CN108203386A - A kind of method for preparing 1,3- cyclohexyldimethylamines - Google Patents
A kind of method for preparing 1,3- cyclohexyldimethylamines Download PDFInfo
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- CN108203386A CN108203386A CN201611188308.9A CN201611188308A CN108203386A CN 108203386 A CN108203386 A CN 108203386A CN 201611188308 A CN201611188308 A CN 201611188308A CN 108203386 A CN108203386 A CN 108203386A
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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
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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Abstract
1 is prepared the present invention relates to a kind of, the method of 3 cyclohexyldimethylamines, two-stage hydrogenation is carried out under same solvent, first segment adds hydrogen using Raney's nickel as catalyst, methanol, methylamine or 1, one or more of 4 dioxane are solvent, organic amine, liquefied ammonia, water or sodium hydroxide are auxiliary agent, it it is 40 80 DEG C in reaction temperature, reaction pressure is under 5 8MPa, isophthalodinitrile and hydrogen are reacted, reaction time is 1 5h, obtain m-xylene diamine reaction solution, second segment adds hydrogen to be supported with the activated carbon of ruthenium as catalyst, it it is 80 130 DEG C in reaction temperature, reaction pressure is under 5 8MPa, m-xylene diamine reaction solution and hydrogen continue to react, reaction time is 1 6h, it is prepared 1, 3 cyclohexyldimethylamines.The total recovery of the present invention is up to 90%.The technological operation is simple, high income, easy rectifying, can be directly improved in existing MXDA production technologies, be easy to industrialize.
Description
Technical field
The present invention relates to a kind of preparation methods of pesticide intermediate, and 1,3- cyclohexyldimethylamines are prepared more particularly, to a kind of
Method.
Background technology
1,3-BAC, entitled 1, the 3- cyclohexyldimethylamines of Chinese or 1,3- diamines hexahydrotoluene, English entitled 1,3-
Bis (aminomethyl) Cyclohexane or 1,3-Cyclohexanedimethanamine (CA), molecular formula C8
H18 N2,1,3-BAC is colourless, micro- transparency liquid for having ammonia taste, and 220 DEG C of boiling point, solidification point is at -70 DEG C hereinafter, 113 DEG C of flash-point
(Cleveland opens cup type), proportion (20 DEG C) 0.942, viscosity 9.06 (cp, 20 DEG C), vapour pressure 14mmHg (120 DEG C).It is solvable
Yu Shui, alcohol, ether, n-hexane, hexamethylene, benzene equal solvent.It is mainly used as the curing agent of epoxy resin, urethane intermediates and anti-corrosion
Antirust agent.
Nowadays it is external mainly to there are the producers such as Mitsubishi's gas, BASF to produce 1,3-BAC, and the domestic very few nothing of manufacturer
Several, the self-produced MXDA of my company has good economic advantages for 1,3-BAC of production.Particularly when MXDA is put into toxic chemical
After product, 1,3-BAC can steeply rise as the demand of substitute.According to raw material is used to classify, 1,3-BAC preparation method
It is divided into two kinds, respectively IPN methods and MXDA methods.Both methods will be introduced respectively in terms of document below.
IPN methods prepare 1,3-BAC.Mitsubishi's gas applies for a patent US5371293 within 1994, which uses 5% support type
Ruthenium charcoal or ruthenium aluminium oxide are catalyst, under reaction system existing for dioxane and liquefied ammonia, 100atm reaction pressure and
Hydrogenation reaction is carried out under 100 DEG C or so of reaction temperature, 1,3-BAC molar yield is about 88%.Patent US4070399 with
5% support type Ru-Pd/C is catalyst, with lower aliphatic alcohols, dioxane, low-grade aliphatic amine etc. for solvent, in reaction system
With the presence of ammonia, hydrogenation reaction, the quality of Isosorbide-5-Nitrae-BAC are carried out under the pressure of about 100atm and to TPN at a temperature of 100-150 DEG C
Yield is up to 98%.For patent US3998881 using 5% support type rhodium aluminium oxide as catalyst, solvent uses dioxane, tetrahydrochysene
Furans, chloroform etc., reaction pressure about 100atm, reaction temperature are 100-150 DEG C, and the total recovery after rectifying is 71%.Above-mentioned IPN
Method, which prepares 1,3-BAC, has the shortcomings that selectivity is poor.
