CN106946741B - A kind of preparation method of dicyclohexyl methyl hydride diisocyanate - Google Patents
A kind of preparation method of dicyclohexyl methyl hydride diisocyanate Download PDFInfo
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- CN106946741B CN106946741B CN201710281633.8A CN201710281633A CN106946741B CN 106946741 B CN106946741 B CN 106946741B CN 201710281633 A CN201710281633 A CN 201710281633A CN 106946741 B CN106946741 B CN 106946741B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
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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
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
- C07C263/20—Separation; Purification
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Abstract
The excellent dicyclohexyl methyl hydride diisocyanate (H of storage yellowing resistance is prepared the present invention relates to a kind of12MDI method).Comprising: a) to raw material dicyclohexylmethane diamine (H12MDA it) is purified, obtains the H comprising 0.1wt% fragrant monoamine compound below12MDA；B) to the H comprising 0.1wt% fragrant monoamine compound below12MDA carries out phosgenation, obtains H12MDI.H is made by this method12MDI has the excellent characteristic of storage yellowing resistance, stores same time under the same conditions, H is made in this method12MDI color number is more stable.
Description
Technical field
The present invention relates to the preparation method of isocyanates, it is specifically related to a kind of prepare dicyclohexyl methyl hydride diisocyanate
Method.
Background technique
Dicyclohexyl methyl hydride diisocyanate (H12It MDI is) by dicyclohexylmethane diamine (H12MDA phosgenation) is anti-
It answers obtained.But due to raw material composition, preparation process and post-processing (such as removing solvent, separating monomer) various reasons, lead to
Often H obtained12MDI monomer storage yellowing resistance is poor, i.e., will appear color burn during storage, this is to downstream application
Unfavorable.
Causing the reason of isocyanates storage yellowing resistance difference to have much needs different methods to avoid.
Impurity is fallen in CN101003498A removing from isocyanates in such a way that rectifying and crystallization are applied in combination, and obtains
The higher isocyanate products of purity, gained isocyanates storage stability is more preferable, identical condition of storage and under the time, the party
Isocyanates appearance and crystallinity compared with the isocyanates only purified by rectification method obtained by method are more preferable, but this method
To isocyanate products purifying using rectifying and crystallization combination, because impurity in isocyanates and target product boiling point are close,
Rectifying separating difficulty is big, energy consumption is high, and this method also creates product yield reduction.
JP2001055427A is modified to improve isocyanates storage stability by urethane, but is not directed to Storage period
Between isocyanates color stability improvement.CN102718683A, CN104945585A pass through carbodiimide modified method and increase
Isocyanates storage stability.Above-mentioned modified scheme changes product characteristics, accordingly also changes original isocyanic acid
The application performance of ester.
The prior art is usually including to be purified again to product and modification by post-processing to product,
To improve product shelf life secondary color stability, the mode that these methods are improved both for product, high, drop that there are energy consumptions
Low product yield changes the drawbacks such as product characteristics.Therefore it needs to find new method, it is low under the premise of not changing product characteristics
The improvement isocyanate products of energy consumption store yellowing resistance.
Summary of the invention
The present invention provides a kind of dicyclohexyl methyl hydride diisocyanate (H that storage yellowing resistance is excellent12MDI preparation side)
Method.The method is by reducing phosgenation reaction raw material dicyclohexylmethane diamine (H12MDA fragrant monoamine compound in)
Content, so that final H12It is excellent that MDI product stores yellowing resistance.The method does not change product characteristics, to H12It is fragrant in MDA
Monoamine compound removal effect is good, low energy consumption.
To reach technical purpose of the invention, using following technical scheme.
The present invention is based on the study found that preparing H in diaminodiphenylmethane (MDA) plus hydrogen12During MDA, because of itself plus hydrogen
The factor of technique, catalyst system and solvent etc., it may appear that a phenyl ring does not add hydrogen in MDA, on another ring amino because
The case where deamination reaction is removed under high temperature generates a certain proportion of fragrant monoamine compound, for this reason,
H12Fragrant monoamine compound in MDA containing 0.3~0.6wt%；And in subsequent phosgenation H12MDA prepares H12MDI step
In, H12Fragrance monoamine compound present in MDA can form fragrant monoisocyanates class compound by phosgenation.These
Fragrant monoisocyanates class compound boiling point and H12MDI is close, efficiently separates by the way that conventional separation means are difficult to realize, and
Remain in H12Fragrant monoisocyanates class compound in MDI frequently can lead to H12MDI is coloured during storing.Using the present invention
Method, by pretreatment make phosgenation reaction raw material H12In MDA the content control of fragrant monoamine compound 0.05~
0.1wt%, preferably 0.05~0.06wt%, such H12MDA carries out H made from phosgenation reaction12Fragrance is single in MDI product
The content of isocyanate ester compound will be greatly reduced, so that product H12Stability increases during MDI is stored, and color is kept substantially
It is constant.
Excellent dicyclohexyl methyl hydride diisocyanate (the H of storage yellowing resistance is prepared the present invention provides a kind of12MDI)
Method, comprising the following steps: with comprising 0.05~0.1wt%, preferably 0.05~0.06wt% fragrance monoamine compound
H12MDA is raw material, carries out phosgenation reaction, obtains H12MDI, the content of the fragrance monoamine compound is with contained in raw material
H12It is calculated on the basis of the weight of MDA.
The content of following fragrance monoamine compound is with H contained in mixture12It is calculated on the basis of the weight of MDA.
Fragrance monoamine compound of the present invention is MDA under hydrogenation conditions, with the benzene of an amino bond even
Hydrogenation reaction do not occur for ring, and the amino on another phenyl ring is removed because deamination reaction occurs for high temperature, which occurs or not
Hydrogenation reaction occurs.
The specific example of fragrance monoamine compound of the present invention has 1- (4- aminophenyl) -1- cyclohexyl-methane, 1-
(4- aminophenyl) -1- phenylmethane, 1- (4- aminophenyl) -1- (1- cyclohexenyl group) methane, 1- (4- aminophenyl) -1-
(2- cyclohexenyl group) methane, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane, 1- (2- aminophenyl) -1- cyclohexyl first
Alkane, 1- (2- aminophenyl) -1- phenylmethane, 1- (2- aminophenyl) -1- (1- cyclohexenyl group) methane, 1- (2- aminobenzene
Base) -1- (2- cyclohexenyl group) methane, 1- (2- aminophenyl) -1- (3- cyclohexenyl group) methane.
Of the present invention includes 0.05~0.1wt%, preferably 0.05~0.06wt% fragrance monoamine compound
H12MDA is obtained by purification.Before purification, H12Fragrant monoamine compound in MDA containing 0.3~0.6wt%.
