CN105820056B - A kind of synthetic method and production system of 4,4 '-dimethyl diphenylamines - Google Patents
A kind of synthetic method and production system of 4,4 '-dimethyl diphenylamines Download PDFInfo
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- CN105820056B CN105820056B CN201610325619.9A CN201610325619A CN105820056B CN 105820056 B CN105820056 B CN 105820056B CN 201610325619 A CN201610325619 A CN 201610325619A CN 105820056 B CN105820056 B CN 105820056B
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- paracresol
- hydrolysis
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- reaction
- diphenylamines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/045—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen
- C07C37/05—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen by substitution of a NH2 group
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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
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to technical field of chemical synthesis, and in particular to a kind of synthetic method and production system of 4,4 ' dimethyl diphenylamines.In catalyst and hydrolyzed under acidic conditions, paracresol is prepared in para-totuidine by method provided by the present invention, and paracresol is reacted with para-totuidine in turn, and 4,4 ' dimethyl diphenylamines are prepared.It is few with wastewater flow rate that the technique has many advantages, such as that simple for process, reaction condition is mild, production process is safe and reliable, production cost is low, by-product is few, raw material is easy to get.
Description
Technical field
The invention belongs to technical field of chemical synthesis, and in particular to a kind of synthetic method of 4,4 '-dimethyl diphenylamines and
Production system.
Background technology
Current domestic and international 4,4 '-dimethyl diphenylamines synthetic method mainly has 2 kinds.First method：Since fragrant halogenation is closed
Object is reacted with aryl primary amine not only generates diaryl-amine, also generates triaryl amine, so generating 4,4'- to iodotoluene and para-totuidine reaction
Dimethyl diphenylamines generates a large amount of 4,4', 4 "-trimethyl triphenylamines simultaneously.Second method：Para-totuidine be acylated again with it is right
Iodotoluene reacts, and the method being finally hydrolyzed prepares 4,4'- dimethyl diphenylamines.The reaction compensates for fragrant halogen compound and virtue
The deficiency that primary amine directly reacts, yield is although low, but does not generate 4,4', 4 "-trimethyl triphenylamines.However, the above several method
There are product by-product is more, hardly possible separation, the disadvantages such as quality is not high, and product yield is low.
Invention content
To solve the deficiencies in the prior art, the present invention provides a kind of synthetic method of 4,4 '-dimethyl diphenylamines and lifes
Production system.The present invention prepares paracresol using the direct catalyzing hydrolysis of para-totuidine, and synthesizes 4,4 '-dimethyl diphenylamines in turn,
With simple for process, reaction condition is mild, production process is safe and reliable, production cost is low, by-product is few, raw material is easy to get and waste water
The advantages that amount is few.
A kind of synthetic method of 4,4 '-dimethyl diphenylamines, is included in the following steps carried out under the conditions of acid catalyst：It will
Paracresol is prepared in para-totuidine hydrolysis, and paracresol is reacted with para-totuidine in turn, and 4,4 '-dimethyl hexichol are prepared
Amine.
Reaction principle is as follows：
CH3C6H4NH2+H2O+H+→CH3C6H4OH+NH4 +
CH3C6H4OH+CH3C6H4NH2→CH3C6H4NHC6H4CH3+H20
After answering, 85% or so paracresol and the 4 of 15% or so, 4 '-dimethyl diphenylamines can be obtained.
Specifically, the acid catalyst is perfluorinated sulfonic resin or zirconium base inoganic solids acid catalyst.Specifically, hydrolysis
Operating pressure is 20~30kg/cm2, hydrolysis operation temperature is at 300 DEG C hereinafter, the pH value of hydrolysis is 2~4.
Specifically, reaction pressure is 0.5~0.6Mpa, the reaction time is 15~16h, and reaction temperature is 280~300 DEG C.
Further, the solution obtained after hydrolysis and reaction is sent into quantizer stratification, takes upper organic phase
Extractant is added to be detached in extraction tower, 4,4 '-dimethyl diphenylamine solution of crude product paracresol solution and crude product is obtained, then
Rectifying and drying successively respectively, obtains paracresol product and 4,4 '-dimethyl diphenylamines.Condensed time of extractant after rectifying
It receives, recycles.
Preferably, extractant is ethyl acetate.
