis- chloro- 4,6- dinitros Benzene；It is passed through into ammonium hydroxide ammonolysis at 150 DEG C again, obtains 4,6- dinitro -1,3- phenylenediamines；Then hydrogenating reduction obtains TAB, then It is conducted into olefin(e) acid solution and prepares 1,2,3,5- tetramino hydrochlorides, 1,2,3, the 5- tetramino salt prepared using this kind of method Hydrochlorate, yield increase, but since raw material m-dichlorobenzene higher price, production cost rise, are unfavorable for industrialized production.
In conclusion the synthetic method of the TAB reported at present is primarily present the problem of two aspects：On the one hand, TAB's is total Yield is relatively low；On the other hand, using ammonium hydroxide as ammonolysis agent, ammonolysis purity is relatively low, and the higher price of raw material m-dichlorobenzene, unfavorable In industrialized production.
Benzene Chloride is a kind of important industrial chemicals and organic intermediate, with the fast development of Benzene Chloride industry, chlorination Benzene production capacity improves rapidly；Contain organic matter however, often producing the big appointment of 1 ton of Benzene Chloride during benzene chloride production and generating 1 ton By-product, direct emission not only pollutes environment, do not meet emission request and a kind of serious wasting of resources.Promote chlorination The research of utilization of benzene by-product had not only avoided the pollution to environment, but also realized the increase in value of Benzene Chloride by-product.
Invention content
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of synthetic method of 1,2,4,5- tetramino benzene and Using, with 1,2,3- trichloro-benzenes of Benzene Chloride by-product be raw material, prepare 1,2,4,5- tetramino benzene, further synthesize poly- Isosorbide-5-Nitrae- (2,5- dihydroxy) phenylene -2,6- benzo diimidazole resins (PDBI).One aspect of the present invention realizes Benzene Chloride by-product 1, The comprehensive utilization of 2,3- trichloro-benzenes improves resource utilization；On the other hand production cost is reduced, can also be that exploitation is produced downstream Product provide raw material support.
The present invention solve its technical problem the technical solution adopted is that：
A kind of preparation method of 1,2,4,5- tetramino benzene, includes the following steps：
(1) 1,2,3- trichloro-benzenes is subjected to nitration reaction, obtains yellow solid 4,6- dinitros -1,2,3- trichloro-benzenes；
(2) step (1) products therefrom is dissolved in organic solvent A, moves into and leads to NH in autoclave3Ammonolysis reaction is carried out, ammonolysis obtains To chloro- 1, the 3- phenylenediamines of 4,6- dinitros -2-, wherein organic solvent A is alcohols or ether solvent；
(3) step (2) products therefrom is dissolved in organic solvent B, carries out hydrogenolysis under the conditions of heating compressive reaction, is catalyzed hydrogen Solution reduction directly obtains 1,2,4,5- tetramino benzene of target product, and wherein organic solvent B is alcohol, tetrahydrofuran, the N-N- of C1-C3 Any one in dimethylformamide or N-N dimethylanilines.
As the optimal technical scheme of the application, the nitrating agent that nitration reaction uses in the step (1) is 65% dense nitre Acid or nitrate, dropping temperature are 35-90 DEG C.
As the optimal technical scheme of the application, the condition of nitration reaction is in the step (1)：50-100 DEG C of temperature, Reaction time 2-7h.
As the optimal technical scheme of the application, organic solvent A is tetrahydrofuran, ethylene glycol or first in the step (2) Any one in alcohol.
As the optimal technical scheme of the application, ammonolysis reaction condition is in the step (2)：Temperature is 100-180 DEG C, Ammonia presses 0.2-2.0MPa, reaction time 6-10h.
As the optimal technical scheme of the application, the temperature of hydrogenolysis is 75-110 DEG C in the step (3), hydrogen pressure 1.0-2.0MPa, catalyst are RaneyNi or Pd/C, reaction time 2-10h.
Preferably, the catalyst is 3%Pd/C, and the catalyst charge is chloro- 1, the 3- benzene two of 4,6- dinitros -2- The 2%-10% of amine quality.
1,2,4,5- tetramino benzene 1,2,4,5- tetraminos benzene obtained by above-mentioned technical proposal is preparing poly- 1,4- (2,5- bis- Hydroxyl) application in phenylene -2,6- benzo diimidazoles.
As the optimal technical scheme of the application, the 1 of gained, 2,4,5- tetramino benzene is added in acid solution, nitrogen Protection adds in compound 2,5-Dihydroxyterephthalic acid, and for subsequent gradient increased temperature to 200 DEG C, polymerization obtains poly- Isosorbide-5-Nitrae-(2,5- bis- Hydroxyl) phenylene -2,6- benzo diimidazole acid liquid crystal stoste, wash, detach, being dried to obtain poly- Isosorbide-5-Nitrae-(2,5- dihydroxy) Phenylene -2,6- benzo diimidazole, wherein, described 1,2,4,5- tetramino benzene：The molar ratio of 2,5- dihydric para-phthalic acids For 1.2-2.0：1.