The purification can be realized by distillation and/or rectifying or crystallization or chemical reduction method, preferably be crystallized by two-stage
Method is to raw material H12MDA is purified, the two-stage method for crystallising the following steps are included:
A1) by the H containing 0.3~0.6wt% fragrance monoamine compound12MDA raw material is sent into first degree crystalline device and is divided
From obtaining fragrant monoamine kind compound content is 0.1~0.2wt%, the preferably H of 0.1~0.15wt%12MDA；
It a2 is) 0.1~0.2wt%, the preferably H of 0.1~0.15wt% by fragrant monoamine kind compound content12MDA is sent into
Secondary crystallizer is separated, and obtaining fragrant monoamine kind compound content is 0.05~0.1wt%, preferably 0.05~0.06wt%
H12MDA。
Specifically, two-stage crystallization process of the present invention, comprising the following steps:
1) by H12MDA feedstock to temperature is 30~40 DEG C, in preferably 30~35 DEG C of first degree crystalline device, control cooling
Time is 5~10 minutes, and preferably 7.5~10 minutes, temperature was at the uniform velocity down to 10~20 DEG C, preferably 10~18 DEG C；
2) at 10~20 DEG C, preferably 10~18 DEG C of constant temperature, constant temperature time is 0.5~1.5 hour, preferably 1~1.5 hour；
3) it controls temperature fall time 1~3 hour, preferably 1.5~3 hours, temperature was at the uniform velocity down to 5~15 DEG C, preferably 5~12
DEG C, the liquid in first degree crystalline device is discharged, the liquid is that fragrant monoamine kind compound content is 0.5~0.7wt%, preferably
The H of 0.6~0.7wt%12MDA；
4) it controls the heating-up time 1~4 hour, preferably 2~4 hours, temperature at the uniform velocity rose to 15~20 DEG C, preferably 18~20
DEG C, the liquid in first degree crystalline device is discharged, the liquid is that the fragrant monoamine kind compound content melted in temperature-rise period is
0.6~0.8wt%, the preferably H of 0.7~0.8wt%12MDA；
5) the control heating-up time is 1~5 minute, and preferably 3~5 minutes, temperature at the uniform velocity rose to 25~35 DEG C, preferably 30~35
DEG C, it is 0.1~0.2%wt, preferably 0.1~0.15%wt that solid melts, which obtain fragrant monoamine kind compound content, in temperature-rise period
H12MDA liquid；
6) by H obtained by step 5)12MDA liquid feedstock to temperature is 35~45 DEG C, preferably 35~40 DEG C of secondary crystallizer
In, control temperature fall time is 5~10 minutes, and preferably 6~8 minutes, temperature was at the uniform velocity down to 10~20 DEG C, preferably 12~18 DEG C；
7) at 10~20 DEG C, preferably 12~18 DEG C of constant temperature, constant temperature time is 1~2 hour, preferably 1.5~2 hours；
8) it controls temperature fall time 1~4 hour, preferably 2~4h, temperature is at the uniform velocity down to 5~15 DEG C, preferably 6~13 DEG C, by two
Liquid discharge in grade crystallizer, the liquid is that fragrant monoamine kind compound content is 0.4~0.5wt%, preferably 0.4~
The H of 0.45wt%12MDA；
9) it controls the heating-up time 1~4 hour, preferably 2~4 hours, temperature at the uniform velocity rose to 15~20 DEG C, preferably 18~20
DEG C, the liquid in secondary crystallizer is discharged, the liquid is that the fragrant monoamine kind compound content melted in temperature-rise period is
0.45~0.55wt%, the preferably H of 0.5~0.55wt%12MDA；
10) the control heating-up time is 2~8 minutes, and preferably 4~6 minutes, temperature at the uniform velocity rose to 30~40 DEG C, preferably 35~
40 DEG C, in temperature-rise period solid melts obtain fragrant monoamine kind compound content be 0.05~0.1wt%, preferably 0.05~
The H of 0.06wt%12MDA liquid, discharge obtain final products.
It is preferred that the liquid of step 8) discharge is as H12MDA feedstock circulation returns step 1).
It is preferred that the liquid of step 9) discharge is as H12MDA feedstock circulation returns step 1).
General crystallization processes carry out under normal pressure, and it is absolute pressure 115KPa that crystallization processes of the present invention, which need to control pressure,
~135KPa, preferably absolute pressure 120KPa~125KPa.It is controlled by pressure, crystallization process, which is formed by crystal layer, more neatly to be had
Sequence, Crystallization Separation effect is more excellent compared with atmospheric operation, and finally obtaining fragrant monoamine kind compound content of the invention is 0.05
~0.1wt%, the preferably H of 0.05~0.06wt%12MDA。
Atmosphere in first degree crystalline device and secondary crystallizer of the present invention is preferably inert gas；The inert gas
It can be nitrogen and/or argon gas, preferably nitrogen.
The preferred static mold of crystallizer of the present invention, more preferably rectangular lamella heat exchanger.
Cooling medium in crystallizer of the present invention can be arbitrary medium well known in the art, preferably ethylene glycol
With water mixed liquid, the mass ratio of the ethylene glycol and water is 0.1~1:1, preferably 0.2~0.5:1.
Fragrance monoamine kind compound content of the present invention is 0.05~0.1wt%, preferably 0.05~0.06wt%'s
H12MDA is used to prepare the excellent dicyclohexyl methyl hydride diisocyanate (H of storage yellowing resistance12MDI)。
It is a kind of to prepare the excellent dicyclohexyl methyl hydride diisocyanate (H of storage yellowing resistance12MDI method), including with
Lower step: to include 0.05~0.1wt%, the H of preferably 0.05~0.06wt% fragrance monoamine compound12MDA is raw material, into
Row phosgenation reaction, obtains H12MDI。
Phosgenation reaction of the present invention carries out in the gas phase, H12It is mixed after MDA gasification with inert media, institute of the present invention
State inert media for one of nitrogen, aromatic compound (such as chlorobenzene, dichloro benzene,toluene,xylene) or a variety of, preferably
One of nitrogen, chlorobenzene and dichloro-benzenes are a variety of.The dosage of inert media of the present invention is with the inert media gas after gasifying
Body volume calculates, inert media gas and H12The volume ratio of MDA gas is 0.001~5:1, preferably 0.01~3:1.
Phosgene and H in phosgenation reaction of the present invention12The molar ratio of MDA is 2~20:1, preferably 4~10:1.
The temperature of phosgenation reaction of the present invention is 300~500 DEG C, preferably 300~450 DEG C.It is of the present invention
Phosgenation reaction absolute pressure be 0.05~0.3MPa, preferably 0.07~0.2MPa.
The reduction of phosgenation reaction product temperatur is realized in single stage or multistage spray washing using atent solvent.This
The atent solvent of the invention spray washing can be the hydrocarbon that optional halogen atom replaces, optionally indicate with or without,
Such as one of chlorobenzene, dichloro-benzenes, toluene and dimethylbenzene or a variety of, preferably one or both of chlorobenzene and toluene.
During spray washing, H12MDI selectivity enters atent solvent.The H obtained by spray washing12MDI
Solution preferably obtains the H of not containing hydrogen chloride and phosgene by rectification and purification12MDI solution, and divide in further distilation steps
From at solvent, low-boiling by-product, H12Several material streams such as MDI product and high boiling by-product.
