CN106810451A - 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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- CN106810451A CN106810451A CN201510860814.7A CN201510860814A CN106810451A CN 106810451 A CN106810451 A CN 106810451A CN 201510860814 A CN201510860814 A CN 201510860814A CN 106810451 A CN106810451 A CN 106810451A
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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
Abstract
1 is prepared the present invention relates to one kind, the method of 3- cyclohexyldimethylamines, two-stage hydrogenation is carried out under same solvent, first paragraph is hydrogenated with Raney's nickel as catalyst, methyl alcohol, methylamine or 1, one or more in 4- dioxane are solvent, organic amine, liquefied ammonia, water or NaOH 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, it is catalyst that second segment is hydrogenated with to be supported with the activated carbon of ruthenium, it it is 80-130 DEG C in reaction temperature, reaction pressure is under 5-8MPa, m-xylene diamine reaction solution and hydrogen proceed reaction, reaction time is 1-6h, prepare 1, 3- cyclohexyldimethylamines.Total recovery of the invention is up to 90%.The technological operation is simple, and high income, easy rectifying directly can be improved, it is easy to industrialize in existing MXDA production technologies.
Description
Technical field
The present invention relates to a kind of preparation method of pesticide intermediate, the method that 1,3- cyclohexyldimethylamines are prepared more particularly, to one kind.
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 is C8H18N2, and 1,3-BAC is colourless, micro- transparency liquid for having an ammonia taste, 220 DEG C of boiling point, freezing point
Below -70 DEG C, 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 water-soluble, alcohol, ether, n-hexane, hexamethylene, benzene equal solvent.It is mainly used as epoxy resin
Curing agent, urethane intermediates and corrosion prevention rust preventer.
Nowadays mainly there are the manufacturer productions such as Mitsubishi's gas, BASF 1,3-BAC in foreign countries, and the manufacturer of the country is very few, my company
Self-produced MXDA, has good economic advantages for 1,3-BAC of production.Particularly after MXDA is put into toxic chemical, 1,3-BAC
The demand of product can steeply rise as an alternative.Classify according to using raw material, 1,3-BAC preparation method is divided into two kinds, respectively IPN methods
With MXDA methods.Both approaches below will be respectively introduced in terms of document.
IPN methods prepare 1,3-BAC.Mitsubishi's gas applies for a patent US5371293 within 1994, and the patent is aoxidized using 5% supported ruthenium charcoal or ruthenium
Aluminium is catalyst, under the reaction system that dioxane and liquefied ammonia are present, under the reaction pressure of 100atm and 100 DEG C or so of reaction temperature
Hydrogenation reaction is carried out, 1,3-BAC molar yield is about 88%.Patent US4070399 with 5% support type Ru-Pd/C be catalyst, with
Lower aliphatic alcohols, dioxane, low-grade aliphatic amine etc. be solvent, with the presence of ammonia in reaction system, under the pressure of about 100atm and
Hydrogenation reaction is carried out at a temperature of 100-150 DEG C to TPN, the mass yield of Isosorbide-5-Nitrae-BAC is up to 98%.Patent US3998881 is with 5%
Support type rhodium aluminum oxide is catalyst, and solvent uses dioxane, tetrahydrofuran, chloroform etc., reaction pressure about 100atm, and reaction temperature is
100-150 DEG C, the total recovery after rectifying is 71%.Above-mentioned IPN methods prepare 1,3-BAC has the shortcomings that selectivity is poor.
MXDA methods prepare 1,3-BAC.Patent EP0703213 uses supported ruthenium, nickel, rhodium (or their compound) catalyst,
The solvent that uses of reaction is methylamine, dimethylamine, ethylenediamine, BAC, methyl alcohol etc., and MXDA is 1: 3-1: 20 with the volume ratio of solvent,
Reaction pressure is 50-150atm, and reaction temperature is 80-130 DEG C, and mass yield is up to 94%.Patent US4181680 is urged using supported ruthenium
Agent, the percentage that the quality of metal Ru accounts for catalyst gross mass (including catalyst and carrier) is 0.1-10%, the solvent that reaction is used
It is distilled water, MXDA is 1: 1-1: 10 with the volume ratio of solvent, reaction pressure is 100-150atm, reaction temperature is 75-130 DEG C,
Molar yield is up to 88% or so.Because MXDA is obtained by IPN hydrogenation, therefore it is that raw material prepares 1,3-BAC cost mistakes with MXDA
It is high.
