CN1253428C - Method for synthesizing 4-nitro diphenylamine and 4-nitroso diphenylamine or/and their salts - Google Patents
Method for synthesizing 4-nitro diphenylamine and 4-nitroso diphenylamine or/and their salts Download PDFInfo
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- CN1253428C CN1253428C CN 03148198 CN03148198A CN1253428C CN 1253428 C CN1253428 C CN 1253428C CN 03148198 CN03148198 CN 03148198 CN 03148198 A CN03148198 A CN 03148198A CN 1253428 C CN1253428 C CN 1253428C
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- salt
- nitrosodiphenylamine
- synthetic
- amine according
- nitrodiphenyl amine
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- XXYMSQQCBUKFHE-UHFFFAOYSA-N 4-nitro-n-phenylaniline Chemical compound C1=CC([N+](=O)[O-])=CC=C1NC1=CC=CC=C1 XXYMSQQCBUKFHE-UHFFFAOYSA-N 0.000 title claims abstract description 30
- OIJHFHYPXWSVPF-UHFFFAOYSA-N para-Nitrosodiphenylamine Chemical compound C1=CC(N=O)=CC=C1NC1=CC=CC=C1 OIJHFHYPXWSVPF-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 29
- 150000003839 salts Chemical class 0.000 title claims abstract description 28
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000006482 condensation reaction Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 21
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 7
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 7
- 150000005621 tetraalkylammonium salts Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- GNGCALKASVBYMT-UHFFFAOYSA-N 2-nitroso-n-phenylaniline Chemical compound O=NC1=CC=CC=C1NC1=CC=CC=C1 GNGCALKASVBYMT-UHFFFAOYSA-N 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 239000011552 falling film Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 34
- 239000000463 material Substances 0.000 abstract description 15
- 239000002131 composite material Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000003518 caustics Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 230000008569 process Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 2
- 206010053219 non-alcoholic steatohepatitis Diseases 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- RUKISNQKOIKZGT-UHFFFAOYSA-N 2-nitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC=CC=C1NC1=CC=CC=C1 RUKISNQKOIKZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for synthesizing 4-nitrodiphenylamine and 4-nitrosodiphenylamine or/and salt thereof from aniline and nitrobenzene as raw material through continuous condensation reaction in the presence of composite catalysts. The method comprises: cheap composite base catalysts are adopted, aniline, nitrobenzene and composite base catalysts are put into a reactor according to a certain proportion; the material passes through one reactor or a plurality of reactors and a forced heat exchanger under certain pressure and at certain temperature, a forced circulation pump is utilized to locally circulate the material, and the material reacts while dehydrated. The method of the present invention has the advantages of mild reaction condition, few byproducts, no generation of corrosive substances, low device requirements, stable production, convenient realization of automatic control and reduction of production cost. The conversion rate of nitrobenzene is larger than 99%, and the selectivity is larger than 97%.
Description
Technical field
The present invention relates to a kind of organic synthetic method, being specifically related to aniline and oil of mirbane is raw material, selects a kind of compound alkaline catalysts and technical process for use, the method for synthetic continuously 4 nitrodiphenyl amine and 4-nitrosodiphenylamine and/or their salt.
Background technology
At present, the method of synthetic 4 nitrodiphenyl amine and 4-nitrosodiphenylamine and/or their salt is to adopt the nucleophilic aromatic ring to replace H-H reaction (NASH), and the functionalization carbanion that promptly contains leaving group replaces the reaction of nitro-aromatic, the assorted ring hydrogen of virtue in the presence of alkaline.Most compounds replaces on the ortho position, and yield is generally between 5-65%, in the presence of at tetramethyl ammonium hydroxide, aniline and oil of mirbane carry out the NASH reaction, synthetic 4 nitrodiphenyl amine and 4-nitrosodiphenylamine (referring to USP51147063, USP5253737, USP5331099, USP5453541, USP5552531 and USP5633407), when aniline reacts at the ortho position of oil of mirbane, generate by product 2-nitrodiphenylamine and 2-nitrosodiphenylamine, reduced 4 nitrodiphenyl amine and 4-nitrosodiphenylamine degree of purity of production.This method has been used expensive tetramethyl ammonium hydroxide, and this catalyzer is difficult to reclaiming, thereby wastes raw material, and increases production cost.Highly basic is the key that catalyzer is selected.Dehydration is bigger to the influence of condensation parallel reactor, usually alkali catalyst needs dehydration in advance, control moisture requirement height, when requiring condensation reaction to begin when promptly reacting the ratio of water and alkali is not less than 4: 1 and reaction is not less than (CN1307556A) when finishing at 0.6: 1 o'clock, adopting in the specific embodiment dewaters afterwards to enter earlier carries out condensation reaction in the reactor, operation is numerous and diverse, is difficult to effective control, and treatment capacity is little.