The present invention also provides a kind of production systems of 4,4 '-dimethyl diphenylamines, including the hydrolysis being sequentially connected in series
Kettle, quantizer, extraction tower, rectifying column and vacuum desiccator.
Further, cooling reactor and transfering material pump have also been sequentially connected in series between the hydrolytic reaction pot and the quantizer.
Further, crude product storage tank is also in series between the extraction tower and the rectifying column.
Further, the rear end of the vacuum desiccator is provided with fine work storage tank.
Further, condenser and recycling design slot have also been sequentially connected in series between the rectifying column and the extraction tower.
The condensed recycling of extractant after rectifying, can be recycled.
Preparation process has apparent cost advantage to this technique more currently on the market.Realize inexpensive, pollution-free, nothing three
For useless, 4,4 '-dimethyl diphenylamines purity of gained 99.50% or more, related physical and chemical indexes have all reached higher level, overall
On, it has the following advantages：
1) this technique synthesizes 4,4 '-dimethyl diphenylamines, not only solves environmental problem, and improve the receipts of product
Rate greatly reduces cost, and reaction process is simple, easy to operate, environmentally safe.
2) this technological reaction mild condition, easy to operate, production process is safe and reliable.
3) this technology three waste discharge meets environmental requirement.
Description of the drawings
Fig. 1 is the system diagram of the production system of provided by the present invention 4,4 '-dimethyl diphenylamines.
Specific implementation mode
The principles and features of the present invention are described below, and illustrated embodiment is served only for explaining the present invention, is not intended to
Limit the scope of the present invention.
In a specific embodiment, as shown in Figure 1, a kind of production system of 4,4 '-dimethyl diphenylamines, including according to
Secondary concatenated hydrolytic reaction pot, cooling reactor, transfering material pump, quantizer, extraction tower, crude product storage tank, rectifying column, vacuum desiccator and essence
Product storage tank.Condenser and recycling design slot have also been sequentially connected in series between rectifying column and the extraction tower.
Raw material toluidines is hydrolyzed and is reacted under catalyst adjusting in hydrolytic reaction pot.Reaction solution is after cooling reactor cools down
It is pumped into quantizer by transfering material pump.Organic phase extraction and separation in extraction tower after layering, obtain crude product paracresol solution and 4,
4 '-dimethyl diphenylamine solutions.Cooling, rectifying column rectifying and vacuum drying through subcooler are collected in crude product storage tank respectively again
Device is dried, and fine work is collected in fine work storage tank.Extractant in rectifying column is recycled by recycling design slot, after it is cold by condenser
It is solidifying, reuse in extraction tower can be put into.
Embodiment 1
By para-totuidine in catalyst and hydrolyzed under acidic conditions, be prepared paracresol, paracresol so that with to toluene
Amine reacts, and 4,4 '-dimethyl diphenylamines are prepared.The solution obtained after hydrolysis and reaction is sent into quantizer and stood and is divided
Layer takes upper organic phase that extractant is added and is detached in extraction tower, obtains 4,4 '-diformazan of crude product paracresol solution and crude product
Base diphenylamine solution, then rectifying and drying successively respectively, obtain paracresol product and 4,4 '-dimethyl diphenylamines.
Wherein, it is 22kg/cm that acid catalyst, which selects perfluorinated sulfonic resin, hydrolysis operation pressure,2, hydrolysis operation temperature exists
285 DEG C, the pH value of hydrolysis is 2；Reaction pressure is 0.5Mpa, and reaction time 16h, reaction temperature is 280 DEG C.
4,4 '-dimethyl diphenylamines yields 9.8%, purity 99.60%.
Embodiment 2
By para-totuidine in catalyst and hydrolyzed under acidic conditions, be prepared paracresol, paracresol so that with to toluene
Amine reacts, and 4,4 '-dimethyl diphenylamines are prepared.The solution obtained after hydrolysis and reaction is sent into quantizer and stood and is divided
Layer takes upper organic phase that extractant is added and is detached in extraction tower, obtains 4,4 '-diformazan of crude product paracresol solution and crude product
Base diphenylamine solution, then rectifying and drying successively respectively, obtain paracresol product and 4,4 '-dimethyl diphenylamines.
Wherein, it is 30kg/cm that acid catalyst, which selects perfluorinated sulfonic resin, hydrolysis operation pressure,2, hydrolysis operation temperature exists
298 DEG C, the pH value of hydrolysis is 4；Reaction pressure is 0.6Mpa, and reaction time 15h, reaction temperature is 300 DEG C.