MXDA methods prepare 1,3-BAC.Patent EP0703213 is urged using supported ruthenium, nickel, rhodium (or their compound)
Agent reacts the solvent that uses for methylamine, dimethylamine, ethylenediamine, BAC, and methanol etc., the volume ratio of MXDA and solvent is 1: 3-1:
20, reaction pressure 50-150atm, reaction temperature are 80-130 DEG C, and mass yield is up to 94%.Patent US4181680 is used
Load ruthenium catalyst, the percentage that the quality of metal Ru accounts for catalyst gross mass (including catalyst and carrier) are 0.1-
10%, the solvent that uses is reacted for distilled water, and the volume ratio of MXDA and solvent is 1: 1-1: 10, reaction pressure 100-
150atm, reaction temperature are 75-130 DEG C, and molar yield is up to 88% or so.Since MXDA is to be added hydrogen by IPN and obtained, with
MXDA is excessively high for raw material preparation 1,3-BAC costs.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of technological operation is simple,
High income, the preparation 1 of easy rectifying, the method for 3- cyclohexyldimethylamines.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of method for preparing 1,3- cyclohexyldimethylamines, which is characterized in that this method carries out two sections under same solvent
Adding hydrogen, first segment adds hydrogen using Raney's nickel as catalyst, methanol, and one or more of methylamine or Isosorbide-5-Nitrae-dioxane are solvent,
Organic amine, liquefied ammonia, water or sodium hydroxide are auxiliary agent, are 40-80 DEG C in reaction temperature, and reaction pressure is isophthalic two under 5-8MPa
Formonitrile HCN and hydrogen are reacted, reaction time 1-5h, obtain m-xylene diamine reaction solution, and second segment adds hydrogen to be supported with ruthenium
Activated carbon is catalyst, is 80-130 DEG C in reaction temperature, and reaction pressure is m-xylene diamine reaction solution and hydrogen under 5-8MPa
Continue to react, 1,3- cyclohexyldimethylamines are prepared in reaction time 1-6h.
Preferred Isosorbide-5-Nitrae-the dioxane of the solvent；The auxiliary agent preferred concentration is the sodium hydroxide of 50wt%.
The solvent accounts for the 50-90wt% of first segment hydrogenation reaction object total amount, and it is total that auxiliary agent accounts for first segment hydrogenation reaction object
The 0.6-6wt% of amount, Raney's nickel account for the 2.5-6wt% of first segment hydrogenation reaction object total amount.
The solvent accounts for the 60-80wt% of first segment hydrogenation reaction object total amount, and it is total that auxiliary agent accounts for first segment hydrogenation reaction object
The 1-4wt% of amount, Raney's nickel account for the 3-6wt% of first segment hydrogenation reaction object total amount.
The first segment adds preferred 50-70 DEG C of the reaction temperature of hydrogen, the preferred 5-7MPa of reaction pressure, and the reaction time is preferred
1-3h。
5wt% containing ruthenium in the catalyst of the activated carbon for being supported with ruthenium, the addition of catalyst account for second segment and add hydrogen
The 1-5wt% of reaction-ure mixture.
The addition of the catalyst accounts for the 2-4wt% of second segment hydrogenation reaction object total amount.
The second segment adds preferred 90-110 DEG C of the reaction temperature of hydrogen, the preferred 5-7MPa of reaction pressure, and the reaction time is excellent
Select 1-4h.
Compared with prior art, the present invention has the characteristics of technological operation is simple, high income, easy rectifying, total after rectifying
Yield can directly be improved in existing MXDA production technologies up to 90%, be easy to industrialize.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1
Put into 60g m-xylene diamines successively in autoclave, 120g dioxane, 5.62g50% sodium hydroxide solutions and
8g Raney's nickel catalysts, close kettle, after H2 displacements three times, are passed through H2 to 5MPa, open and be heated with stirring to 60 DEG C, it is reinflated extremely
6MPa waits reactions to inhale hydrogen, when pressure is down to 5MPa, is inflated to 6MPa, so operates until no longer hydrogen is inhaled, reacts at this time repeatedly
About 80 minutes.It is cooled to room temperature, is vented hydrogen, opens kettle, pour out supernatant liquor (MXDA reaction solutions), lower catalyst agent is applied mechanically.
It puts into a certain amount of above-mentioned MXDA reaction solutions and the ruthenium Pd/carbon catalyst of 4g5% successively in autoclave, closes kettle, use
After H2 displacements three times, H2 to 6MPa is passed through, opens and is heated with stirring to 90 DEG C, reinflated to 7MPa, hydrogen, pressure are inhaled in reaction
When being down to 6MPa, 7MPa is inflated to, so operates until no longer hydrogen is inhaled, reacts at this time about 140 minutes repeatedly.It is cooled to room
Kettle is opened in temperature, emptying, is discharged, and is filtered, and filter cake (catalyst) is applied mechanically, and total recovery of the filtrate after precipitation rectifying is 88.3%.
Embodiment 2
Put into 37.5g m-xylene diamines successively in autoclave, 150g dioxane, 5.7g50% sodium hydroxide solutions and
8g Raney's nickel catalysts, close kettle, after H2 displacements three times, are passed through H2 to 5MPa, open and be heated with stirring to 70 DEG C, it is reinflated extremely
6MPa, reaction inhale hydrogen, when pressure is down to 5MPa, are inflated to 6MPa, so operate until no longer hydrogen is inhaled, are reacted at this time about repeatedly
60 minutes.It is cooled to room temperature, kettle is opened in emptying, pours out supernatant liquor (MXDA reaction solutions), lower catalyst agent is applied mechanically.
It puts into a certain amount of above-mentioned MXDA reaction solutions and the ruthenium Pd/carbon catalyst of 4g5% successively in autoclave, closes kettle, use H2
After displacement three times, H2 to 6MPa is passed through, opens and is heated with stirring to 100 DEG C, it is reinflated to 7MPa, reactions is waited to inhale hydrogen, pressure is down to
During 6MPa, 7MPa is inflated to, is so operated repeatedly until no longer hydrogen is inhaled, is reacted about 120 minutes at this time and be cooled to room temperature, put
It is spaced apart kettle, discharges, filter, filter cake (catalyst) is applied mechanically, and total recovery of the filtrate after precipitation rectifying is 90%.
Embodiment 3
Put into 37.5g m-xylene diamines successively in autoclave, 150g dioxane, 5.7g50% sodium hydroxide solutions and
8g Raney's nickel catalysts, close kettle, after H2 displacements three times, are passed through H2 to 5MPa, open and be heated with stirring to 70 DEG C, it is reinflated extremely
6MPa waits reactions to inhale hydrogen, when pressure is down to 5MPa, is inflated to 6MPa, so operates until no longer hydrogen is inhaled, reacts at this time repeatedly
About 100 minutes.It is cooled to room temperature, kettle is opened in emptying, pours out supernatant liquor (MXDA reaction solutions), lower catalyst agent is applied mechanically.In height
A certain amount of above-mentioned MXDA reaction solutions and the ruthenium Pd/carbon catalyst of 5g5% are put into successively in pressure kettle, close kettle, after H2 displacements three times,
H2 to 6MPa is passed through, opens and is heated with stirring to 100 DEG C, it is reinflated to 7MPa, reactions is waited to inhale hydrogen, when pressure is down to 6MPa, are inflated to
7MPa is so operated until no longer hydrogen is inhaled, is reacted about 100 minutes at this time and be cooled to room temperature repeatedly, and kettle is opened in emptying, is discharged, and is taken out
Filter, filter cake (catalyst) are applied mechanically, and total recovery of the filtrate after precipitation rectifying is 90%.