Summary of the invention
Technical problem to be solved by this invention is to select the technical process of appropriate catalyst and reaction, the control reaction conditions, and the reaction that makes aniline and oil of mirbane condensation generate 4 nitrodiphenyl amine and 4-nitrosodiphenylamine and/or their salt is carried out continuously.
The present invention promptly by forced heat-exchanging, dehydration, reaction, forms the local circulation operation by selecting a kind of compound alkaline catalysts and reaction process flow process for use, and condensation reaction is carried out continuously.
Particular content of the present invention is as follows:
To oil of mirbane, aniline and compound alkaline catalysts be entered the forced heat-exchanging device in proportion continuously by volume pump earlier and dewater, reaction, water vapour is through being condensed into water; And, squeeze into A reactor from its top with the condensated liquid in the forced heat-exchanging device, continue dehydration, reaction; Then, the condensation recycle pump by reactor bottom returns condensated liquid to the forced heat-exchanging device again, and material constitutes the local circulation system of condensation reaction of the present invention through circulation constantly like this.Material constantly dewaters, reaction, along with increasing of condensated liquid in the A reactor, the upflow tube by this reactor side enters second reactor and staged reactor, dewater, react, generate the condensated liquid that contains 4 nitrodiphenyl amine and 4-nitrosodiphenylamine and/or their salt at last.
Condensation reaction is a succession of, parallel reactor, and it is bigger to its influence to dewater, and balance deviates to positive dirction to move with the continuous quilt of moisture.The decomposition of composite catalyst is a first order reaction, along with quickening is decomposed in the rising of temperature.Therefore the temperature of reaction, time, catalyst concn, dropping mode, proportioning, dewatering type etc. all can improve the decomposition rate of composite catalyst when improving speed of response and transformation efficiency, thereby influence production cost.
In the condensation reaction, the rate of addition of oil of mirbane is bigger to reaction influence, drips too fastly, can reduce selectivity, so the lower aq of oil of mirbane in the maintenance solution just can be kept the highly selective of reaction.Therefore, local circulation of the present invention system, condensation reaction is continuous by recycle pump, intermittent mode with the oil of mirbane dropping, change into and use the pump continuously feeding, this recycle system mainly is made of forced heat-exchanging device and reactor, and material constantly circulates in this system by the condensation recycle pump.Keep a large amount of condensated liquids in the working cycle, after oil of mirbane enters the recycle system, be diluted into low concentration very soon, thereby can keep the highly selective of reacting, make oil of mirbane be able to continuously feeding, avoided dehydration in the periodical operation process, dripped, react three independent steps.These three independent steps are merged, oil of mirbane, aniline are dewatered in this local circulation system, reaction is carried out continuously.
In the condensation reaction, dehydration is bigger to the condensation reaction influence, because the heat interchanging area of reactor is limit by reactor volume, the present invention has increased the forced heat-exchanging device outside reactor, by the condensation recycle pump, condensated liquid is injected forced heat-exchanging device heat exchange dehydration, both increased mass transfer coefficient, increased heat interchanging area again.
The present invention adopts continuous mode and intermittently condensation reaction is different, intermittently in the condensated liquid of condensation reaction, the concentration of 4 nitrodiphenyl amine and 4-nitrosodiphenylamine and/or their salt is to increase gradually with the reaction times, and the concentration substantially constant of 4 nitrodiphenyl amine and 4-nitrosodiphenylamine and/or their salt is constant in the condensated liquid of the same reactor of continuously feeding, between each stage reactor contract and liquid in, the concentration of 4 nitrodiphenyl amine and 4-nitrosodiphenylamine and/or their salt increases successively.
Can design the concentration of material in each stage reactor according to reactor progression, and concentration keeps stable in certain certain scope, nitro phenenyl concentration equals exit concentration in the last step reactor.Raw material enters A reactor continuously at certain certain value, the dehydration of condensation course continous-stable, and 4 nitrodiphenyl amine and 4-nitrosodiphenylamine and/or their salt continous-stable under vacuum condition is discharged from the last step reactor.
Forced heat-exchanging device of the present invention, comprise climbing-film evaporator, falling-film evaporator or their coupling, add forced heat-exchanging device heating agent and adopt alcohol steam or hot water or steam or methanol steam, preferably ethanol steam, under the restricted situation of temperature of reaction, the selection by heating medium improves heat transfer coefficient as far as possible.
