CN105820056A - Synthesizing method of 4,4'-dimethyltriphenylamine and production system - Google Patents
Synthesizing method of 4,4'-dimethyltriphenylamine and production system Download PDFInfo
- Publication number
- CN105820056A CN105820056A CN201610325619.9A CN201610325619A CN105820056A CN 105820056 A CN105820056 A CN 105820056A CN 201610325619 A CN201610325619 A CN 201610325619A CN 105820056 A CN105820056 A CN 105820056A
- Authority
- CN
- China
- Prior art keywords
- dimethyl
- diphenylamines
- dimethyl diphenylamines
- production system
- hydrolysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
Abstract
The invention belongs to the technical field of chemical synthesis, and particularly relates to a synthesizing method of 4,4'-dimethyltriphenylamine and a production system .The method includes the steps that paratoluidine is hydrolyzed through a catalyst under the acid condition to prepare p-cresol, and p-cresol reacts with paratoluidine to prepare 4,4'-dimethyltriphenylamine .The method has the advantages that the method is simple in process, mild in reaction condition, safe and reliable in production process, low in production cost, small in by-product and small in sewage amount, and raw materials are easy to obtain.
Description
Technical field
The invention belongs to technical field of chemical synthesis, be specifically related to a kind of 4,4 '-dimethyl diphenylamines
Synthetic method and production system.
Background technology
The most domestic and international 4,4 '-dimethyl diphenylamines synthetic method mainly has 2 kinds.First method:
Not only generate diaryl-amine owing to virtue halogen compound reacts with aryl primary amine, also generate triaryl amine, so to iodotoluene
Generate 4,4'-dimethyl diphenylamines with para-totuidine reaction and generate substantial amounts of 4,4', 4 "-trimethyl triphens simultaneously
Amine.Second method: para-totuidine is acylated to react with to iodotoluene again, the method system being finally hydrolyzed
Standby 4,4'-dimethyl diphenylamines.This reaction compensate for the deficiency of virtue halogen compound and aryl primary amine direct reaction,
Although yield is low, but do not produce 4,4', 4 "-trimethyl triphenylamines.But, there is product in above several method
By-product is many, difficult separation, the shortcomings such as quality is the highest, and product yield is low.
Summary of the invention
For solving the deficiencies in the prior art, the invention provides a kind of 4, the conjunction of 4 '-dimethyl diphenylamines
One-tenth method and production system.The present invention uses the direct catalyzing hydrolysis of para-totuidine to prepare paracresol, and and then
Synthesis 4,4 '-dimethyl diphenylamines, have that technique is simple, reaction condition is gentle, production process safely may be used
The advantage such as lean on, production cost is low, by-product is few, raw material is easy to get and wastewater flow rate is few.
A kind of 4, the synthetic method of 4 '-dimethyl diphenylamines, carry out under the conditions of being included in acid catalyst
Following steps: para-totuidine hydrolysis is prepared paracresol, paracresol and then react with para-totuidine,
Prepare 4,4 '-dimethyl diphenylamines.
Reaction principle is as follows:
CH3C6H4NH2+H2O+H+→CH3C6H4OH+NH4 +
CH3C6H4OH+CH3C6H4NH2→CH3C6H4NHC6H4CH3+H20
After should terminating, the paracresol and the 4 of about 15% of available about 85%, 4 '-dimethyl diphenylamines.
Concrete, described acid catalyst is perfluorinated sulfonic resin or zirconio inoganic solids acid catalyst.Tool
Body, hydrolysis operation pressure is 20～30kg/cm2, hydrolysis operation temperature below 300 DEG C, hydrolysis
PH value is 2～4.
Concrete, reaction pressure is 0.5～0.6Mpa, and the response 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
Layer organic facies adds extractant and separates in extraction tower, obtains crude product paracresol solution and crude product 4,4 '
-dimethyl diphenylamine solution, more respectively rectification and being dried the most successively, obtain paracresol product and 4, and 4 '-two
Methyldiphenylamine.The condensed recovery of extractant after rectification, recycles.