The H that the present invention is prepared12MDI product, the characteristic for having storage yellowing resistance excellent, is made by conventional method
H12After MDI is stored 12 months, color number generally rises to 30Hazen or more by 10Hazen or less, this method preparation
H12After MDI stores 12 months under the same conditions, product color number is still within 15Hazen.
Detailed description of the invention
Fig. 1 is H12The preferred embodiment flow chart of fragrant monoamine compound removing in MDA.
Specific embodiment
The present invention is existing, and following non-limiting embodiment is described in further detail.
H12The content of fragrant monoamine compound in MDA is using Agilent GC7890 gas chromatograph and uses DB-5 type
Chromatographic column (fid detector, injector temperature: 300 DEG C, column temperature temperature program: after 150 DEG C of holding 2min, with the speed of 8 DEG C/min
Degree is warming up to 300 DEG C of holding 2min, detector temperature: 325 DEG C) it is measured, as a result obtained by area normalization method.
In all embodiments, the coloration of the target isocyanate product obtained measures it by GB/T3143-1982
Platinum cobalt color number value；
The present invention is further illustrated below by embodiment, but the present invention is not only restricted to this:
Embodiment 1
As shown in Figure 1, cooling water group becomes ethylene glycol and water quality ratio 0.1:1, level-one, second level are sufficiently displaced from using nitrogen
Crystallizer, controlling pressure in crystal system is absolute pressure 115KPa, and cooling water temperature is adjusted to 30 DEG C in first degree crystalline device, will be contained
1- (4- aminophenyl) -1- cyclohexyl-methane 0.15wt%, 1- (4- aminophenyl) -1- phenylmethane 0.1wt%, 1- (4- ammonia
Base phenyl) -1- (1- cyclohexenyl group) methane 0.05wt% H12MDA liquid charging stock is fed into first degree crystalline device by container 1, control
Cooling water is at the uniform velocity cooled to 10 DEG C for 5 minutes by system, controls 10 DEG C of cooling water constant temperature 0.5 hour, and controlling after constant temperature 1 hour will
Cooling water temperature is 5 DEG C at the uniform velocity near, after cooling discharge containing 1- (4- aminophenyl) -1- cyclohexyl-methane 0.25wt%,
1- (4- aminophenyl) -1- phenylmethane 0.15wt%, 1- (4- aminophenyl) -1- (1- cyclohexenyl group) methane 0.1wt%'s
H12MDA liquid controls 1 hour after drain and temperature is at the uniform velocity risen to 15 DEG C into container 3, and discharge contains 1- after heating
(4- aminophenyl) -1- cyclohexyl-methane 0.3wt%, 1- (4- aminophenyl) -1- phenylmethane 0.2wt%, 1- (4- aminobenzene
Base) -1- (1- cyclohexenyl group) methane 0.1wt% H12MDA liquid controls 1 minute after drain into container 3 and at the uniform velocity rises temperature
To 25 DEG C, discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.06wt%, 1- (4- aminophenyl)-after heating
The H of 1- phenylmethane 0.03wt%, 1- (4- aminophenyl) -1- (1- cyclohexenyl group) methane 0.01wt%12MDA liquid is to container
2。
Cooling water temperature is adjusted to 35 DEG C in secondary crystallizer, by liquid feedstock in container 2 into secondary crystallizer, control
Cooling water is at the uniform velocity cooled to 10 DEG C for 5 minutes, controls 10 DEG C of cooling water constant temperature 1 hour, controlling 1 hour after constant temperature will cool down
Coolant-temperature gage is 5 DEG C at the uniform velocity near, and discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.2wt%, 1- (4- after cooling
Aminophenyl) -1- phenylmethane 0.12wt%, 1- (4- aminophenyl) -1- (1- cyclohexenyl group) methane 0.08wt% H12MDA
Liquid is recycled into container 1, controls 1 hour after drain and temperature is at the uniform velocity risen to 15 DEG C, and discharge contains after heating
There are 1- (4- aminophenyl) -1- cyclohexyl-methane 0.22wt%, 1- (4- aminophenyl) -1- phenylmethane 0.14wt%, 1- (4-
Aminophenyl) -1- (1- cyclohexenyl group) methane 0.09wt% H12MDA liquid is recycled into container 1, and 2 are controlled after drain
Temperature is at the uniform velocity risen to 30 DEG C by minute, and the liquid melted after heating is to contain 1- (4- aminophenyl) -1- cyclohexyl-methane
0.03wt%, 1- (4- aminophenyl) -1- phenylmethane 0.01wt%, 1- (4- aminophenyl) -1- (1- cyclohexenyl group) methane
The H of 0.01wt%12MDA is drained into container 4.
By H in above-mentioned gained container 412MDA and nitrogen are according to nitrogen and H12The volume ratio of MDA gas be 2:1, phosgene and
H12The molar ratio of MDA is 5:1, gas phase phosgenation reaction is carried out under 400 DEG C and absolute pressure 0.1MPa, using chlorobenzene to reaction product
Spray washing is carried out, the H obtained by spray washing12MDI solution obtains not containing hydrogen chloride and phosgene by rectification and purification
H12MDI solution, and solvent, low-boiling by-product, H are separated into further distilation steps12MDI product and higher boiling
The material streams such as by-product.
Embodiment 2:
Cooling water group becomes ethylene glycol and water quality ratio 0.2:1, is sufficiently displaced from level-one, secondary crystallizer using nitrogen, controls
Pressure is absolute pressure 120KPa in crystal system processed, and cooling water temperature is adjusted to 33 DEG C in first degree crystalline device, will contain 1- (4- amino
Phenyl) -1- cyclohexyl-methane 0.2wt%, 1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.12wt%, 1- (4- amino
Phenyl) -1- (3- cyclohexenyl group) methane 0.08wt% H12MDA liquid charging stock is fed into first degree crystalline device by container 1, control
Cooling water is at the uniform velocity cooled to 14 DEG C for 6 minutes, controls 14 DEG C of cooling water constant temperature 1 hour, controlling after constant temperature 1.5 hours will be cold
But coolant-temperature gage is 8 DEG C at the uniform velocity near, and discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.3wt%, 1- after cooling
(4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.2wt%, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane
The H of 0.1wt%12MDA liquid controls 2 hours after drain and temperature is at the uniform velocity risen to 18 DEG C, after heating into container 3
Discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.35wt%, 1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane
The H of 0.23wt%, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane 0.12wt%12MDA liquid is into container 3, after drain
Temperature is at the uniform velocity risen to 30 DEG C in 3 minutes by control, and discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane after heating
0.07wt%, 1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.04wt%, 1- (4- aminophenyl) -1- (3- cyclohexene
Base) methane 0.015wt% H12MDA liquid is to container 2.
