CN102173994A - Preparation method of 3,3',4,4'-tetraamino biphenyl - Google Patents
Preparation method of 3,3',4,4'-tetraamino biphenyl Download PDFInfo
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- CN102173994A CN102173994A CN2011100671163A CN201110067116A CN102173994A CN 102173994 A CN102173994 A CN 102173994A CN 2011100671163 A CN2011100671163 A CN 2011100671163A CN 201110067116 A CN201110067116 A CN 201110067116A CN 102173994 A CN102173994 A CN 102173994A
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- tetramino biphenyl
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Abstract
The invention discloses a preparation method of 3,3',4,4'-tetraamino biphenyl. The preparation method comprises the following steps of: 1, reacting dichloro biphenyl diamine with an ammoniation reagent under the action of a catalyst to obtain a 3,3',4,4'-tetraamino biphenyl crude product; and 2, treating the crude product by using a decoloring agent and a reducing agent to obtain the high-purity 3,3',4,4'-tetraamino biphenyl. The preparation method is mile in reaction condition, high in yield and purity of the product and good in industrialized application prospect.
Description
Technical field
The present invention relates to a kind of 3,3'4, the preparation method of 4'-tetramino biphenyl, be specifically related to a kind of DCBP diamines under catalyst action and the ammonification reagent react generate 3,3 ' 4, the preparation method of 4 '-tetramino biphenyl.
Background technology
3,3 ' 4,4 '-tetramino biphenyl (English be called for short DAB) is a kind of high-grade macromolecular material monomer that the country of developed country, particularly aerospace and military project prosperity in recent years begins primary study and application, is mainly used in synthetic heat-stable macromolecule resin and synthon.Has property such as chemical-resistant stability and snugness of fit under superelevation thermotolerance, flame retardant resistance, size thermostability, the high temperature with its synthetic macromolecule resin, fiber, be the incomparable and alternate of other materials, so the DAB Products Development is being subjected to comprising the international counterparts common concern already of China.Fast development along with global economy, with improving constantly of countries in the world high-tech state of the art, industries such as Aeronautics and Astronautics, military project, building, machinery will have bigger development space, can continue to enlarge to high-performance, novel, functional material demand, corresponding D AB market demand is ascendant trend linearly also.
This project adopts advanced catalysis ammonia to separate technology and full-automatic operating device on some existing hydrogenation reduction process technical foundation in reference in the world, with DCBP diamines (DCB) is main raw material, in the presence of catalyzer, separate into product with containing the ammonia raw material ammonia, and then refining purify the finished product.This explained hereafter cost is low, working strength of workers is low, technological operation safety, quality product height, the more important thing is that the technology cleaning do not have " three wastes " generation substantially.The smooth operation of this project can be further large-scale industrial production valuable technical basis is provided, and has filled up domestic blank, and quality product has reached international most advanced level.Product both can substitute the needs that the domestic market is satisfied in import, drove the development of domestic relevant industries, and the demand of world market is partly satisfied in also foreign exchange earning simultaneously, further improves the competitive power of China in the world market.
US2895948, US3174947 and 20041008399.2 disclose by the DCBP diamines and have separated preparation 3,3 ' 4, the method for 4 '-tetramino biphenyl through catalysis ammonia.Wherein, there are distinct disadvantage such as product yield, purity are low in preceding two kinds of methods, and a kind of method in back adopts urea as ammonification reagent, though productive rate improves, but ability and DCBP diamine reactant behind the urea need thermal degradation generation ammonia, so speed of response is slower, the reaction times is longer.
Summary of the invention
For overcoming above-mentioned the deficiencies in the prior art, the invention provides a kind of 3,3'4, the preparation method of 4'-tetramino biphenyl makes productive rate and purity obtain providing high.
Technical solution of the present invention is as follows:
The first step, under catalyst action, DCBP diamines and ammonification reagent react obtain 3,3'4,4'-tetramino biphenyl crude product, described catalyzer comprises Primary Catalysts and secondary catalyzer, and this Primary Catalysts is copper, zinc, calcium, tin or iron, and this pair catalyzer is cuprous chloride, tin protochloride, calcium chloride, zinc chloride or iron(ic) chloride; Concrete steps are as follows:
Add described chlordiphenyl diamines, ammonification reagent and Primary Catalysts in autoclave, heating is also opened and is stirred, and being warming up to temperature of reaction is 100～250
oC, reaction pressure was reacted 3～6 hours at 0.5～8Mpa, added the aqueous solution of described secondary catalyzer, continued reaction 2～4 hours, obtained 3,3'4,4'-tetramino biphenyl crude product;
In second step, it is highly purified 3 that described crude product obtains after discoloring agent and reductive agent are handled, 3'4,4'-tetramino biphenyl.