The content of the invention
The purpose of the present invention is exactly that a kind of technological operation is provided for the defect for overcoming above-mentioned prior art to exist simply, high income, easy rectifying
The method for preparing 1,3- cyclohexyldimethylamines.
The purpose of the present invention can be achieved through the following technical solutions：
The method that one kind prepares 1,3- cyclohexyldimethylamines, it is characterised in that the method carries out two-stage hydrogenation, first under same solvent
Section is hydrogenated with Raney's nickel as catalyst, methyl alcohol, and one or more in methylamine or Isosorbide-5-Nitrae-dioxane are solvent, organic amine, liquefied ammonia, water
It it is 40-80 DEG C in reaction temperature or NaOH is auxiliary agent, reaction pressure is under 5-8MPa, isophthalodinitrile and hydrogen are reacted, instead
It is 1-5h between seasonable, obtains m-xylene diamine reaction solution, it is catalyst that second segment is hydrogenated with to be supported with the activated carbon of ruthenium, is in reaction temperature
80-130 DEG C, reaction pressure is under 5-8MPa, m-xylene diamine reaction solution and hydrogen proceed reaction, and the reaction time is 1-6h, system
It is standby to obtain 1,3- cyclohexyldimethylamines.
Preferred Isosorbide-5-Nitrae-the dioxane of described solvent；Described auxiliary agent preferred concentration is the NaOH of 50wt%.
Described solvent accounts for the 50-90wt% of first paragraph hydrogenation reaction thing total amount, and auxiliary agent accounts for the 0.6-6wt% of first paragraph hydrogenation reaction thing total amount,
Raney's nickel accounts for the 2.5-6wt% of first paragraph hydrogenation reaction thing total amount.
Described solvent accounts for the 60-80wt% of first paragraph hydrogenation reaction thing total amount, and auxiliary agent accounts for the 1-4wt% of first paragraph hydrogenation reaction thing total amount, thunder
Buddhist nun's nickel accounts for the 3-6wt% of first paragraph hydrogenation reaction thing total amount.
Preferred 50-70 DEG C of the reaction temperature of described first paragraph hydrogenation, the preferred 5-7MPa of reaction pressure, reaction time preferred 1-3h.
Described is supported with 5wt% containing ruthenium in the catalyst of the activated carbon of ruthenium, and the addition of catalyst accounts for second segment hydrogenation reaction thing total amount
1-5wt%.
The addition of described catalyst accounts for the 2-4wt% of second segment hydrogenation reaction thing total amount.
Preferred 90-110 DEG C of the reaction temperature of described second segment hydrogenation, the preferred 5-7MPa of reaction pressure, reaction time preferred 1-4h.
Compared with prior art, the present invention has technological operation simple, high income, the characteristics of easy rectifying, the total recovery after rectifying up to 90%,
Directly can be improved in existing MXDA production technologies, it is 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, 120g dioxane, 5.62g50% sodium hydroxide solutions and 8g raney ni catalysis successively in autoclave
Agent, closes kettle, after replacing three times with H2, is passed through H2 to 5MPa, opens and is heated with stirring to 60 DEG C, reinflated to 6MPa, waits reaction
Hydrogen is inhaled, when pressure is down to 5MPa, 6MPa is inflated to, so operated repeatedly to no longer hydrogen is inhaled, now reacted about 80 minutes.It is cold
But to room temperature, hydrogen is vented, drives kettle, pour out supernatant liquor (MXDA reaction solutions), lower catalyst agent is applied mechanically.
Put into the ruthenium Pd/carbon catalyst of a certain amount of above-mentioned MXDA reaction solutions and 4g5% successively in autoclave, close kettle, use
After H2 replaces three times, H2 to 6MPa is passed through, opens and be 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 operated repeatedly to no longer hydrogen is inhaled, now reacted about 140 minutes.Room temperature is cooled to, is put
Air switch kettle, discharging, suction filtration, filter cake (catalyst) is applied mechanically, and filtrate is 88.3% through the total recovery after precipitation rectifying.
Embodiment 2
Put into 37.5g m-xylene diamines successively in autoclave, 150g dioxane, 5.7g50% sodium hydroxide solutions and 8g Raney's nickels are urged
Agent, closes kettle, after replacing three times with H2, is passed through H2 to 5MPa, opens and is heated with stirring to 70 DEG C, reinflated to 6MPa, reaction
Hydrogen is inhaled, when pressure is down to 5MPa, 6MPa is inflated to, so operated repeatedly to no longer hydrogen is inhaled, now reacted about 60 minutes.It is cold
But to room temperature, kettle is driven in emptying, pours out supernatant liquor (MXDA reaction solutions), and lower catalyst agent is applied mechanically.
Put into the ruthenium Pd/carbon catalyst of a certain amount of above-mentioned MXDA reaction solutions and 4g5% successively in autoclave, close kettle, after replacing three times with H2,
H2 to 6MPa is passed through, is opened and is heated with stirring to 100 DEG C, it is reinflated to 7MPa, wait reaction to inhale hydrogen, when pressure is down to 6MPa, it is inflated to
7MPa, so operates to no longer hydrogen is inhaled repeatedly, now reacts about 120 minutes and is cooled to room temperature, and kettle is driven in emptying, discharges, suction filtration,
Filter cake (catalyst) is applied mechanically, and filtrate is 90% through the total recovery after precipitation rectifying.
Embodiment 3
Put into 37.5g m-xylene diamines successively in autoclave, 150g dioxane, 5.7g50% sodium hydroxide solutions and 8g Raney's nickels are urged
Agent, closes kettle, after replacing three times with H2, is passed through H2 to 5MPa, opens and is heated with stirring to 70 DEG C, reinflated to 6MPa, waits anti-
Hydrogen should be inhaled, when pressure is down to 5MPa, 6MPa is inflated to, so operated repeatedly to no longer hydrogen is inhaled, now reacted about 100 minutes.It is cold
But to room temperature, kettle is driven in emptying, pours out supernatant liquor (MXDA reaction solutions), and lower catalyst agent is applied mechanically.Put into successively in autoclave a certain amount of
Above-mentioned MXDA reaction solutions and 5g5% ruthenium Pd/carbon catalyst, close kettle, with H2 replace three times after, be passed through H2 to 6MPa, open stirring
It is heated to 100 DEG C, it is reinflated to 7MPa, wait reaction to inhale hydrogen, when pressure is down to 6MPa, 7MPa is inflated to, so operate repeatedly to not
Untill inhaling hydrogen again, now react about 100 minutes and be cooled to room temperature, kettle is driven in emptying, discharges, and suction filtration, filter cake (catalyst) is applied mechanically,
Filtrate is 90% through the total recovery after precipitation rectifying.
Claims (2)
1. the method that one kind prepares 1,3- cyclohexyldimethylamines, it is characterised in that the method is in same solvent
Under carry out two-stage hydrogenation, first paragraph is hydrogenated with Raney's nickel as catalyst, methyl alcohol, methylamine or Isosorbide-5-Nitrae-two
One or more in the ring of oxygen six are solvent, and organic amine, liquefied ammonia, water or NaOH are auxiliary agent,
Reaction temperature be 40-80 DEG C, reaction pressure be 5-8MPa under, isophthalodinitrile and hydrogen are reacted,
Reaction time is 1-5h, obtains m-xylene diamine reaction solution, and second segment is hydrogenated with to be supported with the activated carbon of ruthenium
Be catalyst, reaction temperature be 80-130 DEG C, reaction pressure be 5-8MPa under, m-xylene diamine
Reaction solution and hydrogen proceed reaction, and the reaction time is 1-6h, prepares 1,3- cyclohexyl two
Methylamine.
2. the method that one kind according to claim 1 prepares 1,3- cyclohexyldimethylamines, its feature exists
In the preferred Isosorbide-5-Nitrae-dioxane of described solvent；Described auxiliary agent preferred concentration is the hydrogen of 50wt%
Sodium oxide molybdena.
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Cited By (1)
| 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 |
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Cited By (2)
| 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 |
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Application publication date: 20170609 |