Preferably, extractant is ethyl acetate.
Present invention also offers a kind of 4, the production system of 4 '-dimethyl diphenylamines, including being sequentially connected in series
Hydrolytic reaction pot, quantizer, extraction tower, rectifying column and vacuum desiccator.
Further, be also sequentially connected in series between described hydrolytic reaction pot and described quantizer cooling reactor and
Transfering material pump.
Further, between described extraction tower and described rectifying column, crude product storage tank also it is in series with.
Further, the rear end at described vacuum desiccator is provided with fine work storage tank.
Further, between described rectifying column and described extraction tower, condenser and recovery also it have been sequentially connected in series
Flux bath.
The condensed recovery of extractant after rectification, can be recycled.
This technique preparation technology more in the market has obvious cost advantage.Realize low cost, without dirty
Dye, without the three wastes, gained 4,4 '-dimethyl diphenylamines purity more than 99.50%, be correlated with physical and chemical indexes
All reach higher level, generally, had the advantage that
1) this technique synthesis 4,4 '-dimethyl diphenylamines, not only solve environmental problem, and improve
The yield of product, greatly reduces cost, and course of reaction is simple, easy to operate, environmentally safe.
2) this technological reaction mild condition, simple to operate, production process is safe and reliable.
3) this Technology three waste discharge meets environmental requirement.
Accompanying drawing explanation
Fig. 1 is provided by the present invention 4, the system diagram of the production system of 4 '-dimethyl diphenylamines.
Detailed description of the invention
Principle and feature to the present invention are described below, and illustrated embodiment is served only for explaining the present invention,
It is not intended to limit the scope of the present invention.
In a detailed description of the invention, as it is shown in figure 1, a kind of 4, the life of 4 '-dimethyl diphenylamines
Product system, including the hydrolytic reaction pot being sequentially connected in series, cooling reactor, transfering material pump, quantizer, extraction tower,
Crude product storage tank, rectifying column, vacuum desiccator and fine work storage tank.Also depend between rectifying column and described extraction tower
Secondary it is in series with condenser and recycling design groove.
Raw material toluidines hydrolyzes under catalyst regulates in hydrolytic reaction pot and reacts.Reactant liquor is cooled
Pumped in quantizer by transfering material pump after still cooling.Organic facies after layering extract and separate in extraction tower,
To crude product paracresol solution and 4,4 '-dimethyl diphenylamine solution.It is collected in the most respectively in crude product storage tank
Being dried through subcooler cooling, rectifying column rectification and vacuum desiccator, fine work is collected in fine work storage tank.
Extractant in rectifying column is reclaimed by recycling design groove, after through condenser condense, extraction tower can be put into
Middle reuse.
Embodiment 1
By para-totuidine at catalyst and hydrolyzed under acidic conditions, prepare paracresol, paracresol and then
React with para-totuidine, prepare 4,4 '-dimethyl diphenylamines.To obtain after hydrolysis and reaction
Solution send into quantizer stratification, take upper organic phase add extractant separate in extraction tower,
Obtain crude product paracresol solution and crude product 4,4 '-dimethyl diphenylamine solution, more successively rectification and
It is dried, obtains paracresol product and 4,4 '-dimethyl diphenylamines.
Wherein, perfluorinated sulfonic resin selected by acid catalyst, and hydrolysis operation pressure is 22kg/cm2, hydrolysis behaviour
Making temperature at 285 DEG C, the pH value of hydrolysis is 2；Reaction pressure is 0.5Mpa, and the response time is 16h,
Reaction temperature is 280 DEG C.
4,4 '-dimethyl diphenylamines yield 9.8%, purity 99.60%.
Embodiment 2
By para-totuidine at catalyst and hydrolyzed under acidic conditions, prepare paracresol, paracresol and then
React with para-totuidine, prepare 4,4 '-dimethyl diphenylamines.To obtain after hydrolysis and reaction
Solution send into quantizer stratification, take upper organic phase add extractant separate in extraction tower,
Obtain crude product paracresol solution and crude product 4,4 '-dimethyl diphenylamine solution, more successively rectification and
It is dried, obtains paracresol product and 4,4 '-dimethyl diphenylamines.