Cooling water temperature is adjusted to 37 DEG C in secondary crystallizer, by liquid feedstock in container 2 into secondary crystallizer, control
Cooling water is at the uniform velocity cooled to 12 DEG C for 6 minutes, controls 12 DEG C of cooling water constant temperature 1.5 hours, controlling after constant temperature 2 hours will be cold
But coolant-temperature gage is 6 DEG C at the uniform velocity near, and discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.21wt%, 1- after cooling
(4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.13wt%, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane
The H of 0.085wt%12MDA liquid is recycled into container 1, controls 2 hours after drain and temperature is at the uniform velocity risen to 18 DEG C,
Discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.25wt%, 1- (4- aminophenyl) -1- (2- ring after heating
Hexenyl) methane 0.15wt%, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane 0.1wt% H12MDA liquid is to container
It is recycled in 1, is controlled 4 minutes after drain and temperature is at the uniform velocity risen to 35 DEG C, the liquid melted after heating is to contain 1- (4-
Aminophenyl) -1- cyclohexyl-methane 0.033wt%, 1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.011wt%, 1-
The H of (4- aminophenyl) -1- (3- cyclohexenyl group) methane 0.011wt%12MDA is drained into container 4.It will be in above-mentioned gained container 4
H12MDA is reacted according to the identical scheme of embodiment 1 by gas phase phosgenation and rectifying separation preparation H12MDI product.
Embodiment 3
Cooling water group becomes ethylene glycol and water quality ratio 0.3:1, is sufficiently displaced from level-one, secondary crystallizer using nitrogen, controls
Pressure is absolute pressure 123KPa in crystal system processed, and cooling water temperature is adjusted to 35 DEG C in first degree crystalline device, will contain 1- (4- amino
Phenyl) -1- cyclohexyl-methane 0.22wt%, 1- (2- aminophenyl) -1- cyclohexyl-methane 0.14wt%, 1- (2- aminobenzene
Base) -1- phenylmethane 0.09wt% H12MDA liquid charging stock is fed into first degree crystalline device by container 1, and controlling 7.5 minutes will
Cooling water is at the uniform velocity cooled to 18 DEG C, controls 18 DEG C of cooling water constant temperature 1.25 hours, 2 hours are controlled after constant temperature by coolant water temperature
At the uniform velocity near 12 DEG C are spent, discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.33wt%, 1- (2- ammonia after cooling
Base phenyl) -1- cyclohexyl-methane 0.21wt%, 1- (2- aminophenyl) -1- phenylmethane 0.11wt% H12MDA liquid extremely holds
It in device 3, is controlled 3 hours after drain and temperature is at the uniform velocity risen to 19 DEG C, discharge contains 1- (4- aminophenyl)-after heating
1- cyclohexyl-methane 0.37wt%, 1- (2- aminophenyl) -1- cyclohexyl-methane 0.24wt%, 1- (2- aminophenyl) -1- benzene
The H of methylmethane 0.14wt%12MDA liquid controls 4 minutes after drain and temperature is at the uniform velocity risen to 33 DEG C, heating terminates into container 3
Discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.075wt%, 1- (2- aminophenyl) -1- cyclohexyl-methane afterwards
The H of 0.045wt%, 1- (2- aminophenyl) -1- phenylmethane 0.03wt%12MDA liquid is to container 2.
Cooling water temperature is adjusted to 40 DEG C in secondary crystallizer, by liquid feedstock in container 2 into secondary crystallizer, control
Cooling water is at the uniform velocity cooled to 15 DEG C for 7 minutes, controls 15 DEG C of cooling water constant temperature 1.75 hours, controlling after constant temperature 3 hours will
Cooling water temperature is 10 DEG C at the uniform velocity near, after cooling discharge containing 1- (4- aminophenyl) -1- cyclohexyl-methane 0.22wt%,
The H of 1- (2- aminophenyl) -1- cyclohexyl-methane 0.14wt%, 1- (2- aminophenyl) -1- phenylmethane 0.09wt%12MDA
Liquid is recycled into container 1, controls 3 hours after drain and temperature is at the uniform velocity risen to 19 DEG C, and discharge contains after heating
There are 1- (4- aminophenyl) -1- cyclohexyl-methane 0.26wt%, 1- (2- aminophenyl) -1- cyclohexyl-methane 0.16wt%, 1-
The H of (2- aminophenyl) -1- phenylmethane 0.105wt%12MDA liquid is recycled into container 1, is controlled 5 minutes after drain
Temperature is at the uniform velocity risen to 37 DEG C, the liquid melted after heating is to contain 1- (4- aminophenyl) -1- cyclohexyl-methane
0.035wt%, 1- (2- aminophenyl) -1- cyclohexyl-methane 0.013wt%, 1- (2- aminophenyl) -1- phenylmethane
The H of 0.012wt%12MDA is drained into container 4.
By H in above-mentioned gained container 412MDA is reacted according to the identical scheme of embodiment 1 by gas phase phosgenation and rectifying point
From preparation H12MDI product.
Embodiment 4
Cooling water group becomes ethylene glycol and water quality ratio 0.5:1, is sufficiently displaced from level-one, secondary crystallizer using nitrogen, controls
Pressure is absolute pressure 125KPa in crystal system processed, and cooling water temperature is adjusted to 35 DEG C in first degree crystalline device, will contain 1- (4- amino
Phenyl) -1- cyclohexyl-methane 0.25wt%, 1- (2- aminophenyl) -1- phenylmethane 0.15wt%, 1- (2- aminophenyl) -
The H of 1- (1- cyclohexenyl group) methane 0.1wt%12MDA liquid charging stock is fed into first degree crystalline device by container 1, and controlling 8 minutes will
Cooling water is at the uniform velocity cooled to 18 DEG C, controls 18 DEG C of cooling water constant temperature 1.25 hours, 2 hours are controlled after constant temperature by coolant water temperature
At the uniform velocity near 12 DEG C are spent, discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.33wt%, 1- (2- ammonia after cooling
Base phenyl) -1- phenylmethane 0.21wt%, 1- (2- aminophenyl) -1- (1- cyclohexenyl group) methane 0.11wt% H12MDA liquid
Body controls 3 hours after drain and temperature is at the uniform velocity risen to 19 DEG C into container 3, and discharge contains 1- (4- amino after heating
Phenyl) -1- cyclohexyl-methane 0.37wt%, 1- (2- aminophenyl) -1- phenylmethane 0.24wt%, 1- (2- aminophenyl) -
The H of 1- (1- cyclohexenyl group) methane 0.14wt%12MDA liquid controls 4 minutes after drain into container 3 and at the uniform velocity rises to temperature
33 DEG C, discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.075wt%, 1- (2- aminophenyl) -1- after heating
The H of phenylmethane 0.045wt%, 1- (2- aminophenyl) -1- (1- cyclohexenyl group) methane 0.03wt%12MDA liquid is to container
2。
Cooling water temperature is adjusted to 40 DEG C in secondary crystallizer, by liquid feedstock in container 2 into secondary crystallizer, control
Cooling water is at the uniform velocity cooled to 18 DEG C for 8 minutes, controls 18 DEG C of cooling water constant temperature 1.75 hours, controlling after constant temperature 3 hours will
Cooling water temperature is 13 DEG C at the uniform velocity near, after cooling discharge containing 1- (4- aminophenyl) -1- cyclohexyl-methane 0.22wt%,
1- (2- aminophenyl) -1- phenylmethane 0.14wt%, 1- (2- aminophenyl) -1- (1- cyclohexenyl group) methane 0.09wt%'s
H12MDA liquid is recycled into container 1, controls after drain and temperature is at the uniform velocity risen to 19 DEG C for 3 hours, heating terminates heel row
Out containing 1- (4- aminophenyl) -1- cyclohexyl-methane 0.26wt%, 1- (2- aminophenyl) -1- phenylmethane 0.16wt%,
The H of 1- (2- aminophenyl) -1- (1- cyclohexenyl group) methane 0.105wt%12MDA liquid is recycled into container 1, after drain
Temperature is at the uniform velocity risen to 37 DEG C in 6 minutes by control, and the liquid melted after heating is to contain 1- (4- aminophenyl) -1- cyclohexyl
Methane 0.035wt%, 1- (2- aminophenyl) -1- phenylmethane 0.013wt%, 1- (2- aminophenyl) -1- (1- cyclohexene
Base) methane 0.012wt% H12MDA is drained into container 4.
