CN113527111A - Method for preparing RT base by normal pressure condensation - Google Patents

Method for preparing RT base by normal pressure condensation Download PDF

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Publication number
CN113527111A
CN113527111A CN202010279748.5A CN202010279748A CN113527111A CN 113527111 A CN113527111 A CN 113527111A CN 202010279748 A CN202010279748 A CN 202010279748A CN 113527111 A CN113527111 A CN 113527111A
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China
Prior art keywords
base
reaction
catalyst
condensation
nitrobenzene
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CN202010279748.5A
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CN113527111B (en
Inventor
秦涛
吕明倩
张伟
黄伟
祝东红
刘卓
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China Petroleum and Chemical Corp
Sinopec Nanjing Chemical Industry Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Sinopec Nanjing Chemical Industry Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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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
    • C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino 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
    • C07C209/30—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
    • 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
    • C07C209/38—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 nitroso groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a method for preparing RT base by normal pressure condensation, which is mainly characterized by adopting a solid base catalyst and a process method for preparing RT base by catalytic condensation under 1 standard atmospheric pressure. The method overcomes the defects of the prior art, uses a suitable solid base catalyst in the production process of the RT base, adopts the normal pressure condition for reaction through process improvement, and avoids the use of a vacuum pump from the source, thereby optimizing the process flow, reducing the discharge of three wastes and realizing the environment-friendly production of the RT base.

Description

Method for preparing RT base by normal pressure condensation
Technical Field
The invention belongs to the field of rubber additives, and particularly relates to a process method for preparing a rubber antioxidant intermediate RT base by normal pressure condensation.
Background
RT base (p-aminodiphenylamine) is widely applied to rubber auxiliaries, dyes, textile, printing, pharmaceutical industry and the like, and is mainly used for rubber anti-aging agents 4010NA, 6PPD and the like.
The annual total energy of domestic RT base is about 18 million tons, the existing ten-thousand-ton grade RT base device of China petrochemical south chemical company is produced by adopting a nitrobenzene method, tetramethylammonium hydroxide is used as a catalyst in the condensation reaction in the existing nitrobenzene method, the catalyst is easy to absorb carbon dioxide in air to form carbonate, and the catalytic effect of the carbonate is lost, so that in the actual industrial production, the condensation reaction adopts a vacuumizing protection mode, and the inactivation caused by the contact of the tetramethylammonium hydroxide and the air is avoided.
Generally, the vacuum system is realized by a vacuum pump, which is a moving device and has a short maintenance time period due to mechanical wear and the like. In order to maintain the expected vacuum degree, the vacuum pump needs to regularly replace a fresh medium, the common medium is vacuum pump oil, and the replaced waste oil is treated in a three-waste mode through burning, so that the environment is polluted to a certain extent, and the industrial cost is increased.
Therefore, a process method for preparing RT base by condensation under normal pressure needs to be developed, so that the use of a vacuum pump is avoided from the source, and the process flow is further optimized.
In the process for preparing RT base by nitrobenzene condensation, the determinant factor of the vacuum system is the use of the catalyst tetramethylammonium hydroxide. The tetramethylammonium hydroxide exists in the reaction system in the form of aqueous solution, firstly, the vacuumizing is to protect the tetramethylammonium hydroxide from being poisoned by carbon dioxide, secondly, water in the reaction system can be removed in a reduced pressure distillation mode at a lower temperature, so that the reaction balance is carried out rightwards, the conversion rate of nitrobenzene is improved, thirdly, the tetramethylammonium hydroxide is easy to decompose under heating, a device capable of realizing dehydration at a lower temperature is needed, and the vacuum pump can meet the three requirements. If the catalyst is replaced, the catalyst has the capabilities of resisting poison and high temperature and exists in a non-aqueous solution or solid state, the vacuum pump is no longer used.
The solid base catalyst has the advantages of no corrosion, high selectivity, high catalytic activity, easy separation of products and the like, and is widely applied to organic reactions of various alkaline systems.
At present, the main design concept of the solid base catalyst applied to the condensation preparation of RT base is that tetramethyl ammonium hydroxide is used as an active site, potassium hydroxide is used as regenerated base, resin is used as a carrier, the service life of the catalyst is prolonged through the regeneration effect of potassium hydroxide, but the solid base catalyst is not suitable for catalyzing condensation reaction under normal pressure (CN 102259029A).
The other idea is that potassium hydroxide is used as an alkaline catalyst, tetrabutylammonium bromide is used as a phase transfer catalyst, and the potassium hydroxide and the tetrabutylammonium bromide catalyze the condensation reaction under the synergistic action. Compared with tetramethylammonium hydroxide, potassium hydroxide and tetrabutylammonium bromide have strong anti-toxicity and high-temperature resistance, and the method does not need to remove a large amount of water, so that the method has the possibility of atmospheric pressure catalysis, but the patent CN102372640A does not relate to relevant information.
Disclosure of Invention
The invention provides a method for preparing RT base by normal pressure condensation.
The invention aims to overcome the defects in the prior art, and the proper solid base catalyst is used in the production process of RT base, the reaction is carried out under normal pressure conditions through process improvement, and the use of a vacuum pump is avoided from the source, so that the process flow is optimized, the three-waste emission is reduced, and the environment-friendly production of RT base is realized.
The preparation method provided by the invention is realized by the following modes:
mixing raw materials of aniline, nitrobenzene and a solid base catalyst by a one-pot method under normal pressure, heating to a reaction temperature, and reacting for a period of time to obtain a condensation liquid of RT base. The method is mainly characterized by normal-pressure reaction, and the use of a vacuum pump is avoided.
The method for preparing RT base by normal pressure condensation is applied to the preparation of RT base by condensation reaction, and the reaction pressure is 1 standard atmospheric pressure.
Furthermore, the raw materials of the condensation reaction are aniline and nitrobenzene.
Further, the catalyst for the condensation reaction includes a basic catalyst and a phase transfer catalyst.
The alkaline catalyst comprises sodium hydroxide, potassium hydroxide, alkaline resin and an alumina catalyst loaded with various alkaline components.
The phase transfer catalyst comprises tetramethyl ammonium hydroxide, tetrabutyl ammonium bromide and sodium dodecyl benzene sulfonate.
The method for preparing RT base by normal pressure condensation comprises the steps of adding aniline, nitrobenzene and a catalyst into a reaction kettle, mixing, heating to a reaction temperature, reacting for a period of time to obtain a condensation liquid, wherein the selectivity of target products (4-nitrosodiphenylamine and 4-nitrodiphenylamine) is 60% -90%.
Further, the reaction temperature is 70-200 ℃, and the reaction time is 4-20 h.
Further, the molar ratio of aniline to nitrobenzene is 5-10: 1, the weight ratio of the catalyst to the nitrobenzene is 0.0005-0.5: 1.
the invention has the advantages of
In the preparation process of the RT base, a vacuum system is not needed, so that the equipment expenditure of a vacuum pump is saved, and the process route is optimized; the treatment problem of the vacuum pump oil waste liquid is avoided, and the discharge of three wastes is reduced; the use of solid base catalysts reduces the corrosion of equipment.
The method overcomes the defects of the prior art, uses a proper solid base catalyst in the production process of the RT base, adopts the normal pressure condition for reaction through process improvement, and avoids the use of a vacuum pump from the source, thereby optimizing the process flow, reducing the discharge of three wastes and realizing the environment-friendly production of the RT base.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Preparation of RT base:
2.2 g of basic resin catalyst and 0.4 g of tetrabutylammonium bromide were weighed into a three-necked flask, and 30 g of aniline was added. Building a reaction device, weighing 8.0 g of nitrobenzene in a constant pressure dropping funnel, placing the funnel at the side opening of a three-neck flask, building a reflux device, heating the funnel to 100 ℃ in an oil bath under 1 standard atmospheric pressure, stirring for 1 h, then dropwise adding nitrobenzene, reacting for 5-8 h to obtain a condensation liquid, wherein the selectivity of a target product is 69.4% -84.3%.
Example 2
Preparation of RT base:
2.2 g of basic resin catalyst and 0.4 g of tetrabutylammonium bromide were weighed into a three-necked flask, and 30 g of aniline was added. Building a reaction device, weighing 8.0 g of nitrobenzene in a constant pressure dropping funnel, placing the funnel at the side opening of a three-neck flask, building a reflux device, heating the funnel to 120 ℃ in an oil bath under 1 standard atmospheric pressure, stirring for 1 h, then dropwise adding nitrobenzene, reacting for 5-8 h to obtain a condensation liquid, wherein the selectivity of a target product is 67.8% -81.2%.
Example 3
Preparation of RT base:
1.5 g of basic resin catalyst and 0.4 g of sodium dodecylbenzenesulfonate were weighed into a three-necked flask, and 30 g of aniline was added. Building a reaction device, weighing 5.2 g of nitrobenzene in a constant pressure dropping funnel, placing the funnel at the side opening of a three-neck flask, building a reflux device, heating the funnel to 120 ℃ in an oil bath under 1 standard atmospheric pressure, stirring for 1 h, then dropwise adding nitrobenzene, reacting for 8-16 h to obtain a condensation liquid, wherein the selectivity of a target product is 69.8% -83.6%.
Example 4
Preparation of RT base:
1.5 g of MgO/Al are weighed2O3Catalyst, 0.4 g tetrabutylammonium bromide in a three-necked flask, 30 g aniline was added. Setting up a reaction device, weighing 5.2 g of nitrobenzene in a constant pressure dropping funnel, placing the nitrobenzene in a side opening of a three-neck flask, setting up a reflux device, and heating the nitrobenzene in an oil bath under 1 standard atmospheric pressureAnd (3) stirring for 1 h at 120 ℃, then dropwise adding nitrobenzene, reacting for 8-16 h to obtain a condensation liquid, wherein the selectivity of the target product is 71.2-89.4%.
Example 5
Preparation of RT base:
1.5 g of MgO/Al are weighed2O3Catalyst, 0.4 g sodium dodecylbenzene sulfonate, and 30 g aniline were added to a three-necked flask. Building a reaction device, weighing 5.2 g of nitrobenzene in a constant pressure dropping funnel, placing the funnel at the side opening of a three-neck flask, building a reflux device, heating the funnel to 200 ℃ in an oil bath under 1 standard atmospheric pressure, stirring for 1 h, then dropwise adding nitrobenzene, reacting for 12-16 h to obtain a condensation liquid, wherein the selectivity of a target product is 65.7% -82.4%.
Example 6
Preparation of RT base:
1.5 g KOH/Al was weighed2O3Catalyst, 0.4 g tetrabutylammonium bromide in a three-necked flask, 30 g aniline was added. Building a reaction device, weighing 5.2 g of nitrobenzene in a constant pressure dropping funnel, placing the funnel at the side opening of a three-neck flask, building a reflux device, heating the funnel to 120 ℃ in an oil bath under 1 standard atmospheric pressure, stirring for 1 h, then dropwise adding nitrobenzene, reacting for 12-16 h to obtain a condensation liquid, wherein the selectivity of a target product is 62.5% -80.1%.
Example 7
Preparation of RT base:
1.5 g KOH/Al was weighed2O3Catalyst, 0.4 g sodium dodecylbenzene sulfonate, and 30 g aniline were added to a three-necked flask. Building a reaction device, weighing 5.2 g of nitrobenzene in a constant pressure dropping funnel, placing the funnel at the side opening of a three-neck flask, building a reflux device, heating the funnel to 200 ℃ in an oil bath under 1 standard atmospheric pressure, stirring for 1 h, then dropwise adding nitrobenzene, reacting for 12-16 h to obtain a condensation liquid, wherein the selectivity of a target product is 60.2% -78.4%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention, such as changing the conversion conditions of the biological system and the reaction material ratio of aniline, etc. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. The method for preparing RT base by normal pressure condensation is characterized in that the method is used for preparing RT base by condensation reaction, and the reaction pressure is normal pressure.
2. The process of claim 1, wherein the reaction pressure is 1 atm.
3. The method of claim 1, wherein the raw materials for the condensation reaction are aniline and nitrobenzene.
4. The method of claim 1, wherein the condensation catalyst comprises a basic catalyst and a phase transfer catalyst.
5. The method of claim 4, wherein the basic catalyst comprises sodium hydroxide, potassium hydroxide, basic resin, and alumina catalyst supporting various types of basic components.
6. The method of claim 4, wherein the phase transfer catalyst comprises tetramethylammonium hydroxide, tetrabutylammonium bromide, sodium dodecylbenzenesulfonate.
7. The method as claimed in one of claims 1 to 6, wherein the raw materials aniline, nitrobenzene and catalyst are added into a reaction kettle, mixed and heated to reaction temperature, and condensation liquid is obtained after reaction, wherein the selectivity of the target product (4-nitrosodiphenylamine, 4-nitrodiphenylamine) is 60% -90%.
8. The method according to claim 1-3 or 7, wherein the reaction temperature is 70 to 200 ℃ and the reaction time is 4 to 20 hours.
9. The process according to any one of claims 1 to 8, wherein the molar ratio of aniline to nitrobenzene is from 5 to 10: 1, the weight ratio of the catalyst to the nitrobenzene is 0.0005-0.5: 1.
CN202010279748.5A 2020-04-10 2020-04-10 Method for preparing RT (reverse transcription) sauce by normal pressure condensation Active CN113527111B (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020045779A1 (en) * 1998-12-11 2002-04-18 Emanuel Beska Method of preparation of 4-aminodiphenylamine
WO2003010126A1 (en) * 2001-07-23 2003-02-06 Flexsys America L.P. Process for preparing 4-aminodiphenylamine
RU2004126787A (en) * 2004-09-08 2006-02-20 Николай Васильевич Мартынов (RU) SOLUTION FOR SYNTHESIS OF 4-AMINODIPHENYLAMINE, METHOD FOR ITS PRODUCTION AND METHOD FOR PRODUCING 4-AMINODIPHENYLAMINE
CN1865224A (en) * 2005-05-20 2006-11-22 中国石油天然气集团公司 Method for improving 4-amino diphenylamine yield
CN101381315A (en) * 2008-10-17 2009-03-11 王庆峰 Preparation method of p-aminodiphenylamine
CN102259029A (en) * 2010-05-24 2011-11-30 江苏圣奥化学科技有限公司 Solid alkali catalyst
CN102344376A (en) * 2011-08-17 2012-02-08 中国石油化工股份有限公司 Method for preparing p-aminodiphenylamine
CN102372639A (en) * 2010-08-20 2012-03-14 中国石油化工集团公司 Method for preparing 4-aminodiphenyamine

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020045779A1 (en) * 1998-12-11 2002-04-18 Emanuel Beska Method of preparation of 4-aminodiphenylamine
WO2003010126A1 (en) * 2001-07-23 2003-02-06 Flexsys America L.P. Process for preparing 4-aminodiphenylamine
CN1545497A (en) * 2001-07-23 2004-11-10 Process for preparing 4-aminodiphenylamine
RU2004126787A (en) * 2004-09-08 2006-02-20 Николай Васильевич Мартынов (RU) SOLUTION FOR SYNTHESIS OF 4-AMINODIPHENYLAMINE, METHOD FOR ITS PRODUCTION AND METHOD FOR PRODUCING 4-AMINODIPHENYLAMINE
CN1865224A (en) * 2005-05-20 2006-11-22 中国石油天然气集团公司 Method for improving 4-amino diphenylamine yield
CN101381315A (en) * 2008-10-17 2009-03-11 王庆峰 Preparation method of p-aminodiphenylamine
CN102259029A (en) * 2010-05-24 2011-11-30 江苏圣奥化学科技有限公司 Solid alkali catalyst
US20130079560A1 (en) * 2010-05-24 2013-03-28 Jiangsu Sinorgchem Technology Co., Ltd. Solid base catalyst and method for making and using the same
CN102372639A (en) * 2010-08-20 2012-03-14 中国石油化工集团公司 Method for preparing 4-aminodiphenyamine
CN102344376A (en) * 2011-08-17 2012-02-08 中国石油化工股份有限公司 Method for preparing p-aminodiphenylamine

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