Wherein, perfluorinated sulfonic resin selected by acid catalyst, and hydrolysis operation pressure is 30kg/cm2, hydrolysis behaviour
Making temperature at 298 DEG C, the pH value of hydrolysis is 4；Reaction pressure is 0.6Mpa, and the response time is 15h,
Reaction temperature is 300 DEG C.
4,4 '-dimethyl diphenylamines yield 8.7%, purity 99.70%.
Embodiment 3
By para-totuidine at catalyst and hydrolyzed under acidic conditions, prepare paracresol, paracresol and then
React with para-totuidine, prepare 4,4 '-dimethyl diphenylamines.To obtain after hydrolysis and reaction
Solution send into quantizer stratification, take upper organic phase add extractant separate in extraction tower,
Obtain crude product paracresol solution and crude product 4,4 '-dimethyl diphenylamine solution, more successively rectification and
It is dried, obtains paracresol product and 4,4 '-dimethyl diphenylamines.
Wherein, zirconio inorganic solid acid selected by acid catalyst, and hydrolysis operation pressure is 25kg/cm2, hydrolysis
Operation temperature is at 293 DEG C, and the pH value of hydrolysis is 3；Reaction pressure is 0.55Mpa, and the response time is
15.5h, reaction temperature is 290.
4,4 '-dimethyl diphenylamines yield 9.3%, purity 99.85%.
By method and system provided by the present invention, high-purity 4,4 '-dimethyl hexichol can be prepared
Amine, the most a large amount of coproduction paracresol.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all in the present invention
Spirit and principle within, any modification, equivalent substitution and improvement etc. made, should be included in this
Within bright protection domain.
Claims (10)
1. one kind 4, the synthetic method of 4 '-dimethyl diphenylamines, it is characterised in that be included in acid catalysis
The following steps carried out under the conditions of agent: para-totuidine hydrolysis is prepared paracresol, paracresol so that with
Para-totuidine reacts, and prepares 4,4 '-dimethyl diphenylamines.
The most according to claim 14, the synthetic method of 4 '-dimethyl diphenylamines, its feature exists
In: described acid catalyst is perfluorinated sulfonic resin or zirconio inoganic solids acid catalyst.
The most according to claim 14, the synthetic method of 4 '-dimethyl diphenylamines, its feature exists
In: hydrolysis operation pressure is 20～30kg/cm2, hydrolysis operation temperature below 300 DEG C, the pH of hydrolysis
Value is 2～4.
The most according to claim 14, the synthetic method of 4 '-dimethyl diphenylamines, its feature exists
In: reaction pressure is 0.5～0.6Mpa, and the response time is 15～16h, and reaction temperature is 280～300 DEG C.
5. according to Claims 1-4 arbitrary described 4, the synthetic method of 4 '-dimethyl diphenylamines,
It is characterized in that, further comprising the steps of: the solution obtained after hydrolysis and reaction is sent into quantizer
Stratification, takes upper organic phase addition extractant and separates in extraction tower, obtain crude product paracresol
Solution and crude product 4,4 '-dimethyl diphenylamine solution, then rectification, with dry, obtains first the most successively
Phenolic product and 4,4 '-dimethyl diphenylamines.
6. one kind 4, the production system of 4 '-dimethyl diphenylamines, it is characterised in that: include being sequentially connected in series
Hydrolytic reaction pot, quantizer, extraction tower, rectifying column and vacuum desiccator.
The most according to claim 64, the production system of 4 '-dimethyl diphenylamines, its feature exists
In: between described hydrolytic reaction pot and described quantizer, also it has been sequentially connected in series cooling reactor and transfering material pump.
The most according to claim 74, the production system of 4 '-dimethyl diphenylamines, its feature exists
In: between described extraction tower and described rectifying column, also it is in series with crude product storage tank.