By H in above-mentioned gained container 412MDA is reacted according to the identical scheme of embodiment 1 by gas phase phosgenation and rectifying point
From preparation H12MDI product.
Embodiment 5
Cooling water group becomes ethylene glycol and water quality ratio 1:1, is sufficiently displaced from level-one, secondary crystallizer using nitrogen, controls
Pressure is absolute pressure 135KPa in crystal system, and cooling water temperature is adjusted to 40 DEG C in first degree crystalline device, will contain 1- (4- aminobenzene
Base) -1- cyclohexyl-methane 0.3wt%, 1- (2- aminophenyl) -1- (2- cyclohexenyl group) methane 0.2wt%, 1- (2- aminobenzene
Base) -1- (3- cyclohexenyl group) methane 0.1wt% H12MDA liquid charging stock is fed into first degree crystalline device by container 1, control 10
Cooling water is at the uniform velocity cooled to 20 DEG C by minute, controls 20 DEG C of cooling water constant temperature 1.5 hours, controlling after constant temperature 3 hours will be cold
But coolant-temperature gage is 15 DEG C at the uniform velocity near, and discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.35wt%, 1- after cooling
(2- aminophenyl) -1- (2- cyclohexenyl group) methane 0.23wt%, 1- (2- aminophenyl) -1- (3- cyclohexenyl group) methane
The H of 0.12wt%12MDA liquid controls 4 hours after drain and temperature is at the uniform velocity risen to 20 DEG C, after heating into container 3
Discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.4wt%, 1- (2- aminophenyl) -1- (2- cyclohexenyl group) methane
The H of 0.25wt%, 1- (2- aminophenyl) -1- (3- cyclohexenyl group) methane 0.15wt%12MDA liquid is into container 3, after drain
Temperature is at the uniform velocity risen to 35 DEG C in 5 minutes by control, and discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane after heating
0.1wt%, 1- (2- aminophenyl) -1- (2- cyclohexenyl group) methane 0.06wt%, 1- (2- aminophenyl) -1- (3- cyclohexene
Base) methane 0.04wt% H12MDA liquid is to container 2.
Cooling water temperature is adjusted to 45 DEG C in secondary crystallizer, by liquid feedstock in container 2 into secondary crystallizer, control
Cooling water is at the uniform velocity cooled to 20 DEG C for 10 minutes, controls 20 DEG C of cooling water constant temperature 2 hours, controlling after constant temperature 4 hours will be cold
But coolant-temperature gage is 15 DEG C at the uniform velocity near, and discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.25wt%, 1- after cooling
(2- aminophenyl) -1- (2- cyclohexenyl group) methane 0.15wt%, 1- (2- aminophenyl) -1- (3- cyclohexenyl group) methane
The H of 0.1wt%12MDA liquid is recycled into container 1, controls after drain and temperature is at the uniform velocity risen to 20 DEG C for 4 hours, is risen
Discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.27wt%, 1- (2- aminophenyl) -1- (2- hexamethylene after temperature
Alkenyl) methane 0.17wt%, 1- (2- aminophenyl) -1- (3- cyclohexenyl group) methane 0.11wt% H12MDA liquid is to container 1
In recycle, controlled 8 minutes after drain and temperature at the uniform velocity risen to 40 DEG C, the liquid melted after heating be contain 1- (4-
Aminophenyl) -1- cyclohexyl-methane 0.06wt%, 1- (2- aminophenyl) -1- (2- cyclohexenyl group) methane 0.03wt%, 1-
The H of (2- aminophenyl) -1- (3- cyclohexenyl group) methane 0.01wt%12MDA is drained into container 4.
By H in above-mentioned gained container 412MDA is reacted according to the identical scheme of embodiment 1 by gas phase phosgenation and rectifying point
From preparation H12MDI product.
Comparative example 1
Using without crystallisation of the present invention it is purified contain 1- (4- aminocarbonyl phenyl) -1- cyclohexyl-methane
0.15wt%, 1- (4- aminocarbonyl phenyl) -1- phenylmethane 0.1wt%, 1- (4- aminocarbonyl phenyl) -1- (1- cyclohexenyl group) methane
The H of 0.05wt%12MDA is reacted according to the identical scheme of embodiment 1 by gas phase phosgenation and rectifying separation preparation H12MDI is produced
Product.
Comparative example 2
Cooling water group becomes ethylene glycol and water quality ratio 0.2:1, is sufficiently displaced from level-one, secondary crystallizer using nitrogen, controls
Pressure is normal pressure in crystal system processed, and cooling water temperature is adjusted to 33 DEG C in first degree crystalline device, will contain 1- (4- aminophenyl)-
1- cyclohexyl-methane 0.2wt%, 1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.12wt%, 1- (4- aminophenyl) -
The H of 1- (3- cyclohexenyl group) methane 0.08wt%12MDA liquid charging stock is fed into first degree crystalline device by container 1, is controlled 6 minutes
Cooling water is at the uniform velocity cooled to 14 DEG C, 14 DEG C of cooling water constant temperature 1 hour is controlled, 1.5 hours is controlled after constant temperature by cooling water
Temperature is 8 DEG C at the uniform velocity near, and discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.22wt%, 1- (4- ammonia after cooling
Base phenyl) -1- (2- cyclohexenyl group) methane 0.14wt%, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane 0.09wt%
H12MDA liquid controls 2 hours after drain and temperature is at the uniform velocity risen to 18 DEG C into container 3, and discharge contains after heating
1- (4- aminophenyl) -1- cyclohexyl-methane 0.27wt%, 1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane
The H of 0.17wt%, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane 0.11wt%12MDA liquid is into container 3, after drain
Temperature is at the uniform velocity risen to 30 DEG C in 3 minutes by control, and discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane after heating
0.13wt%, 1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.08wt%, 1- (4- aminophenyl) -1- (3- cyclohexene
Base) methane 0.04wt% H12MDA liquid is to container 2.
