CN105884622A - Method for preparing 1,5-diaminonaphthlene - Google Patents
Method for preparing 1,5-diaminonaphthlene Download PDFInfo
- Publication number
- CN105884622A CN105884622A CN201610396871.9A CN201610396871A CN105884622A CN 105884622 A CN105884622 A CN 105884622A CN 201610396871 A CN201610396871 A CN 201610396871A CN 105884622 A CN105884622 A CN 105884622A
- Authority
- CN
- China
- Prior art keywords
- diaminonaphthalene
- reaction
- preparation
- sulfite
- catalyst
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/18—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a process for preparing 1,5-diaminonaphthlene, in particular to a method for preparing 1,5-diaminonaphthlene. In a deionized water solution, 1,5-dihydroxy naphthalene is used as raw material, sulfite is used as catalyst, insoluble gas is introduced into a reaction system, reaction temperature is controlled to be 120-200 DEG C, ammonia gas is introduced to make reaction pressure stay at 1-10 MPa, cooling crystallization is conducted after reaction ends, pressure is relieved, a solid constituent is filtered out, mother liquor is collected, 1/3-2/3 of mother liquor by weight is used for the next time of reaction, and finally the solid constituent is washed with deionized water and then dried to obtain 1,5-diaminonaphthlene. By the adoption of the method, product yield can reach 90% or more, product purity can reach 99% or more, the usage of catalyst in reaction is reduced, and sewage discharge can be reduced.
Description
Technical field
The present invention relates to the preparation technology of 1,5-diaminonaphthalene, particularly relate to the preparation of a kind of 1,5-diaminonaphthalene
Method.
Background technology
1,5-diaminonaphthalene is important industrial chemicals intermediate, be applied to organic synthesis, pigment, dyestuff,
Multiple fine chemical product raw material and the intermediate such as medicine, pesticide, macromolecular material, sensitive material.At present
Being mainly used in synthesis 1,5-naphthalene diisocyanate, 1,5-naphthalene diisocyanate is extraordinary isocyanates industry
Important monomer, can prepare high-performance polyurethane elastomer with it, and purposes is quite varied.
1,5-diaminonaphthalene synthetic technology is a lot of at present, employing 1,5-dihydroxy naphthlene ammonification synthetic method (as
US4973758, US5113025, examined patent publication 59-29061 publication etc.), domestic periodical " Institutes Of Technology Of Tianjin
Report " 2006 years, volume 22, the 3rd phase 79～page 80 have also been made relevant research；Use 1,5-dinitro
Naphthalene hydrogen reduction is (such as US 4026944, CN101544569A, CN101575295A, CN103497113A
Deng)；Use naphthalene bromination ammonolysis synthetic method (such as US 6538158)；Use 1,5-dinitronaphthalene electrochemical synthesis
Method (such as CN101187031A)；Employing ortho-methylnitrobenzene is raw material, by with acrylonitrile base catalysis addition, acid
Catalysis closed loop, catalytic hydrogenation synthetic method (such as US 0143137)；Employing naphthalene one-step synthesis (as
CN103420851A).More than research only 1,5-dinitronaphthalene reducing process prepares 1,5-diaminonaphthalene industrialization
Produce report, by 1,5-dihydroxy naphthlene synthetic technology, do not have industrialization to be largely determined by cost of material in the past
Higher, synthesis condition is harsh (high temperature, high pressure) and catalyst amount is relatively big, along with 1, on 5-dihydroxy naphthlene
The development of trip technology and equipment manufacturing technology progress, use 1 at present, and 5-dihydroxy naphthlene carries out ammonolysis synthesis to be prepared
1,5-diaminonaphthalene technology can apply in commercial production, but product appearance, and yield, purity has
To be modified, and substantial amounts of catalyst can be used in reacting, the most also produce large amount of sewage.The present invention is exactly
On the basis of original technical conditions, carried out technological improvement based on this, prepare high-quality, the 1,5-of high yield
The technical method of diaminonaphthalene, is more beneficial for industrialized production.
Summary of the invention
The technical problem to be solved is: for the deficiencies in the prior art, it is provided that a kind of 1,5-diamino
The preparation method of base naphthalene, this preparation method can increase product yield, raising product purity, can reduce catalyst
Consumption, additionally can reduce quantity of wastewater effluent.
For solving above-mentioned technical problem, the technical scheme is that
A kind of preparation method of 1,5-diaminonaphthalene, it is characterised in that: in deionized water solution, with 1,5-
Dihydroxy naphthlene is raw material, with sulphite as catalyst, is passed through slightly solubility gas in reaction system, controls
Reaction temperature, at 120-200 DEG C, then passes to ammonia and makes reaction pressure be maintained between 1-10MPa to react,
Reaction terminates rear decrease temperature crystalline, lays down pressure, filters out solid constituent, collects mother solution and takes its mother solution weight
1/3-2/3 be inserted in next batch reaction, be finally washed with deionized solid constituent and obtain through drying
Product 1,5-diaminonaphthalene.
As the preferred technical scheme of one, described sulphite is sodium sulfite, Potassium acid sulfite, Asia
One or two kinds of in ammonium hydrogen sulfate, sodium sulfite, potassium sulfite and ammonium sulfite.
As a kind of further preferred technical scheme, described sulphite is sodium sulfite or sulfurous acid
Hydrogen ammonium.
As the preferred technical scheme of one, described slightly solubility gas is nitrogen, hydrogen or argon.
As the preferred technical scheme of one, described 1,5-dihydroxy naphthlene dry product quality in reaction system is dense
Degree is 10-30%.
As the preferred technical scheme of one, the amount of described catalyst is described 1, the dry product weight of 5-dihydroxy naphthlene
The 10-40% of amount.
As the preferred technical scheme of one, described reaction temperature controls at 150-180 DEG C.
As the preferred technical scheme of one, described reaction pressure is maintained at 2.5-5.5MPa.
After have employed technique scheme, the invention has the beneficial effects as follows:
Compared with prior art, the present invention uses ammonolysis process mainly to have following excellent to prepare 1,5-diaminonaphthalene
Point:
(1) being passed through slightly solubility gas can prevent raw material and catalyst by the dioxygen oxidation in air, the most also may be used
To increase ammonia dissolubility in the liquid phase, promote reaction；In addition slightly solubility gas can also make product appearance
Good-looking；
(2) use mother liquid recycle, the catalyst in mother solution can be made to be used again, decrease the use of catalyst
Amount, the most also reduces the discharge capacity of later stage sewage；
(3) yield of product 1,5-diaminonaphthalene is increased so that it is purity is more than 99%, and yield is 90%
Above.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment,
The present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to
Explain the present invention, be not intended to limit the present invention.
Example 1
Air in 500L autoclave is first with vacuum extraction still, then uses nitrogen breaking vacuum, successively
Addition 1,5-dihydroxy naphthlene dry product 75KG (purity is more than 99.0%), sodium sulfite 21KG, deionization
Water 350KG, opens stirring and heats up, and when temperature rises to 170 DEG C, opens ammonia valve and is slowly introducing ammonia,
Ensure that temperature, at 170 ± 5 DEG C, stops logical ammonia, starts constant temperature timing when reacting kettle inner pressure reaches 3.0MPa
Reaction, isothermal reaction 2 hours, open elevated pressure nitrogen air valve nitrogen charging in autoclave, be charged to pressure to 4.0MPa,
Continuing isothermal reaction 6 hours, then start cooling, temperature is down to room temperature, overbottom pressure in removal reactor, so
After filter, the solid 100KG deionized water drip washing solid at twice filtered out, filtrate merge make
Entering mother liquor tank for mother solution, obtain 1,5-diaminonaphthalene 68.5KG after solid vacuum drying, purity is 99.26%,
Yield is 92.6%, and product appearance is preferable.
Example 2
Air in 500L autoclave is first with vacuum extraction still, then uses nitrogen breaking vacuum, successively
Addition 1,5-dihydroxy naphthlene dry product 75KG (purity is more than 99.0%), sodium sulfite 15KG, deionization
Mother solution (mother solution ammon amount is 15.67%) 150KG in water 220KG, example 1, is then turned on stirring and heats up,
When temperature rises to 170 DEG C, open ammonia valve be slowly introducing ammonia, it is ensured that temperature at 170 ± 5 DEG C, when
Stop logical ammonia when reacting kettle inner pressure reaches 3.0MPa, start constant temperature clock reaction, isothermal reaction 2 hours,
Open elevated pressure nitrogen air valve nitrogen charging in autoclave, be charged to pressure to 4.0MPa, continuation isothermal reaction 6 hours, so
After start cooling, temperature is down to room temperature, overbottom pressure in removal reactor, is then filtered, filter out
Solid 100KG deionized water drip washing solid at twice, filtrate is incorporated as mother solution and enters mother liquor tank, solid
Obtaining 1,5-diaminonaphthalene 68.1KG after vacuum drying, purity is 99.13%, and yield is 92.0%, and produces
Product outward appearance is preferable.
Example 3
Air in 500L autoclave is first with vacuum extraction still, then uses nitrogen breaking vacuum, successively
Add 1,5-dihydroxy naphthlene dry product 75KG, sodium sulfite 15KG, deionized water 210KG, mother solution in example 2
(mother liquid ammonia content 14.88%) 160KG, opens stirring and heats up, and when temperature rises to 170 DEG C, opens ammonia valve
Door is slowly introducing ammonia, it is ensured that temperature, at 170 ± 5 DEG C, stops logical when reacting kettle inner pressure reaches 3.0MPa
Ammonia, starts constant temperature clock reaction, isothermal reaction 2 hours, opens elevated pressure nitrogen air valve nitrogen charging in autoclave,
Being charged to pressure to 4.0MPa, continue isothermal reaction 6 hours, then start cooling, temperature is down to room temperature, removal
Overbottom pressure in reactor, then filters, the twice drip washing solid of solid 100KG moisture filtered out,
Consider liquid and be incorporated as mother solution entrance mother liquor tank, after solid vacuum drying, obtain 1,5-diaminonaphthalene 68.7KG, pure
Degree is 99.02%, and yield is 92.8%.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Any amendment, equivalent and the improvement etc. made within bright spirit and principle, should be included in the present invention
Protection domain within.
Claims (8)
1. the preparation method of a 1,5-diaminonaphthalene, it is characterised in that: in deionized water solution, with
1,5-dihydroxy naphthlene is raw material, with sulphite as catalyst, is passed through slightly solubility gas in reaction system,
Control reaction temperature at 120-200 DEG C, then pass to ammonia and make reaction pressure be maintained between 1-10MPa to carry out
Reaction, reaction terminates rear decrease temperature crystalline, lays down pressure, filters out solid constituent, collects mother solution and takes its mother
The 1/3-2/3 of liquid weight is inserted in next batch reaction, is finally washed with deionized solid constituent and through overbaking
Dry obtain product 1,5-diaminonaphthalene.
The preparation method of a kind of 1,5-diaminonaphthalene the most according to claim 1, it is characterised in that: institute
State sulphite be sodium sulfite, Potassium acid sulfite, ammonium bisulfite, sodium sulfite, potassium sulfite and
One or two kinds of in ammonium sulfite.
The preparation method of a kind of 1,5-diaminonaphthalene the most according to claim 1, it is characterised in that: institute
Stating sulphite is sodium sulfite or ammonium bisulfite.
The preparation method of a kind of 1,5-diaminonaphthalene the most according to claim 1, it is characterised in that: institute
Stating slightly solubility gas is nitrogen, hydrogen or argon.
The preparation method of a kind of 1,5-diaminonaphthalene the most according to claim 1, it is characterised in that: institute
Stating 1,5-dihydroxy naphthlene mass concentration in reaction system is 10-30%.
The preparation method of a kind of 1,5-diaminonaphthalene the most according to claim 1, it is characterised in that: institute
State the 10-40% of the dry product weight that amount is described 1,5-dihydroxy naphthlene of catalyst.
The preparation method of a kind of 1,5-diaminonaphthalene the most according to claim 1, it is characterised in that: institute
State reaction temperature to control at 150-180 DEG C.