The raw material oil of mirbane that the present invention adopts is 1 with the ratio of aniline: 1-1: 15 (moles), and preferably than being 1: 4-1: 10 (moles).The aniline consumption is high more, and speed of reaction is fast more, and the reaction yield in the identical time is also high more.But the consumption of aniline is too high, under the identical device prerequisite, can influence the output of 4 nitrodiphenyl amine and 4-nitrosodiphenylamine.
The present invention adopts compound alkaline catalysts to replace tetramethyl ammonium hydroxide to replace the catalyzer of H-H reaction as the nucleophilic aromatic ring.The aqueous solution that compound alkaline catalysts is made up of tetraalkylammonium hydroxide, alkali metal hydroxide or its oxide compound and tetraalkylammonium salt, wherein tetraalkylammonium hydroxide, alkali metal hydroxide and tetraalkylammonium salt three's ratio is (2-9): (0.5-3): (0.5-3) (mole), if adopt alkalimetal oxide, then its ratio in catalyzer can convert by corresponding oxyhydroxide and get.In the compound alkaline catalysts, tetraalkylammonium hydroxide, alkali metal hydroxide and tetraalkylammonium salt three concentration summation are 15-50 (weight %), be preferably 25-38 (weight %), if adopt alkalimetal oxide, then its consumption can convert by corresponding oxyhydroxide and get.The ratio of hydroxide ion and oil of mirbane is 1 in the compound alkaline catalysts: 4-4: 1 (mole).The condensation transformation efficiency (in oil of mirbane) that uses this compound alkaline catalysts is greater than 99%, and selectivity is greater than 97%.
Temperature of reaction of the present invention be 20-150 (℃), if temperature of reaction be lower than 20 (℃), speed of reaction is slack-off; If temperature of reaction be higher than 150 (℃), can produce by product, and the rate of decomposition of compound alkali is big.Preferred temperature of the present invention be 50-90 (℃), control reaction temperature is not higher than 90 ℃, make condensation course composite catalyst rate of decomposition less than 0.5%, reaction pressure (absolute pressure) is 0.005-0.1 (MPa), material reaction times in reactor be 3.5-6 (hour).
The present invention is in the presence of compound alkaline catalysts, adopting aniline and oil of mirbane is that raw material passes through a local circulation system, become and intermittently be continuous mode, increased the forced heat-exchanging device, accelerated rate of water loss, the method for material prepared in reaction 4 nitrodiphenyl amine and 4-nitrosodiphenylamine and/or their salt while dewatering, its selected compound alkaline catalysts is cheap, capable of circulation applying mechanically, simple to operate, the reaction conditions gentleness, by product is few, the transformation efficiency of oil of mirbane is greater than 99%, and selectivity does not have corrosives greater than 97%, to equipment require low, and eliminated pollution to environment, production cost is low, is suitable for the large-tonnage industrial-scale production.
Description of drawings
Figure is the process flow sheet of the method for synthetic 4 nitrodiphenyl amine and 4-nitrosodiphenylamine and/or their salt
1-round-robin condensated liquid 2-water
The final condensated liquid of 3-condensation recycle pump 4-
Embodiment
Open composite catalyst simultaneously, aniline and oil of mirbane transferpump, regulate flow to 150 kilograms/hour of aniline, 30 kilograms/hour in oil of mirbane, (its component is by tetramethyl ammonium hydroxide for compound alkaline catalysts, the aqueous solution that sodium hydroxide and tetramethyl-volatile salt are formed, three's concentration summation is 29.9%, three's mol ratio is 1: 1: 0.5) 80 kilograms/hour, enter continuously in the forced heat-exchanging device, the heating agent of forced heat-exchanging device adopts alcohol steam, condensated liquid in the forced heat-exchanging device is squeezed into A reactor from its top, continue dehydration, reaction, open A reactor bottom valve and condensation recycle pump then, regulate condensation circulating-pump outlet valve, material is turned back in the forced heat-exchanging device, form the local circulation system, material constantly circulates like this, dehydration, reaction.75 ℃ of control reaction temperature, pressure (absolute pressure) 0.008MPa, the Control Circulation flow quantity 2 meters 3/ hour.Along with raw material constantly enters, material in the A reactor constantly increases, when treating that material in the A reactor rises to A reactor to the pipe connecting of second reactor, the material overflow is to second reactor, in second reactor dewater more fully, condensation reaction.The total residence time of control material in reactor 5 hours, oil of mirbane transformation efficiency 99.1%, selectivity 98%.