The most according to claim 84, the production system of 4 '-dimethyl diphenylamines, its feature exists
In: the rear end of described vacuum desiccator is provided with fine work storage tank.
The most according to claim 94, the production system of 4 '-dimethyl diphenylamines, its feature
It is: between described rectifying column and described extraction tower, be also sequentially connected in series condenser and recycling design groove.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610325619.9A CN105820056B (en) | 2016-05-17 | 2016-05-17 | A kind of synthetic method and production system of 4,4 '-dimethyl diphenylamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610325619.9A CN105820056B (en) | 2016-05-17 | 2016-05-17 | A kind of synthetic method and production system of 4,4 '-dimethyl diphenylamines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105820056A true CN105820056A (en) | 2016-08-03 |
| CN105820056B CN105820056B (en) | 2018-07-17 |
Family
ID=56530677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610325619.9A Active CN105820056B (en) | 2016-05-17 | 2016-05-17 | A kind of synthetic method and production system of 4,4 '-dimethyl diphenylamines |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105820056B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (4)
| 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 |
| 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS165293B1 (en) * | 1973-02-09 | 1975-12-22 |
-
2016
- 2016-05-17 CN CN201610325619.9A patent/CN105820056B/en active Active
Patent Citations (4)
| 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 |
| 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 |
|---|
| KATRITZKY, ALAN R.: "Aqueous high-temperature chemistry of carbo- and heterocycles", 《ENERGY & FUELS》 * |
| 田璇: "间苯二酚的低污染合成工艺研究", 《南京理工大学硕士论文集》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105820056B (en) | 2018-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3476837B1 (en) | Method for preparing azoxystrobin intermediates | |
| CN103772145B (en) | A kind of separation method of acetone hydrogenation preparing isopropanol | |
| CN105130778A (en) | Production process of methyl isobutyl ketone | |
| CN104761429A (en) | Dimethyl carbonate and ethylene glycol production process | |
| CN107793319A (en) | A kind of preparation technology of 2,6 diethylaniline | |
| CN102070521A (en) | Method for preparing quinoline derivative | |
| CN103012074B (en) | Prepare the method for aromatic methyl ether compound | |
| CN105000564B (en) | Production method of dichlorosilane for preparing silane | |
| CN103772205A (en) | Method for separating ethidene diamine and water | |
| CN103274913A (en) | Method and device for producing methyl isobutyl ketone | |
| CN103641780B (en) | A kind of method of purifying isoquinoline from coal tar crude product | |
| CN108314617B (en) | Method and device for recovering acetaldehyde in pentaerythritol production | |
| CN111072602A (en) | Preparation of 3-acetamido-5-acetylfuran from chitin monomer N-acetylglucosamine catalyzed by amino acid ionic liquid | |
| CN105820056A (en) | Synthesizing method of 4,4'-dimethyltriphenylamine and production system | |
| CN102304055B (en) | Method for preparing ethanolamine hydrochlorides and coproduct ethanolamine | |
| CN104447198A (en) | Novel separation technology for preparation of isopropanol by acetone hydrogenation | |
| CN102633314A (en) | Low-concentration formaldehyde wastewater resource recycling process | |
| CN212247087U (en) | Production equipment of phenylethylamine | |
| CN112679329A (en) | Continuous production process of 1,4-cyclohexanedione | |
| CN105924328B (en) | A kind of highly selective green hydrolysis technique for preparing benzyl alcohol | |
| CN105585503B (en) | The method that ethylenediamine is produced using monoethanolamine and liquefied ammonia as raw material | |
| CN204275534U (en) | A kind of dimethoxym ethane process for refining equipment of producing glyphosate by using glycine accessory substance | |
| CN104447199B (en) | The method that extractive distillation with salt method acetone hydrogenation reaction product prepares isopropanol | |
| CN205635425U (en) | Hydrolysis production system of p toluidine preparation paracresol of catalysis | |
| CN204727810U (en) | A kind of purification and recover device for acetonitrile in ceftriaxone sodium synthesis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |