CN102180799A - Method for preparing p-xylylenediamine - Google Patents
Method for preparing p-xylylenediamine Download PDFInfo
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- CN102180799A CN102180799A CN2011100701760A CN201110070176A CN102180799A CN 102180799 A CN102180799 A CN 102180799A CN 2011100701760 A CN2011100701760 A CN 2011100701760A CN 201110070176 A CN201110070176 A CN 201110070176A CN 102180799 A CN102180799 A CN 102180799A
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- dimethylamine
- phthalonitrile
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- loop reactor
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Abstract
The invention discloses a method for preparing p-xylylenediamine, which sequentially comprises the following steps of: refining raw materials, performing hydrogenation reaction, purifying a product and the like. The applicable reaction pressure is low, the temperature is low, and the high yield of the p-xylylenediamine is ensured simultaneously.
Description
Technical field
The present invention relates to a kind of p dimethylamine's preparation method.
Background technology
PXDA, Chinese name p dimethylamine, English name 1,4-Benzenedimethanamine or 1,4-bis-aminomethylbenzen, molecular formula C
8H
12N
2, molecular weight 136.22, CA registration number 539-48-0, structural formula:
It is a kind of white or faint yellow solid, and the almond flavor is arranged, and reveals air for a long time and is yellow, water-soluble and organic solvent.Be mainly used in and make heat-resisting, nontoxic, underwater construction, the quick-setting high-performance epoxy resin solidifying agent of heating, be the raw material of urethane resin, complex functionality epoxy resin, application also arranged at aspects such as rubber item, photo-plastics, agricultural chemicals, coating, nylon products, fibre finish agent, rust-preventive agent, sequestrant, lubricant, paper conversion.
From the synthetic m-xylene diamine of Isophthalodinitrile hydrogenation the lot of documents report has been arranged, but less from the synthetic p dimethylamine's of para-Phthalonitrile report, mainly be that the continuous process of Mitsubishi gas and German BASF is produced the benzene dimethylamine series products.Introductions such as the patent CN1397543 of Mitsubishi's gas, CN1526697, CN1972896 be to adopt loading type nickel-based catalyst, trickle bed technology continuous hydrogenation prepares the benzene dimethylamine series products, the molar yield of benzene dimethylamine is 89～91%, reaction pressure is higher, greater than 10 MPas, about 90 degrees centigrade of temperature.
The patent CN101128416 of BASF has introduced the intermittently technology of hydrogenation preparing benzene dimethylamine of a kind of autoclave method, and reaction pressure is generally greater than 8 MPas, and temperature does not have concrete yield and catalyzer to apply mechanically the data of number of times greater than 80 degrees centigrade.The patent CN1849291 of BASF, CN101273006 etc. have introduced the employing loading type nickel-based catalyst, and the trickle bed continuous hydrogenation prepares the technology of benzene dimethylamine series products, and its reaction pressure is higher, greater than 10 MPas, and molar yield 89～91%.
Summary of the invention
The object of the present invention is to provide a kind of suitable reaction pressure low, temperature is low, guarantees p dimethylamine's the preparation method of p dimethylamine's high yield simultaneously.
Technical solution of the present invention is:
A kind of p dimethylamine's preparation method is characterized in that: comprise the following steps: successively
(1) feed purification: with an organic solvent with water the raw material para-Phthalonitrile is made with extra care;
(2) hydrogenation reaction: the para-Phthalonitrile after refining carries out the high-pressure hydrogenation reaction in loop reactor;
(3) purification of products: the solution after the hydrogenation reaction obtains the product p dimethylamine through precipitation and rectification and purification.
Described organic solvent is to be selected from least a in toluene, dimethylbenzene, trimethylbenzene, the cyanobenzene.
The process for purification of step (1) is: raw material para-Phthalonitrile branch vibration layer after the heating for dissolving in the mixed solvent that organic solvent and water are formed, oil reservoir obtains the purified para-Phthalonitrile behind the crystallisation by cooling again.
The described hydrogenation reaction of step (2), solution with the para-Phthalonitrile after refining carries out under the effect of nickel catalyzator, the working pressure of loop reactor is 4～5 MPas, temperature is 50～60 degrees centigrade, reaction times is 30～60 minutes, unreacted hydrogen is flowed out by loop reactor top, and process hydrogen gas buffer and hydrogen gas compressor enter loop reactor again and react.
Step (3) precipitation and rectifying are carried out under nitrogen protection.
The present invention removes in the raw material the virose impurity of nickel catalyzator by feed purification, not only can prolong catalyst life like this, the more important thing is and has improved single batch reaction yield; By carry out hydrogenation reaction in loop reactor, hydrogen recycle can both be protected catalyzer and reactant by saturated hydrogen, can reduce reaction pressure and temperature of reaction like this; Because the p dimethylamine is more perishable under ingress of air and pyritous situation,, so just improved product yield greatly so in the process of precipitation and rectifying, use nitrogen protection.