Claims (2)
- A kind of 1. method for preparing 1,3- cyclohexyldimethylamines, which is characterized in that this method carries out two sections under same solvent and adds Hydrogen, first segment add hydrogen using Raney's nickel as catalyst, methanol, and one or more of methylamine or Isosorbide-5-Nitrae-dioxane are solvent, are had Machine amine, liquefied ammonia, water or sodium hydroxide are auxiliary agent, are 40-80 DEG C in reaction temperature, and reaction pressure is isophthalic diformazan under 5-8MPa Nitrile and hydrogen are reacted, reaction time 1-5h, obtain m-xylene diamine reaction solution, and second segment adds hydrogen to be supported with the work of ruthenium Property charcoal be catalyst, be 80-130 DEG C in reaction temperature, reaction pressure is under 5-8MPa, m-xylene diamine reaction solution and hydrogen after Continuous to be reacted, 1,3- cyclohexyldimethylamines are prepared in reaction time 1-6h.
- A kind of 2. method for preparing 1,3- cyclohexyldimethylamines according to claim 1, which is characterized in that the solvent It is preferred that Isosorbide-5-Nitrae-dioxane；The auxiliary agent preferred concentration is the sodium hydroxide of 50wt%.
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| CN201611188308.9A CN108203386A (en) | 2016-12-20 | 2016-12-20 | A kind of method for preparing 1,3- cyclohexyldimethylamines |
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| CN201611188308.9A CN108203386A (en) | 2016-12-20 | 2016-12-20 | A kind of method for preparing 1,3- cyclohexyldimethylamines |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100014A (en) * | 2019-11-18 | 2020-05-05 | 名畔科技(镇江)有限公司 | Preparation method of 1, 3-cyclohexyldimethylamine |
| CN112300006A (en) * | 2020-11-25 | 2021-02-02 | 淄博正大聚氨酯有限公司 | Method for preparing 1, 4-cyclohexyl dimethylamine by using hydroamination method |
| CN116589363A (en) * | 2023-05-17 | 2023-08-15 | 河南省君恒实业集团生物科技有限公司 | Preparation method of catalyst for preparing 1, 3-cyclohexanediamine by hydrogenating m-xylylenediamine in micro-packed bed |
-
2016
- 2016-12-20 CN CN201611188308.9A patent/CN108203386A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100014A (en) * | 2019-11-18 | 2020-05-05 | 名畔科技(镇江)有限公司 | Preparation method of 1, 3-cyclohexyldimethylamine |
| CN111100014B (en) * | 2019-11-18 | 2022-05-10 | 名畔科技(镇江)有限公司 | Preparation method of 1, 3-cyclohexyldimethylamine |
| CN112300006A (en) * | 2020-11-25 | 2021-02-02 | 淄博正大聚氨酯有限公司 | Method for preparing 1, 4-cyclohexyl dimethylamine by using hydroamination method |
| CN116589363A (en) * | 2023-05-17 | 2023-08-15 | 河南省君恒实业集团生物科技有限公司 | Preparation method of catalyst for preparing 1, 3-cyclohexanediamine by hydrogenating m-xylylenediamine in micro-packed bed |
| CN116589363B (en) * | 2023-05-17 | 2024-05-03 | 河南省君恒实业集团生物科技有限公司 | Preparation method of catalyst for preparing 1, 3-cyclohexanediamine by hydrogenating m-xylylenediamine in micro-packed bed |
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Application publication date: 20180626 |