Cooling water temperature is adjusted to 37 DEG C in secondary crystallizer, by liquid feedstock in container 2 into secondary crystallizer, control
Cooling water is at the uniform velocity cooled to 12 DEG C for 6 minutes, controls 12 DEG C of cooling water constant temperature 1.5 hours, controlling after constant temperature 2 hours will be cold
But coolant-temperature gage is 6 DEG C at the uniform velocity near, and discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.21wt%, 1- after cooling
(4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.125wt%, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane
The H of 0.085wt%12MDA liquid is recycled into container 1, controls 2 hours after drain and temperature is at the uniform velocity risen to 18 DEG C,
Discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.22wt%, 1- (4- aminophenyl) -1- (2- ring after heating
Hexenyl) methane 0.14wt%, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane 0.09wt% H12MDA liquid extremely holds
It is recycled in device 1, is controlled 4 minutes after drain and temperature is at the uniform velocity risen to 35 DEG C, the liquid melted after heating is to contain 1-
(4- aminophenyl) -1- cyclohexyl-methane 0.1wt%, 1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.06wt%, 1-
The H of (4- aminophenyl) -1- (3- cyclohexenyl group) methane 0.04wt%12MDA is drained into container 4.
By H in above-mentioned gained container 412MDA is reacted according to the identical scheme of embodiment 1 by gas phase phosgenation and rectifying point
From preparation H12MDI product.
Comparative example 3
Cooling water group becomes ethylene glycol and water quality ratio 0.3:1, is sufficiently displaced from level-one, secondary crystallizer using nitrogen, controls
Pressure is absolute pressure 105KPa in crystal system processed, and cooling water temperature is adjusted to 35 DEG C in first degree crystalline device, will contain 1- (4- amino
Phenyl) -1- cyclohexyl-methane 0.22wt%, 1- (2- aminophenyl) -1- cyclohexyl-methane 0.14wt%, 1- (2- aminobenzene
Base) -1- phenylmethane 0.09wt% H12MDA liquid charging stock is fed into first degree crystalline device by container 1, and controlling 7.5 minutes will
Cooling water is at the uniform velocity cooled to 18 DEG C, controls 18 DEG C of cooling water constant temperature 1.25 hours, 2 hours are controlled after constant temperature by coolant water temperature
At the uniform velocity near 12 DEG C are spent, discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.24wt%, 1- (2- ammonia after cooling
Base phenyl) -1- cyclohexyl-methane 0.14wt%, 1- (2- aminophenyl) -1- phenylmethane 0.1wt% H12MDA liquid extremely holds
It in device 3, is controlled 3 hours after drain and temperature is at the uniform velocity risen to 19 DEG C, discharge contains 1- (4- aminophenyl)-after heating
1- cyclohexyl-methane 0.27wt%, 1- (2- aminophenyl) -1- cyclohexyl-methane 0.17wt%, 1- (2- aminophenyl) -1- benzene
The H of methylmethane 0.11wt%12MDA liquid controls 4 minutes after drain and temperature is at the uniform velocity risen to 33 DEG C, heating terminates into container 3
Discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.15wt%, 1- (2- aminophenyl) -1- cyclohexyl-methane afterwards
The H of 0.1wt%, 1- (2- aminophenyl) -1- phenylmethane 0.05wt%12MDA liquid is to container 2.
Cooling water temperature is adjusted to 40 DEG C in secondary crystallizer, by liquid feedstock in container 2 into secondary crystallizer, control
Cooling water is at the uniform velocity cooled to 15 DEG C for 7 minutes, controls 15 DEG C of cooling water constant temperature 1.75 hours, controlling after constant temperature 3 hours will
Cooling water temperature is 10 DEG C at the uniform velocity near, after cooling discharge containing 1- (4- aminophenyl) -1- cyclohexyl-methane 0.21wt%,
1- (2- aminophenyl) -1- cyclohexyl-methane 0.125wt%, 1- (2- aminophenyl) -1- phenylmethane 0.085wt%'s
H12MDA liquid is recycled into container 1, controls after drain and temperature is at the uniform velocity risen to 19 DEG C for 3 hours, heating terminates heel row
Contain 1- (4- aminophenyl) -1- cyclohexyl-methane 0.22wt%, 1- (2- aminophenyl) -1- cyclohexyl-methane out
The H of 0.14wt%, 1- (2- aminophenyl) -1- phenylmethane 0.09wt%12MDA liquid is recycled into container 1, after drain
Temperature is at the uniform velocity risen to 37 DEG C in 5 minutes by control, and the liquid melted after heating is to contain 1- (4- aminophenyl) -1- cyclohexyl
Methane 0.13wt%, 1- (2- aminophenyl) -1- cyclohexyl-methane 0.08wt%, 1- (2- aminophenyl) -1- phenylmethane
The H of 0.04wt%12MDA is drained into container 4.
By H in above-mentioned gained container 412MDA is reacted according to the identical scheme of embodiment 1 by gas phase phosgenation and rectifying point
From preparation H12MDI product.
Comparative example 4
Cooling water group becomes ethylene glycol and water quality ratio 0.2:1, is sufficiently displaced from level-one, secondary crystallizer using nitrogen, controls
Pressure is absolute pressure 140KPa in crystal system processed, and cooling water temperature is adjusted to 33 DEG C in first degree crystalline device, will contain 1- (4- amino
Phenyl) -1- cyclohexyl-methane 0.2wt%, 1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.12wt%, 1- (4- amino
Phenyl) -1- (3- cyclohexenyl group) methane 0.08wt% H12MDA liquid charging stock is fed into first degree crystalline device by container 1, control
Cooling water is at the uniform velocity cooled to 14 DEG C for 6 minutes, controls 14 DEG C of cooling water constant temperature 1 hour, controlling after constant temperature 1.5 hours will be cold
But coolant-temperature gage is 8 DEG C at the uniform velocity near, and discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.3wt%, 1- after cooling
(4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.2wt%, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane
The H of 0.1wt%12MDA liquid controls 2 hours after drain and temperature is at the uniform velocity risen to 18 DEG C, after heating into container 3
Discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.35wt%, 1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane
The H of 0.23wt%, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane 0.12wt%12MDA liquid is into container 3, after drain
Temperature is at the uniform velocity risen to 30 DEG C in 3 minutes by control, and discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane after heating
0.07wt%, 1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.04wt%, 1- (4- aminophenyl) -1- (3- cyclohexene
Base) methane 0.015wt% H12MDA liquid is to container 2.