The mol ratio of described ammonification reagent and DCBP diamines is 2:1～50:1.
Described Primary Catalysts consumption is 5～50 wt% of DCBP diamines, and secondary catalyst levels is 2～30 wt% of DCBP diamines.
Described ammonification reagent is liquefied ammonia, ammoniacal liquor, bicarbonate of ammonia, ammonium chloride; When ammonification reagent was ammoniacal liquor, reaction did not need other media, and other ammonification reagent need to react in the aqueous solution.
The concentration of described DCBP diamines in reaction medium is less than 5mol/L.
Compared with prior art, the invention has the beneficial effects as follows the reaction conditions gentleness, the productive rate height, product purity is greater than 99%.
Description of drawings
Fig. 1 is the liquid chromatography spectrogram among the present invention.
Fig. 2 is the nuclear magnetic spectrogram among the present invention.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail, but should limit protection scope of the present invention with this.
Embodiment 1
In stainless steel cauldron, add DCBP diamines 100 grams, copper powder 23 grams, liquefied ammonia 500 grams.Reacting by heating still to 100 ℃, the reactor pressure-stabilisation is at 0.5MPa.React after 3 hours and to be pumped in the above-mentioned reaction system after cuprous chloride 11 grams are dissolved in water, continue reaction 2 hours.Reactant is cooled to after the room temperature water and gives a baby a bath on the third day after its birth time, after the drying crude product 76.4 grams.
With crude product 2500mL water dissolution; add 30 gram gacs and 4 gram V-Brite Bs; solution back flow reaction 4 hours under nitrogen protection; solution has crystal to separate out after being cooled to room temperature; filter that crystal and vacuum-drying must be shown in the nuclear magnetic spectrogram among Fig. 2 the present invention 3; 3 ' 4,4 '-tetramino biphenyl, 61.5 grams.
Embodiment 2
In stainless steel cauldron, add DCBP diamines 100 grams, glass putty 31 grams, strong aqua 1500mL.Reacting by heating still to 250
oC, the reactor pressure-stabilisation is at 8MPa.React after 4 hours and to be pumped in the above-mentioned reaction system after tin protochloride 16 grams are dissolved in water, continue reaction 3 hours.Reactant is cooled to after the room temperature water and gives a baby a bath on the third day after its birth time, after the drying crude product 78.2 grams.
With crude product 2500mL water dissolution, add 30 gram gacs and 4 gram V-Brite Bs, solution back flow reaction 4 hours under nitrogen protection; solution has crystal to separate out after being cooled to room temperature; filter crystal and vacuum-drying and get 3,3 ' 4,4 '-tetramino biphenyl, 72.4 grams.
Embodiment 3
In stainless steel cauldron, add DCBP diamines 100 grams, copper powder 23 grams, bicarbonate of ammonia 620 grams.Reacting by heating still to 200
oC, the reactor pressure-stabilisation is at 5MPa.React after 6 hours and to be pumped in the above-mentioned reaction system after cuprous chloride 11 grams are dissolved in water, continue reaction 4 hours.Reactant is cooled to after the room temperature water and gives a baby a bath on the third day after its birth time, after the drying crude product 82.7 grams.
With crude product 2500mL water dissolution, add 30 gram gacs and 4 gram V-Brite Bs, solution back flow reaction 4 hours under nitrogen protection; solution has crystal to separate out after being cooled to room temperature; filter crystal and vacuum-drying and get 3,3 ' 4,4 '-tetramino biphenyl, 70.8 grams.
Embodiment 4
In stainless steel cauldron, add DCBP diamines 100 grams, zinc powder 33 grams, liquefied ammonia 500 grams.Reacting by heating still to 155
oC, the reactor pressure-stabilisation is at 2MPa.React after 4 hours and to be pumped in the above-mentioned reaction system after zinc chloride 17 grams are dissolved in water, continue reaction 2 hours.Reactant is cooled to after the room temperature water and gives a baby a bath on the third day after its birth time, after the drying crude product 74.4 grams.