Use preparation method of the present invention to produce the p dimethylamine; temperature of reaction only needs 50～60 degrees centigrade; reaction pressure only needs 4～5 MPas; the reaction molar yield is greater than 97%; again by precipitation under the nitrogen protection and rectifying; obtain content and be the purified product more than 99.5%, its reaction and purified total recovery are greater than 94%.
The invention will be further described below in conjunction with drawings and Examples.
Fig. 1 is loop reactor of the present invention and relevant production equipment synoptic diagram thereof.
1 is high pressure hydrogen storage tank among the figure, and 2 is the hydrogen valve, and 3 is hydrogen gas buffer, and 4 is hydrogen gas compressor, and 5 is loop reactor, and 6 is guide shell, and 7 are the emptying valve.Arrow is depicted as the Flow of Goods and Materials direction.
Embodiment
Embodiment 1
The para-Phthalonitrile of double centner is joined in the soft mixed solvent of 1500 kilograms toluene and 200 kilograms, stir, heat temperature raising to 65 degree centigrade, insulation was left standstill 15 minutes after half an hour, divide the sub-cloud water layer, the upper toluene layer is cooled to 10 degrees centigrade of after-filtration and obtains 95 kilograms of purified para-Phthalonitriles, and filtrate can continue to apply mechanically.
The nickel catalyzator that in loop reactor, drops into 95 kilograms refining para-Phthalonitrile, 400 kilograms toluene, 1 kilogram sodium hydroxide, 1 kilogram of soft water and 15 kilograms reaction 30 minutes under the condition of 5 MPas and 50 degrees centigrade.By analysis, reaction molar yield 97.5%.
Reaction solution through normal pressure precipitation and rectification under vacuum, obtains 95.86 kilograms 99.5% refining p dimethylamine under nitrogen protection, reaction and purified total recovery are 94.5%.
Embodiment 2
The para-Phthalonitrile of double centner is joined in the soft mixed solvent of 1500 kilograms p-Xylol and 200 kilograms, stir, heat temperature raising to 65 degree centigrade, insulation was left standstill 15 minutes after half an hour, divide the sub-cloud water layer, upper strata p-Xylol layer is cooled to 10 degrees centigrade of after-filtration and obtains 95 kilograms of purified para-Phthalonitriles, and filtrate can continue to apply mechanically.
The nickel catalyzator that in loop reactor, drops into 95 kilograms refining para-Phthalonitrile, 400 kilograms p-Xylol, 1 kilogram sodium hydroxide, 1 kilogram of soft water and 15 kilograms reaction 60 minutes under the condition of 4 MPas and 60 degrees centigrade.By analysis, reaction molar yield 98.0%.
Reaction solution through normal pressure precipitation and rectification under vacuum, obtains 95.50 kilograms 99.5% refining p dimethylamine under nitrogen protection, reaction and purified total recovery are 94.1%.
Embodiment 3
The para-Phthalonitrile of double centner is joined in the soft mixed solvent of 1500 kilograms sym-trimethylbenzene and 200 kilograms, stir, heat temperature raising to 65 degree centigrade, insulation was left standstill 15 minutes after half an hour, divide the sub-cloud water layer, the upper strata is cooled to 10 degrees centigrade of after-filtration to the sym-trimethylbenzene layer and obtains 95 kilograms of purified para-Phthalonitriles, and filtrate can continue to apply mechanically.
The nickel catalyzator that in loop reactor, drops into 95 kilograms refining para-Phthalonitrile, 400 kilograms sym-trimethylbenzene, 1 kilogram sodium hydroxide, 1 kilogram of soft water and 15 kilograms reaction 45 minutes under the condition of 4.5 MPas and 55 degrees centigrade.By analysis, reaction molar yield 98.2%.
Reaction solution through normal pressure precipitation and rectification under vacuum, obtains 96.10 kilograms 99.5% refining p dimethylamine under nitrogen protection, reaction and purified total recovery are 94.69%.
Claims (5)
1. a p dimethylamine preparation method is characterized in that: comprise the following steps: successively
(1) feed purification: with an organic solvent with water the raw material para-Phthalonitrile is made with extra care;
(2) hydrogenation reaction: the para-Phthalonitrile after refining carries out the high-pressure hydrogenation reaction in loop reactor;
(3) purification of products: the solution after the hydrogenation reaction obtains the product p dimethylamine through precipitation and rectification and purification.
2. the described p dimethylamine's of claim 1 according to claim 1 preparation method is characterized in that: described organic solvent is to be selected from least a in toluene, dimethylbenzene, trimethylbenzene, the cyanobenzene.