Cooling water temperature is adjusted to 37 DEG C in secondary crystallizer, by liquid feedstock in container 2 into secondary crystallizer, control
Cooling water is at the uniform velocity cooled to 12 DEG C for 6 minutes, controls 12 DEG C of cooling water constant temperature 1.5 hours, controlling after constant temperature 2 hours will be cold
But coolant-temperature gage is 6 DEG C at the uniform velocity near, and discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.21wt%, 1- after cooling
(4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.13wt%, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane
The H of 0.085wt%12MDA liquid is recycled into container 1, controls 2 hours after drain and temperature is at the uniform velocity risen to 18 DEG C,
Discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.25wt%, 1- (4- aminophenyl) -1- (2- ring after heating
Hexenyl) methane 0.15wt%, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane 0.1wt% H12MDA liquid is to container
It is recycled in 1, is controlled 4 minutes after drain and temperature is at the uniform velocity risen to 35 DEG C, the liquid melted after heating is to contain 1- (4-
Aminophenyl) -1- cyclohexyl-methane 0.033wt%, 1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.011wt%, 1-
The H of (4- aminophenyl) -1- (3- cyclohexenyl group) methane 0.011wt%12MDA is drained into container 4.It will be in above-mentioned gained container 4
H12MDA is reacted according to the identical scheme of embodiment 1 by gas phase phosgenation and rectifying separation preparation H12MDI product.
Comparative example 5
Cooling water group becomes ethylene glycol and water quality ratio 0.2:1, is sufficiently displaced from level-one, secondary crystallizer using nitrogen, controls
Pressure is absolute pressure 90KPa in crystal system processed, and cooling water temperature is adjusted to 33 DEG C in first degree crystalline device, will contain 1- (4- amino
Phenyl) -1- cyclohexyl-methane 0.2wt%, 1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.12wt%, 1- (4- amino
Phenyl) -1- (3- cyclohexenyl group) methane 0.08wt% H12MDA liquid charging stock is fed into first degree crystalline device by container 1, control
Cooling water is at the uniform velocity cooled to 14 DEG C for 6 minutes, controls 14 DEG C of cooling water constant temperature 1 hour, controlling after constant temperature 1.5 hours will be cold
But coolant-temperature gage is 8 DEG C at the uniform velocity near, and discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.22wt%, 1- after cooling
(4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.14wt%, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane
The H of 0.09wt%12MDA liquid controls 2 hours after drain and temperature is at the uniform velocity risen to 18 DEG C, after heating into container 3
Discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.27wt%, 1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane
The H of 0.17wt%, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane 0.11wt%12MDA liquid is into container 3, after drain
Temperature is at the uniform velocity risen to 30 DEG C in 3 minutes by control, and discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane after heating
0.13wt%, 1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.08wt%, 1- (4- aminophenyl) -1- (3- cyclohexene
Base) methane 0.04wt% H12MDA liquid is to container 2.
Cooling water temperature is adjusted to 37 DEG C in secondary crystallizer, by liquid feedstock in container 2 into secondary crystallizer, control
Cooling water is at the uniform velocity cooled to 12 DEG C for 6 minutes, controls 12 DEG C of cooling water constant temperature 1.5 hours, controlling after constant temperature 2 hours will be cold
But coolant-temperature gage is 6 DEG C at the uniform velocity near, and discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.21wt%, 1- after cooling
(4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.125wt%, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane
The H of 0.085wt%12MDA liquid is recycled into container 1, controls 2 hours after drain and temperature is at the uniform velocity risen to 18 DEG C,
Discharge contains 1- (4- aminophenyl) -1- cyclohexyl-methane 0.22wt%, 1- (4- aminophenyl) -1- (2- ring after heating
Hexenyl) methane 0.14wt%, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane 0.09wt% H12MDA liquid extremely holds
It is recycled in device 1, is controlled 4 minutes after drain and temperature is at the uniform velocity risen to 35 DEG C, the liquid melted after heating is to contain 1-
(4- aminophenyl) -1- cyclohexyl-methane 0.1wt%, 1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane 0.06wt%, 1-
The H of (4- aminophenyl) -1- (3- cyclohexenyl group) methane 0.04wt%12MDA is drained into container 4.
By H in above-mentioned gained container 412MDA is reacted according to the identical scheme of embodiment 1 by gas phase phosgenation and rectifying point
From preparation H12MDI product.
By above embodiments and comparative example as it can be seen that H12It is exhausted to being lower than using negative pressure or normal pressure during MDA crystallization purifying
It presses the pressure between 115KPa to carry out crystallization operation, is difficult to realize Crystallization Separation effect of the present invention, uses absolute pressure
The pressure operation of 135KPa or more is to H12MDA crystallization purifying is not improved, but will increase cost of equipment and operating cost.
Store anti-yellowing property test
Gained H in embodiment 1-5 and comparative example 1-512The storage anti-yellowing property data of MDI product are as shown in table 1 below.
Table 1H12The storage anti-yellowing property data of MDI product
Claims (14)
1. a kind of preparation method of dicyclohexyl methyl hydride diisocyanate, comprising the following steps: to include 0.05~0.1wt% virtue
The H of fragrant monoamine compound12MDA is raw material, carries out phosgenation reaction, obtains H12MDI, the fragrance monoamine compound
Content is with H contained in raw material12It is calculated on the basis of the weight of MDA；The fragrance monoamine compound is selected from 1- (4- aminobenzene
Base) -1- cyclohexyl-methane, 1- (4- aminophenyl) -1- phenylmethane, 1- (4- aminophenyl) -1- (1- cyclohexenyl group) methane,
1- (4- aminophenyl) -1- (2- cyclohexenyl group) methane, 1- (4- aminophenyl) -1- (3- cyclohexenyl group) methane, 1- (2- amino
Phenyl) -1- cyclohexyl-methane, 1- (2- aminophenyl) -1- phenylmethane, 1- (2- aminophenyl) -1- (1- cyclohexenyl group) first
One in alkane, 1- (2- aminophenyl) -1- (2- cyclohexenyl group) methane and 1- (2- aminophenyl) -1- (3- cyclohexenyl group) methane
Kind is a variety of.