With crude product 2500mL water dissolution, add 30 gram gacs and 4 gram V-Brite Bs, solution back flow reaction 4 hours under nitrogen protection; solution has crystal to separate out after being cooled to room temperature; filter crystal and vacuum-drying and get 3,3 ' 4,4 '-tetramino biphenyl, 63.5 grams.
Embodiment 5
In stainless steel cauldron, add DCBP diamines 100 grams, calcium powder 27 grams, ammonium chloride 460 grams.Reacting by heating still to 185
oC, the reactor pressure-stabilisation is at 4.5MPa.React after 5.5 hours and to be pumped in the above-mentioned reaction system after calcium chloride 17 grams are dissolved in water, continue reaction 3 hours.Reactant is cooled to after the room temperature water and gives a baby a bath on the third day after its birth time, after the drying crude product 77.1 grams.
With crude product 2500mL water dissolution, add 30 gram gacs and 4 gram V-Brite Bs, solution back flow reaction 4 hours under nitrogen protection; solution has crystal to separate out after being cooled to room temperature; filter crystal and vacuum-drying and get 3,3 ' 4,4 '-tetramino biphenyl, 70.4 grams.
Through evidence, by the present invention 3,3'4, the preparation method of 4'-tetramino biphenyl, obtain shown in the liquid chromatography spectrogram among Fig. 1 the present invention 3,3'4,4'-tetramino biphenyl has the productive rate height, product purity is greater than 99% characteristics.
Need to prove that by other conditions of being stated in claims of the present invention, can obtain correspondingly 3,3 ' 4 equally, 4 '-tetramino biphenyl is not enumerated one by one at this, but does not influence protection scope of the present invention.
Claims (5)
1. one kind 3,3'4, the preparation method of 4'-tetramino biphenyl is characterized in that this method comprises the steps:
The first step, under catalyst action, DCBP diamines and ammonification reagent react obtain 3,3'4,4'-tetramino biphenyl crude product, described catalyzer comprises Primary Catalysts and secondary catalyzer, and this Primary Catalysts is copper, zinc, calcium, tin or iron, and this pair catalyzer is cuprous chloride, tin protochloride, calcium chloride, zinc chloride or iron(ic) chloride; Concrete steps are as follows:
Add described dichloro chlordiphenyl diamines, ammonification reagent and Primary Catalysts in autoclave, heating is also opened and is stirred, and being warming up to temperature of reaction is 100～250
oC, reaction pressure was reacted 3～6 hours at 0.5～8Mpa, added the aqueous solution of described secondary catalyzer, continued reaction 2～4 hours, obtained 3,3'4,4'-tetramino biphenyl crude product;
In second step, it is highly purified 3 that described crude product obtains after discoloring agent and reductive agent are handled, 3'4,4'-tetramino biphenyl.
2. according to claim 13,3'4, the preparation method of 4'-tetramino biphenyl is characterized in that, the mol ratio of described ammonification reagent and DCBP diamines is 2:1～50:1.
3. according to claim 13,3'4, the preparation method of 4'-tetramino biphenyl is characterized in that, and described Primary Catalysts consumption is 5～50 wt% of DCBP diamines, and secondary catalyst levels is 2～30 wt% of DCBP diamines.
4. according to claim 13,3'4, the preparation method of 4'-tetramino biphenyl is characterized in that, described ammonification reagent is liquefied ammonia, ammoniacal liquor, bicarbonate of ammonia, ammonium chloride; When ammonification reagent was ammoniacal liquor, reaction did not need other media, and other ammonification reagent need to react in the aqueous solution.
5. according to claim 13,3'4, the preparation method of 4'-tetramino biphenyl is characterized in that, the concentration of described DCBP diamines in reaction medium is less than 5mol/L.