As the optimal technical scheme of the application, the acid solution be poly phosphoric acid solution, 1,2,4,5- tetramino Benzene：The mass ratio of poly phosphoric acid solution is 1：6-18；P in the poly phosphoric acid solution2O5Mass concentration is 75-90%.
As the optimal technical scheme of the application, the acid solution is sulfuric acid solution or phosphoric acid solution, and dosage is 6-20 times of reactant quality.
Its specific synthetic route is as follows：
Compared with prior art, beneficial effects of the present invention are as follows：
(1) recycling to 1,2, the 3- trichloro-benzenes of by-product of Benzene Chloride is had effectively achieved, avoids environmental pollution；
(2) synthesis cost of 1,2,4,5- tetramino benzene is greatly reduced, is more favorable for industrialized production；
(3) hydrogenolysis process collects hydrogenating reduction and halogen hydrogenolysis in a step, and industrialized production preferably is produced downstream for exploitation Product provide raw material support, promote the innovation research of new material.
Specific embodiment
The method of the present invention is described in more detail with reference to specific embodiment, the present embodiment is with the present invention Implemented under premised on technical solution, give detailed embodiment and specific operating process, but the protection of the present invention Range is not limited to following embodiments, and production firm is not specified in agents useful for same or instrument and equipment, is accordingly to be regarded as that city can be passed through The conventional products of field purchase.
Embodiment 1
(1) 72g (0.4mol) 1,2,3- trichloro-benzenes, the 200mL98% concentrated sulfuric acids are added in the there-necked flask of 500mL, heat, 65% concentrated nitric acid 40mL is added dropwise in stirring, dissolved clarification, and dropping temperature is controlled at 55 ± 10 DEG C, and reaction temperature control is 70 ± 5 after drop finishes DEG C, the reaction was continued 5h stops reaction, obtains yellow solid crude product 4,6,-dinitro -1,2,3- trichloro-benzenes, yield 86.9%, Purity is 93.7%.
(2) 25g (0.1mol) 4,6- dinitros -1,2 are added in the autoclave of 250mL, 3- trichloro-benzenes is dissolved in 50mL second Glycol is heated to 150 DEG C, leads to ammonia, and ammonia pressure 1.0MPa reacts 8h, stops reaction, and cooling, filtering obtain crude product, through anhydrous Ethyl alcohol recrystallization obtains chloro- 1, the 3- phenylenediamines of 4,6- dinitros -2-, yield 84.5%, purity 97.6%.
(3) addition chloro- 1, the 3- phenylenediamines of 10g (0.04mol) 4,6- dinitros -2- in 100mL autoclaves, 50mLDMF, 0.3g 3%Pd/C, heating stirring lead to hydrogen, and hydrogen pressure 1.5MPa reacts 8h, stops reaction, and cooling, filtering obtain crude product, pass through 1,2,4,5- tetramino benzene, yield 84.9%, purity 92.3% are obtained after acetone recrystallization.
(4) 12.0gP is sequentially added in reaction bulb2O5With 80% polyphosphoric acids of 36.0g, heating, stirring, dissolved clarification, nitrogen Protection adds in 1,2,4,5- tetramino benzene of 5.21g, 2.2g 2,5-Dihydroxyterephthalic acids, gradient increased temperature to 200 DEG C of reactions Stop reaction after 5h, obtain the polyphosphoric acids liquid crystal stoste of poly- Isosorbide-5-Nitrae-(2,5- dihydroxy) phenylene -2,6- benzo diimidazole, take Go out liquid crystal stoste through washing, being dried to obtain poly- Isosorbide-5-Nitrae-(2,5- dihydroxy) phenylene -2,6- benzo diimidazole, yield 86.2%, Purity 93.5%.
Embodiment 2
Using the method for embodiment 1, the difference is that only：System is nitrified described in step (1) and is changed to the concentrated sulfuric acid-nitric acid Sodium system；Ammonolysis solvent described in step (2) be methanol, 100 DEG C of ammonolysis temperature, ammonia pressure 0.2MPa, reaction time 6h；Step (3) hydrogenolysis solvent described in is tetrahydrofuran, under RaneyNi effects, 75 DEG C of hydrogenolysis temperature, and hydrogen pressure 1.5MPa, reaction time 2h, 1,2,4,5- tetramino benzene of final product, yield 73.2%, purity 92.6%.