Claims (14)
1, a kind of is the method for the synthetic 4 nitrodiphenyl amine of raw material and 4-nitrosodiphenylamine and/or their salt with aniline and oil of mirbane, it is characterized in that selecting for use the mol ratio 1 of hydroxide ion and oil of mirbane in compound alkaline catalysts and the compound alkaline catalysts of control: 4-4: 1, form the local circulation operation by forced heat-exchanging device forced heat-exchanging and dehydration, condensation reaction is carried out continuously, the aqueous solution that the compound alkaline catalysts that is adopted is made up of tetraalkylammonium hydroxide, alkali metal hydroxide or its oxide compound and tetraalkylammonium salt.
2, the method for synthetic 4 nitrodiphenyl amine according to claim 1 and 4-nitrosodiphenylamine and/or their salt, the mol ratio that it is characterized in that three kinds of components in the compound alkaline catalysts is, tetraalkylammonium hydroxide: alkali metal hydroxide: tetraalkylammonium salt=(2-9): (0.5-3): (0.5-3), if adopt alkalimetal oxide, then its ratio in catalyzer converts by corresponding oxyhydroxide and gets.
3, the method for synthetic 4 nitrodiphenyl amine according to claim 1 and 2 and 4-nitrosodiphenylamine and/or their salt, it is characterized in that in the compound alkaline catalysts, tetraalkylammonium hydroxide, alkali metal hydroxide, tetraalkylammonium salt three concentration expressed in percentage by weight summation are 15%-50%, if adopt alkalimetal oxide, then its consumption converts by corresponding oxyhydroxide and gets.
4, the method for synthetic 4 nitrodiphenyl amine according to claim 3 and 4-nitrosodiphenylamine and/or their salt, it is characterized in that in the compound alkaline catalysts, tetraalkylammonium hydroxide, alkali metal hydroxide, tetraalkylammonium salt three concentration expressed in percentage by weight summation are 25%-38%, if adopt alkalimetal oxide, then its consumption converts by corresponding oxyhydroxide and gets.
5, the method for synthetic 4 nitrodiphenyl amine according to claim 1 and 4-nitrosodiphenylamine and/or their salt is characterized in that described local circulation forms through forced heat-exchanging device and reactor by the condensation recycle pump.
6, the method for synthetic 4 nitrodiphenyl amine according to claim 1 and 4-nitrosodiphenylamine and/or their salt is characterized in that described forced heat-exchanging device, is climbing-film evaporator, falling-film evaporator or their coupling.
7, the method for synthetic 4 nitrodiphenyl amine according to claim 1 and 4-nitrosodiphenylamine and/or their salt is characterized in that the heating agent of forced heat-exchanging device adopts alcohol steam or hot water or steam or methanol steam.
8, the method for synthetic 4 nitrodiphenyl amine according to claim 6 and 4-nitrosodiphenylamine and/or their salt is characterized in that the heating agent of forced heat-exchanging device adopts alcohol steam.
9, the method for synthetic 4 nitrodiphenyl amine according to claim 1 and 4-nitrosodiphenylamine and/or their salt, the mol ratio that it is characterized in that oil of mirbane and aniline is 1: 1-1: 15.
10, the method for synthetic 4 nitrodiphenyl amine according to claim 9 and 4-nitrosodiphenylamine and/or their salt, the mol ratio that it is characterized in that oil of mirbane and aniline is 1: 4-1: 10.
11, the method for synthetic 4 nitrodiphenyl amine according to claim 1 and 4-nitrosodiphenylamine and/or their salt is characterized in that setting-up point is 20-150 ℃.
12, the method for synthetic 4 nitrodiphenyl amine according to claim 11 and 4-nitrosodiphenylamine and/or their salt is characterized in that setting-up point is 50-90 ℃.
13, the method for synthetic 4 nitrodiphenyl amine according to claim 1 and 4-nitrosodiphenylamine and/or their salt is characterized in that the condensation reaction absolute pressure is 0.005-0.1MPa.
14, the method for synthetic 4 nitrodiphenyl amine according to claim 1 and 4-nitrosodiphenylamine and/or their salt is characterized in that condensation reaction time is 3.5-6 hour.