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| CN2011100671163A CN102173994A (en) | 2011-03-21 | 2011-03-21 | Preparation method of 3,3',4,4'-tetraamino biphenyl |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319354A (en) * | 2013-05-14 | 2013-09-25 | 西安近代化学研究所 | Synthesis method of 3-amino-1,2-propanediol |
| CN104209130A (en) * | 2014-08-08 | 2014-12-17 | 江苏清泉化学股份有限公司 | Catalyst for catalyzing reaction of dichlorobiphenyl diamine and ammonia and preparation method of tetraminobenzidine |
| CN112920054A (en) * | 2019-12-05 | 2021-06-08 | 北京英力精化技术发展有限公司 | Preparation method of 3,3 ', 4, 4' -tetraaminobiphenyl |
| CN115108918A (en) * | 2021-03-23 | 2022-09-27 | 北京英力精化技术发展有限公司 | Preparation method of 3,3',4,4' -tetraaminobiphenyl |
| US11981616B2 (en) | 2021-03-23 | 2024-05-14 | Hubei Huida High-Tech Co., Ltd | Method for preparing 3,3′-diaminobenzidine |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6335549A (en) * | 1986-07-31 | 1988-02-16 | Asahi Chem Ind Co Ltd | Method for aminating bisbromobenzene compound |
| EP0391606A1 (en) * | 1989-04-05 | 1990-10-10 | Toyo Ink Manufacturing Co., Ltd. | Process for the production of an aromatic hydrazo compound |
| CN1580038A (en) * | 2004-05-17 | 2005-02-16 | 山东泰山染料股份有限公司 | 3,3',4,4'-tetra-amino-biphenyl preparing method |
| CN1693301A (en) * | 2004-05-07 | 2005-11-09 | 杨宝德 | Process for preparing ortho nitrophenylamine |
| CN1923810A (en) * | 2006-09-22 | 2007-03-07 | 四川绵阳利尔化工有限公司 | Chemical synthesis method of 4-amino-3,5,6-trichloropyridine-2-formic acid |
| CN101735073A (en) * | 2008-11-25 | 2010-06-16 | 南京理工大学 | Method for preparing chloroaniline by catalysis hydrogenation |
-
2011
- 2011-03-21 CN CN2011100671163A patent/CN102173994A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6335549A (en) * | 1986-07-31 | 1988-02-16 | Asahi Chem Ind Co Ltd | Method for aminating bisbromobenzene compound |
| EP0391606A1 (en) * | 1989-04-05 | 1990-10-10 | Toyo Ink Manufacturing Co., Ltd. | Process for the production of an aromatic hydrazo compound |
| CN1693301A (en) * | 2004-05-07 | 2005-11-09 | 杨宝德 | Process for preparing ortho nitrophenylamine |
| CN1580038A (en) * | 2004-05-17 | 2005-02-16 | 山东泰山染料股份有限公司 | 3,3',4,4'-tetra-amino-biphenyl preparing method |
| CN1923810A (en) * | 2006-09-22 | 2007-03-07 | 四川绵阳利尔化工有限公司 | Chemical synthesis method of 4-amino-3,5,6-trichloropyridine-2-formic acid |
| CN101735073A (en) * | 2008-11-25 | 2010-06-16 | 南京理工大学 | Method for preparing chloroaniline by catalysis hydrogenation |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319354A (en) * | 2013-05-14 | 2013-09-25 | 西安近代化学研究所 | Synthesis method of 3-amino-1,2-propanediol |
| CN104209130A (en) * | 2014-08-08 | 2014-12-17 | 江苏清泉化学股份有限公司 | Catalyst for catalyzing reaction of dichlorobiphenyl diamine and ammonia and preparation method of tetraminobenzidine |
| CN112920054A (en) * | 2019-12-05 | 2021-06-08 | 北京英力精化技术发展有限公司 | Preparation method of 3,3 ', 4, 4' -tetraaminobiphenyl |
| CN115108918A (en) * | 2021-03-23 | 2022-09-27 | 北京英力精化技术发展有限公司 | Preparation method of 3,3',4,4' -tetraaminobiphenyl |
| WO2022199226A1 (en) * | 2021-03-23 | 2022-09-29 | 北京英力精化技术发展有限公司 | Method for preparing 3,3',4,4'-tetraaminobiphenyl |
| CN115108918B (en) * | 2021-03-23 | 2023-06-02 | 湖北汇达科技发展有限公司 | Preparation method of 3,3', 4' -tetraminobiphenyl |
| US11981616B2 (en) | 2021-03-23 | 2024-05-14 | Hubei Huida High-Tech Co., Ltd | Method for preparing 3,3′-diaminobenzidine |
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Owner name: SHANGHAI POLYMER CHEMICAL TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: SHANGHAI DAB CHEMICAL TECHNOLOGY CO., LTD. Effective date: 20120217 |
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Effective date of registration: 20120217 Address after: 200231, room 1, building 18, No. 1305, Lane 501, Huajing Road, Shanghai, Xuhui District Applicant after: Polymer Chemical Co. Ltd. Address before: 200231, room 2, building 8, No. 1305, Lane 231, Huajing Road, Shanghai, Xuhui District Applicant before: Shanghai Diaibi Chemical Technology Co., Ltd. |
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Application publication date: 20110907 |