3. the described p dimethylamine's of claim 1 according to claim 1 preparation method, it is characterized in that: the process for purification of step (1) is: raw material para-Phthalonitrile branch vibration layer after the heating for dissolving in the mixed solvent that organic solvent and water are formed, oil reservoir obtains the purified para-Phthalonitrile behind the crystallisation by cooling again.
4. according to claim 1, the described p dimethylamine's of 2 or 3 described claims 1 preparation method, it is characterized in that: the described hydrogenation reaction of step (2), solution with the para-Phthalonitrile after refining carries out under the effect of nickel catalyzator, the working pressure of loop reactor is 4 ~ 5 MPas, temperature is 50 ~ 60 degrees centigrade, reaction times is 30 ~ 60 minutes, unreacted hydrogen is flowed out by loop reactor top, and process hydrogen gas buffer and hydrogen gas compressor enter loop reactor again and react.
5. according to claim 1, the described p dimethylamine's of 2 or 3 described claims 1 preparation method, it is characterized in that: step (3) precipitation and rectifying, under nitrogen protection, carry out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100701760A CN102180799A (en) | 2011-03-23 | 2011-03-23 | Method for preparing p-xylylenediamine |
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| CN2011100701760A CN102180799A (en) | 2011-03-23 | 2011-03-23 | Method for preparing p-xylylenediamine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180130154A (en) * | 2017-05-29 | 2018-12-07 | 에스케이씨 주식회사 | Isocyanate composition for optical lenses and preparation method thereof |
Citations (6)
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|---|---|---|---|---|
| US6114277A (en) * | 1997-02-04 | 2000-09-05 | Showa Denko K.K. | Process for preparing cyano group-containing aromatic methylamines |
| US20050277790A1 (en) * | 2003-02-20 | 2005-12-15 | Yoshinori Kanamori | High-selective production method of di(aminomethyl)-substituted aromatic compound |
| CN101107215A (en) * | 2005-01-24 | 2008-01-16 | 巴斯夫股份有限公司 | Method for producing a xylylene diamine |
| US20080154061A1 (en) * | 2005-02-24 | 2008-06-26 | Basf Aktiengesellschaft | Method For Producing a Xylylenediamine |
| CN101768083A (en) * | 2008-12-26 | 2010-07-07 | 三菱瓦斯化学株式会社 | Production method of xylylenediamine |
| CN101955433A (en) * | 2010-04-20 | 2011-01-26 | 南通泰禾化工有限公司 | Preparation method of meta-xylylene diamine |
-
2011
- 2011-03-23 CN CN2011100701760A patent/CN102180799A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6114277A (en) * | 1997-02-04 | 2000-09-05 | Showa Denko K.K. | Process for preparing cyano group-containing aromatic methylamines |
| US20050277790A1 (en) * | 2003-02-20 | 2005-12-15 | Yoshinori Kanamori | High-selective production method of di(aminomethyl)-substituted aromatic compound |
| CN101107215A (en) * | 2005-01-24 | 2008-01-16 | 巴斯夫股份有限公司 | Method for producing a xylylene diamine |
| US20080154061A1 (en) * | 2005-02-24 | 2008-06-26 | Basf Aktiengesellschaft | Method For Producing a Xylylenediamine |
| CN101768083A (en) * | 2008-12-26 | 2010-07-07 | 三菱瓦斯化学株式会社 | Production method of xylylenediamine |
| CN101955433A (en) * | 2010-04-20 | 2011-01-26 | 南通泰禾化工有限公司 | Preparation method of meta-xylylene diamine |
Non-Patent Citations (3)
| Title |
|---|
| STEPHAN ENTHALER 等: "A General and Environmentally Benign Catalytic Reduction of Nitriles to Primary Amines", 《CHEMISTRY-A EUROPEAN JOURNAL》, vol. 14, no. 31, 31 December 2008 (2008-12-31), pages 9491 - 9494 * |
| STEPHAN ENTHALER 等: "A Practical and Benign Synthesis of Primary Amines through Ruthenium-Catalyzed Reduction of Nitriles", 《CHEMSUSCHEM》, vol. 1, no. 12, 31 December 2008 (2008-12-31), pages 1006 - 1010 * |
| 钱宗川 等: "间苯二甲腈粗品的精制", 《江苏农药》, no. 1, 15 March 1997 (1997-03-15), pages 13 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180130154A (en) * | 2017-05-29 | 2018-12-07 | 에스케이씨 주식회사 | Isocyanate composition for optical lenses and preparation method thereof |
| KR101964924B1 (en) * | 2017-05-29 | 2019-04-03 | 에스케이씨 주식회사 | Isocyanate composition for optical lenses and preparation method thereof |
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Application publication date: 20110914 |