Embodiment 3
Using the method for embodiment 1, the difference is that only：Ammonolysis solvent described in step (2) be tetrahydrofuran, ammonolysis 180 DEG C of temperature, ammonia pressure 2.0MPa, reaction time 10h；Hydrogenolysis solvent described in step (3) is DMA, under 3%Pt/C effects, hydrogen 110 DEG C of temperature is solved, hydrogen presses 2.0MPa, reaction time 10h, 1,2,4,5- tetramino benzene of final product, yield 84.2%, purity It is 86.9%.
Embodiment 4
Using the method for embodiment 1, the difference is that only：The step (3) is using 10L autoclaves；Add in 1kg Chloro- 1, the 3- phenylenediamines of (4mol) 4,6- dinitros -2-, 5L DMF, 30g 3%Pd/C, catalytic hydrogenolysis obtain 1,2,4,5- tetra- ammonia Base benzene, yield 83.5%, purity 90.1%.
Embodiment 5
Using the method for embodiment 1, the difference is that only：1,2,4,5- tetraminos employed in the step (4) Benzene：The mass ratio of poly phosphoric acid solution is 1：18；The 1,2,4,5- tetraminos benzene rubs with 2,5- dihydric para-phthalic acids' You are than being 1.2：1, nitrogen protection, for gradient increased temperature to 200 DEG C, polymerization obtains poly- Isosorbide-5-Nitrae-(2,5- dihydroxy) phenylene -2,6- benzene And diimidazole, yield 86.9%, purity 91.3%.
Embodiment 6
Using the method for embodiment 1, it is only that without part：Acid solution employed in step (4) is sulfuric acid solution； The addition of acid solution is 6 times of 1,2,4,5- tetramino benzene quality, described 1,2,4,5- tetramino benzene and 2,5- dihydroxy The molar ratio of terephthalic acid (TPA) is 1.2：1, nitrogen protection, for gradient increased temperature to 200 DEG C, polymerization obtains poly- Isosorbide-5-Nitrae-(2,5- dihydroxy) Phenylene -2,6- benzo diimidazole, yield 76.2%, purity 93.5%.
Embodiment 7
Using the method for embodiment 1, it is only that without part：Acid solution employed in step (4) is sulfuric acid solution； The addition of acid solution is 20 times of 1,2,4,5- tetramino benzene quality, described 1,2,4,5- tetramino benzene and 2,5- dihydroxy The molar ratio of terephthalic acid (TPA) is 2.0：1, nitrogen protection, gradient increased temperature to 200 DEG C, the poly- Isosorbide-5-Nitrae of final product-(2,5- dihydroxies Base) phenylene -2,6- benzo diimidazole, yield 82.1%, purity 89.1%.
The processing range of 1,2,4,5- tetraminos benzene synthesis
Change the reaction dissolvent of step (3), the percentage w1 of catalyst and raw material weight, reaction temperature T in embodiment 1 (DEG C), reaction pressure P (MPa), reaction time t (h), remaining step are as a result shown in step (1), step (2) in embodiment 1 Table 1
Table 1
Serial number Reaction dissolvent Catalyst W1/% T/℃ P/MPa t/h Purity/% Yield/%
1 Methanol 3%Pd/C 5 75 1.0 2 93.7 70.3
2 Ethyl alcohol 3%Pd/C 5 100 1.0 8 71.4 85.1
3 Tetrahydrofuran 3%Pd/C 10 75 1.8 8 86.2 75.8
4 DMF 3%Pd/C 8 80 1.5 8 92.3 87.5
5 DMA Ni 7 100 2.0 10 79.6 95.1
Processing range prepared by PDBI
1,2,4,5- tetramino benzene in step (4) in change embodiment 1：Mass ratio w, 1,2,4,5- of poly phosphoric acid solution Tetramino benzene：Molar ratio RO, the reaction time t/h of 2,5-Dihydroxyterephthalic acid, remaining step is the same as the step in embodiment 1 (1), step (2), step (3), the results are shown in Table 2.
Table 2
Serial number w RO t/h Yield/%
1 1:6 1.2：1 5 91.8
2 1:12 1.3：1 7 94.6
3 1:18 2.0：1 10 92.3
Finally it is also to be noted that listed above is only several embodiments of the invention.Obviously, the present invention is unlimited In above example, acceptable there are many deform.Those of ordinary skill in the art can directly lead from present disclosure All deformations for going out or associating, are considered as protection scope of the present invention.

Claims (10)

1. the synthetic method of 1,2,4,5- tetramino benzene of one kind, which is characterized in that include the following steps：
(1) 1,2,3- trichloro-benzenes is subjected to nitration reaction, obtains yellow solid 4,6- dinitros -1,2,3- trichloro-benzenes；
(2) step (1) products therefrom is dissolved in organic solvent A, moves into and leads to NH in autoclave3Ammonolysis reaction is carried out, ammonolysis obtains 4,6- Chloro- 1, the 3- phenylenediamines of dinitro -2-, wherein organic solvent A are alcohols or ether solvent；
(3) step (2) products therefrom is dissolved in organic solvent B, carries out hydrogenolysis under the conditions of heating compressive reaction, catalytic hydrogenolysis is also Original directly obtains 1,2,4,5- tetramino benzene of target product, and wherein organic solvent B is alcohol, tetrahydrofuran, the N-N- diformazan of C1-C3 Any one in base formamide or N-N dimethylanilines.