Priority Applications (31)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03148198 CN1253428C (en) | 2003-07-04 | 2003-07-04 | Method for synthesizing 4-nitro diphenylamine and 4-nitroso diphenylamine or/and their salts |
| BRPI0412101-5A BRPI0412101A (en) | 2003-07-04 | 2004-07-02 | process for the preparation of 4-aminodiphenylamine |
| PT04738332T PT1645555E (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| AT04738332T ATE526305T1 (en) | 2003-07-04 | 2004-07-02 | METHOD FOR PRODUCING 4-AMINODIPHENYLAMINE |
| DE602004010234T DE602004010234T2 (en) | 2003-07-04 | 2004-07-02 | PROCESS FOR THE PREPARATION OF 4-AMINODIPHENYLAMINE |
| ES04738331T ES2298762T3 (en) | 2003-07-04 | 2004-07-02 | PROCESS TO PREPARE 4-AMINODYPHENYLAMINE. |
| EA200501647A EA009395B1 (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine |
| JP2006517937A JP4546958B2 (en) | 2003-07-04 | 2004-07-02 | Method for producing 4-aminodiphenylamine |
| US10/882,677 US7176333B2 (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| EP04738331A EP1591438B1 (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine |
| KR1020040051541A KR100612922B1 (en) | 2003-07-04 | 2004-07-02 | A process for producing 4-aminodiphenylamine |
| JP2006500463A JP4500302B2 (en) | 2003-07-04 | 2004-07-02 | Method for producing 4-aminodiphenylamine |
| PCT/CN2004/000733 WO2005003078A1 (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine |
| PCT/CN2004/000734 WO2005003079A1 (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| EA200600052A EA009396B1 (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| EP04738332A EP1645555B1 (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| PL04738332T PL1645555T3 (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| ES04738332T ES2373720T3 (en) | 2003-07-04 | 2004-07-02 | METHOD FOR THE PRODUCTION OF 4-AMINODYPHENYLAMINE. |
| CA2515238A CA2515238C (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| US10/883,042 US7084302B2 (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| MXPA05013788A MXPA05013788A (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine. |
| CA2531074A CA2531074C (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| KR1020040051932A KR100612923B1 (en) | 2003-07-04 | 2004-07-05 | A process for preparing 4-aminodiphenylamine |
| US11/477,954 US7235694B2 (en) | 2003-07-04 | 2006-06-30 | Process for preparing 4-aminodiphenylamine |
| US11/757,277 US20080039657A1 (en) | 2003-07-04 | 2007-06-01 | Process for preparing 4-aminodiphenylamine |
| US11/759,897 US8293673B2 (en) | 2003-07-04 | 2007-06-07 | Process for preparing 4-aminodiphenylamine |
| US11/759,901 US20070227675A1 (en) | 2003-07-04 | 2007-06-07 | Process for preparing 4-aminodiphenylamine |
| US12/195,371 US7989662B2 (en) | 2003-07-04 | 2008-08-20 | Process for preparing 4-aminodiphenylamine |
| US12/900,459 US8486223B2 (en) | 2003-07-04 | 2010-10-07 | Falling film evaporator |
| US13/104,900 US8686188B2 (en) | 2003-07-04 | 2011-05-10 | Process for preparing 4-aminodiphenylamine |
| US13/620,588 US9029603B2 (en) | 2003-07-04 | 2012-09-14 | Process for preparing alkylated p-phenylenediamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03148198 CN1253428C (en) | 2003-07-04 | 2003-07-04 | Method for synthesizing 4-nitro diphenylamine and 4-nitroso diphenylamine or/and their salts |
Publications (2)
| Publication Number | Publication Date |
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| CN1470500A CN1470500A (en) | 2004-01-28 |
| CN1253428C true CN1253428C (en) | 2006-04-26 |
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| CN 03148198 Expired - Lifetime CN1253428C (en) | 2003-07-04 | 2003-07-04 | Method for synthesizing 4-nitro diphenylamine and 4-nitroso diphenylamine or/and their salts |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372640A (en) * | 2010-08-20 | 2012-03-14 | 中国石油化工集团公司 | Method for preparing 4-nitrodiphenylamine and 4-nitrosodiphenylamine |
| CN103819346B (en) * | 2014-03-17 | 2015-11-04 | 山东尚舜化工有限公司 | A kind of production unit of precursor of 4-ADPA and production technique |
| CN107686449B (en) * | 2016-08-05 | 2020-02-21 | 中国石油化工股份有限公司 | Reducing tubular reactor device and method for preparing 4-nitrodiphenylamine and 4-nitrosodiphenylamine by using same |
| CN108558675A (en) * | 2018-04-25 | 2018-09-21 | 南通理工学院 | Synthesis method of 4-aminodiphenylamine |
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- 2003-07-04 CN CN 03148198 patent/CN1253428C/en not_active Expired - Lifetime
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