The preparation method of a kind of 1,5-diaminonaphthalene the most according to claim 1, it is characterised in that: institute
State reaction pressure and be maintained at 2.5-5.5MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610396871.9A CN105884622A (en) | 2016-06-03 | 2016-06-03 | Method for preparing 1,5-diaminonaphthlene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610396871.9A CN105884622A (en) | 2016-06-03 | 2016-06-03 | Method for preparing 1,5-diaminonaphthlene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105884622A true CN105884622A (en) | 2016-08-24 |
Family
ID=56710722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610396871.9A Pending CN105884622A (en) | 2016-06-03 | 2016-06-03 | Method for preparing 1,5-diaminonaphthlene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105884622A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113416141A (en) * | 2021-07-14 | 2021-09-21 | 沈阳感光化工研究院有限公司 | Preparation method of 5-amino-1-naphthol hydrochloride |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973758A (en) * | 1988-12-02 | 1990-11-27 | Bayer Aktiengesellschaft | Process for the preparation of 1,5-dihydroxynaphthalene and 1,5-diaminonaphthalene |
| US5113025A (en) * | 1989-10-02 | 1992-05-12 | Ethyl Corporation | Selective reducing agents |
| CN102603537A (en) * | 2012-02-21 | 2012-07-25 | 南通市东昌化工有限公司 | Production method of 2,6-dimethylaniline |
| CN103209953A (en) * | 2010-09-17 | 2013-07-17 | 巴斯夫欧洲公司 | Method for producing aromatic amines |
-
2016
- 2016-06-03 CN CN201610396871.9A patent/CN105884622A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973758A (en) * | 1988-12-02 | 1990-11-27 | Bayer Aktiengesellschaft | Process for the preparation of 1,5-dihydroxynaphthalene and 1,5-diaminonaphthalene |
| US5113025A (en) * | 1989-10-02 | 1992-05-12 | Ethyl Corporation | Selective reducing agents |
| CN103209953A (en) * | 2010-09-17 | 2013-07-17 | 巴斯夫欧洲公司 | Method for producing aromatic amines |
| CN102603537A (en) * | 2012-02-21 | 2012-07-25 | 南通市东昌化工有限公司 | Production method of 2,6-dimethylaniline |
Non-Patent Citations (3)
| Title |
|---|
| 张弥问: "2,3-二氨基萘的合成与应用", 《天津化工》 * |
| 高健等: "《有机胺及其配合物》", 31 January 2010 * |
| 高素华等: "1,5-二氨基萘合成", 《天津理工大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113416141A (en) * | 2021-07-14 | 2021-09-21 | 沈阳感光化工研究院有限公司 | Preparation method of 5-amino-1-naphthol hydrochloride |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105968032B (en) | The synthetic method of Metformin hydrochloride | |
| CN101891683B (en) | Aminopyrine production method | |
| CN105541648B (en) | A kind of supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma | |
| CN107337618B (en) | Production method for simultaneously improving purity and yield of metformin hydrochloride | |
| CN104774165A (en) | Green and industrial preparation method of rubber peptizer DBD | |
| CN105130854A (en) | Improved H acid production process | |
| CN111217764B (en) | Method for preparing 6-nitro-1, 2, 4-acid oxygen | |
| CN105294509B (en) | The System and method for of one-step synthesis method dicyandiamide | |
| CN104447392B (en) | A kind of preparation method of azoic coupling component AS | |
| CN105884622A (en) | Method for preparing 1,5-diaminonaphthlene | |
| CN103420851B (en) | Method for preparing 1,5-diaminonaphthalene through naphthalene in one step and application of catalysts | |
| CN100497305C (en) | Method for preparing ethylsulfonyl acetonitrile | |
| CN109053610A (en) | A kind of good process for cleanly preparing of environment of high-purity cyanuric acid | |
| CN105217693A (en) | A kind of method preparing iron oxide yellow and ammonium chloride | |
| CN102992998A (en) | Preparation method of ferrous gluconate | |
| CN110078672A (en) | The chloro- 5-FU preparation method of 2,4- bis- of high-purity | |
| CN110256348A (en) | A kind of synthetic method of vulcanizer DTDC | |
| CN205328904U (en) | System for synthetic dicyandiamide of one -step method | |
| CN102206175B (en) | Method for preparing DSD (4,4'-Diamino 2,2'-Stilbene Disulphonic) acid by hydrogenating and reducing disodium dinitrosalicylate (DNS) at high temperature | |
| CN111362839B (en) | Preparation method of O-methyl-N-nitroisourea | |
| CN102977045B (en) | 4-(5-amino-6-hydroxybenzoxazole-2-yl)ammonium benzoate as well as preparation method and application thereof | |
| CN106432227B (en) | A kind of method for preparing pirenzepine hydrochloride key intermediate | |
| CN205346849U (en) | System for utilize low boiling organic solvent direct heat transfer manufacture order cyandiamide | |
| CN105562070A (en) | Modified MoS2-Me/HZSM-5 catalyst preparation method | |
| CN104945223B (en) | A kind of method that load molecular sieve catalysis toluene synthesizes ortho-chlorotolu'ene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160824 |
|
| RJ01 | Rejection of invention patent application after publication |