2. the synthetic method of according to claim 11,2,4,5- tetramino benzene, which is characterized in that in the step (1) For the nitrating agent that nitration reaction uses for 65% concentrated nitric acid or nitrate, dropping temperature is 35-90 DEG C.
3. the synthetic method of according to claim 11,2,4,5- tetramino benzene, which is characterized in that in the step (1) The condition of nitration reaction is：50-100 DEG C of temperature, reaction time 2-7h.
4. the synthetic method of according to claim 11,2,4,5- tetramino benzene, which is characterized in that in the step (2) Organic solvent A is any one in tetrahydrofuran, ethylene glycol or methanol.
5. the synthetic method of according to claim 11,2,4,5- tetramino benzene, which is characterized in that in the step (2) Ammonolysis reaction condition is：Temperature is 100-180 DEG C, ammonia pressure 0.2-2.0MPa, reaction time 6-10h.
6. the synthetic method of according to claim 11,2,4,5- tetramino benzene, which is characterized in that in the step (3) The temperature of hydrogenolysis is 75-110 DEG C, and hydrogen pressure 1.0-2.0MPa, catalyst is RaneyNi or Pd/C, reaction time 2- 10h。
7. the synthetic method of according to claim 61,2,4,5- tetramino benzene, which is characterized in that the catalyst is 3%Pd/C, the catalyst charge are the 2%-10% of chloro- 1, the 3- phenylenediamines quality of 4,6- dinitros -2-.
8. the 1,2,4,5- tetraminos benzene obtained by claim 1 is preparing poly- 1,4- (2,5- dihydroxy) phenylene -2,6- benzos Application in diimidazole, which is characterized in that comprise the following specific steps that：By the 1,2,4,5- tetramino benzene obtained by claim 1 It adds in acid solution, nitrogen protection adds in compound 2,5-Dihydroxyterephthalic acid, and subsequent gradient increased temperature gathers to 200 DEG C Conjunction obtains the acid liquid crystal stoste of poly- Isosorbide-5-Nitrae-(2,5- dihydroxy) phenylene -2,6- benzo diimidazole, washing, separation, dry To poly- Isosorbide-5-Nitrae-(2,5- dihydroxy) phenylene -2,6- benzo diimidazole, wherein, described 1,2,4,5- tetramino benzene：2,5- dihydroxies The molar ratio of base terephthalic acid (TPA) is 1.2-2.0：1.
9. 1,2,4,5- tetraminos benzene according to claim 8 is preparing poly- 1,4- (2,5- dihydroxy) phenylene -2,6- Application in benzo diimidazole, which is characterized in that the acid solution be poly phosphoric acid solution, 1,2,4,5- tetramino benzene： The mass ratio of poly phosphoric acid solution is 1：6-18；P in the poly phosphoric acid solution2O5Mass concentration is 75-90%.
10. 1,2,4,5- tetraminos benzene according to claim 8 is preparing poly- 1,4- (2,5- dihydroxy) phenylene -2,6- Application in benzo diimidazole, which is characterized in that the acid solution is sulfuric acid solution or phosphoric acid solution, and dosage is reaction 6-20 times of amount of substance.
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CN108821983A (en) * 2018-07-21 2018-11-16 信阳师范学院 It is a kind of using phenyl ring as heat resistive compounds of parent and its preparation method and application
CN108997132A (en) * 2018-09-03 2018-12-14 信阳师范学院 A kind of fluoro- 1,3,5- triamido -4,6- dinitrobenzene of heat resistive compounds 2- and preparation method thereof
CN110878022A (en) * 2018-09-06 2020-03-13 中国石油化工股份有限公司 Preparation method of 1,2, 3-trichloro-4, 6-dinitrobenzene
CN110982071A (en) * 2019-12-17 2020-04-10 吉林大学 Polybenzimidazole two-dimensional conjugated organic porous material, preparation method and application thereof
CN112679507A (en) * 2021-01-18 2021-04-20 邓颖菁 Conjugated benzimidazole corrosion inhibitor and preparation method thereof
CN112876483A (en) * 2021-01-18 2021-06-01 邓颖菁 Dicationic benzimidazole corrosion inhibitor and preparation method thereof

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CN103102274A (en) * 2011-11-11 2013-05-15 浙江工业大学 Preparation and application of 1,2,4,5-tetra amino benzene and hydrochloride thereof

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