4,4 '-dimethyl diphenylamines yields 8.7%, purity 99.70%.
Embodiment 3
By para-totuidine in catalyst and hydrolyzed under acidic conditions, be prepared paracresol, paracresol so that with to toluene
Amine reacts, and 4,4 '-dimethyl diphenylamines are prepared.The solution obtained after hydrolysis and reaction is sent into quantizer and stood and is divided
Layer takes upper organic phase that extractant is added and is detached in extraction tower, obtains 4,4 '-diformazan of crude product paracresol solution and crude product
Base diphenylamine solution, then rectifying and drying successively respectively, obtain paracresol product and 4,4 '-dimethyl diphenylamines.
Wherein, it is 25kg/cm that acid catalyst, which selects zirconium base inorganic solid acid, hydrolysis operation pressure,2, hydrolysis operation temperature exists
293 DEG C, the pH value of hydrolysis is 3；Reaction pressure is 0.55Mpa, reaction time 15.5h, reaction temperature 290.
4,4 '-dimethyl diphenylamines yields 9.3%, purity 99.85%.
The method and system provided through the invention, can prepare high-purity 4,4 '-dimethyl diphenylamines, while a large amount of
Coproduction paracresol.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (2)
1. the synthetic method of 4,4 '-dimethyl diphenylamines of one kind, which is characterized in that be included in carry out under the conditions of acid catalyst with
Lower step：Paracresol is prepared in para-totuidine hydrolysis, paracresol is reacted with para-totuidine in turn, is prepared 4,4 '-two
Methyldiphenylamine；
The acid catalyst is perfluorinated sulfonic resin or zirconium base inoganic solids acid catalyst；
Hydrolysis operation pressure is 20~30kg/cm2, hydrolysis operation temperature is at 300 DEG C hereinafter, the pH value of hydrolysis is 2~4；
Reaction pressure is 0.5~0.6Mpa, and the reaction time is 15~16h, and reaction temperature is 280~300 DEG C.
2. the synthetic method of according to claim 14,4 '-dimethyl diphenylamines, which is characterized in that further include following step
Suddenly：The solution obtained after hydrolysis and reaction is sent into quantizer stratification, takes upper organic phase that extractant is added and is extracting
Take in tower and detached, obtain 4,4 '-dimethyl diphenylamine solution of crude product paracresol solution and crude product, then respectively successively rectifying and
It is dry, obtain paracresol product and 4,4 '-dimethyl diphenylamines.
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| CN105820056B true CN105820056B (en) | 2018-07-17 |
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| CN107721822A (en) * | 2017-09-18 | 2018-02-23 | 江苏迈达新材料股份有限公司 | A kind of method and system for industrializing continuous production paracresol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS165293B1 (en) * | 1973-02-09 | 1975-12-22 | ||
| CN1958546A (en) * | 2005-11-03 | 2007-05-09 | 常州市常虹化工技术开发有限公司 | Industrialized method for preparing resorcin |
| CN101918387A (en) * | 2007-11-16 | 2010-12-15 | 住友化学株式会社 | Alpha, beta-unsaturated imidate compound and pesticidal composition containing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS48103530A (en) * | 1972-04-11 | 1973-12-25 | ||
| JPH01100152A (en) * | 1987-10-13 | 1989-04-18 | Honsyu Kagaku Kogyo Kk | Production of diphenylamine nucleus-substituted compound |
-
2016
- 2016-05-17 CN CN201610325619.9A patent/CN105820056B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS165293B1 (en) * | 1973-02-09 | 1975-12-22 | ||
| CN1958546A (en) * | 2005-11-03 | 2007-05-09 | 常州市常虹化工技术开发有限公司 | Industrialized method for preparing resorcin |
| CN101918387A (en) * | 2007-11-16 | 2010-12-15 | 住友化学株式会社 | Alpha, beta-unsaturated imidate compound and pesticidal composition containing the same |
Non-Patent Citations (2)
| Title |
|---|
| Aqueous high-temperature chemistry of carbo- and heterocycles;Katritzky, Alan R.;《Energy & Fuels》;19901231;第4卷(第5期);第550页 * |
| 间苯二酚的低污染合成工艺研究;田璇;《南京理工大学硕士论文集》;20071231;第9、31-32、38页 * |
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