2. the method according to claim 1, wherein the raw material is to include 0.05~0.06wt% fragrance monoamine
The H of class compound12MDA。
3. a kind of prepare H described in claim 112The method of MDA, comprising the following steps:
A1) by the H containing 0.3~0.6wt% fragrance monoamine compound12MDA raw material is sent into first degree crystalline device and is separated, and obtains
The H for being 0.1~0.2wt% to fragrant monoamine kind compound content12MDA；
A2) the H for being 0.1~0.2wt% by fragrant monoamine kind compound content12MDA is sent into secondary crystallizer and is separated, and obtains
Fragrant monoamine kind compound content is the H of 0.05~0.1wt%12MDA。
4. according to the method described in claim 3, the following steps are included:
A1) by the H containing 0.3~0.6wt% fragrance monoamine compound12MDA raw material is sent into first degree crystalline device and is separated, and obtains
The H for being 0.1~0.15wt% to fragrant monoamine kind compound content12MDA；
A2) the H for being 0.1~0.15wt% by fragrant monoamine kind compound content12MDA is sent into secondary crystallizer and is separated, and obtains
The H for being 0.05~0.06wt% to fragrant monoamine kind compound content12MDA。
5. according to the method described in claim 3, the following steps are included:
1) by H12In the first degree crystalline device that MDA feedstock is 30~40 DEG C to temperature, control temperature fall time is 5~10 minutes,
Temperature is at the uniform velocity down to 10~20 DEG C；
2) in 10~20 DEG C of constant temperature, constant temperature time is 0.5~1.5 hour；
3) it controls temperature fall time 1~3 hour, temperature is at the uniform velocity down to 5~15 DEG C, and the liquid in first degree crystalline device is discharged, described
Liquid is the H that fragrant monoamine kind compound content is 0.5~0.7wt%12MDA；
4) it controls the heating-up time 1~4 hour, temperature at the uniform velocity rises to 15~20 DEG C, and the liquid in first degree crystalline device is discharged, described
Liquid is the H that the fragrant monoamine kind compound content melted in temperature-rise period is 0.6~0.8wt%12MDA；
5) the control heating-up time is 1~5 minute, and temperature at the uniform velocity rises to 25~35 DEG C, and solid melts obtain fragrance in temperature-rise period
Monoamine kind compound content is the H of 0.1~0.2%wt12MDA liquid；
6) by H obtained by step 5)12In the secondary crystallizer that MDA liquid feedstock is 35~45 DEG C to temperature, control temperature fall time is 5
~10 minutes, temperature was at the uniform velocity down to 10~20 DEG C；
7) in 10~20 DEG C of constant temperature, constant temperature time is 1~2 hour；
8) it controls temperature fall time 1~4 hour, temperature is at the uniform velocity down to 5~15 DEG C, and the liquid in secondary crystallizer is discharged, described
Liquid is the H that fragrant monoamine kind compound content is 0.4~0.5wt%12MDA；
9) it controls the heating-up time 1~4 hour, temperature at the uniform velocity rises to 15~20 DEG C, and the liquid in secondary crystallizer is discharged, described
Liquid is the H that the fragrant monoamine kind compound content melted in temperature-rise period is 0.45~0.55wt%12MDA；
10) the control heating-up time is 2~8 minutes, and temperature at the uniform velocity rises to 30~40 DEG C, and solid melts obtain fragrance in temperature-rise period
Monoamine kind compound content is the H of 0.05~0.1wt%12MDA liquid, discharge obtain final products.
6. according to the method described in claim 5, the following steps are included:
1) by H12In the first degree crystalline device that MDA feedstock is 30~35 DEG C to temperature, control temperature fall time is 7.5~10 points
Clock, temperature are at the uniform velocity down to 10~18 DEG C；
2) in 10~18 DEG C of constant temperature, constant temperature time is 1~1.5 hour；
3) it controls temperature fall time 1.5~3 hours, temperature is at the uniform velocity down to 5~12 DEG C, the liquid in first degree crystalline device is discharged, institute
Stating liquid is the H that fragrant monoamine kind compound content is 0.6~0.7wt%12MDA；
4) it controls the heating-up time 2~4 hours, temperature at the uniform velocity rises to 18~20 DEG C, and the liquid in first degree crystalline device is discharged, described
Liquid is the H that the fragrant monoamine kind compound content melted in temperature-rise period is 0.7~0.8wt%12MDA；
5) the control heating-up time is 3~5 minutes, and temperature at the uniform velocity rises to 30~35 DEG C, and solid melts obtain fragrance in temperature-rise period
Monoamine kind compound content is the H of 0.1~0.15%wt12MDA liquid；
6) by H obtained by step 5)12In the secondary crystallizer that MDA liquid feedstock is 35~40 DEG C to temperature, control temperature fall time is 6
~8 minutes, temperature was at the uniform velocity down to 12~18 DEG C；
7) in 12~18 DEG C of constant temperature, constant temperature time is 1.5~2 hours；
8) it controls temperature fall time 2~4 hours, temperature is at the uniform velocity down to 6~13 DEG C, and the liquid in secondary crystallizer is discharged, described
Liquid is the H that fragrant monoamine kind compound content is 0.4~0.45wt%12MDA；
9) it controls the heating-up time 2~4 hours, temperature at the uniform velocity rises to 18~20 DEG C, and the liquid in secondary crystallizer is discharged, described
Liquid is the H that the fragrant monoamine kind compound content melted in temperature-rise period is 0.5~0.55wt%12MDA；
10) the control heating-up time is 4~6 minutes, and temperature at the uniform velocity rises to 35~40 DEG C, and solid melts obtain fragrance in temperature-rise period
Monoamine kind compound content is the H of 0.05~0.06wt%12MDA liquid, discharge obtain final products.
7. according to the method described in claim 5, it is characterized in that, the liquid of the step 8) discharge is as H12MDA raw material follows
Loopback step 1).
8. according to the method described in claim 5, it is characterized in that, the liquid of the step 9) discharge is as H12MDA raw material follows
Loopback step 1).
9. according to the method described in claim 5, it is characterized in that, step 1)~10) absolute pressure be 115KPa~
135KPa。
10. according to the method described in claim 9, it is characterized in that, step 1)~10) absolute pressure be 120KPa~
125KPa。
11. according to the method described in claim 3, it is characterized in that, atmosphere in the first degree crystalline device and secondary crystallizer
For inert gas, the inert gas is selected from nitrogen and/or argon gas.
12. according to the method described in claim 3, the temperature control medium in the crystallizer is the mixed liquor of ethylene glycol and water, institute
The mass ratio for stating ethylene glycol and water is 0.1~1:1.
13. according to the method for claim 12, which is characterized in that the mass ratio of the ethylene glycol and water is 0.2~0.5:
1。
14. the method according to claim 1, wherein the initial color of the dicyclohexyl methyl hydride diisocyanate
Number within 10Hazen；12 months product colors number of storage are within 15Hazen.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1173890A (en) * | 1968-02-28 | 1969-12-10 | Gnii Pi Azotnoj | Process for the Production of Organic Isocyanates |
| US3697570A (en) * | 1969-07-30 | 1972-10-10 | Upjohn Co | Method of preparing organic isocyanates in the presence of molecular sieves |
| US3859323A (en) * | 1969-04-02 | 1975-01-07 | Allied Chem | Preparation of 4,4'-methylenebis (cyclohexylisocyanate) |
| CN103319372A (en) * | 2012-03-19 | 2013-09-25 | 万华化学集团股份有限公司 | Method for producing light colored dicyclohexyl methane diisocyanate |
| CN106554293A (en) * | 2015-09-24 | 2017-04-05 | 万华化学集团股份有限公司 | A kind of method for preparing colourless or light polyisocyanates |
-
2017
- 2017-04-26 CN CN201710281633.8A patent/CN106946741B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1173890A (en) * | 1968-02-28 | 1969-12-10 | Gnii Pi Azotnoj | Process for the Production of Organic Isocyanates |
| US3859323A (en) * | 1969-04-02 | 1975-01-07 | Allied Chem | Preparation of 4,4'-methylenebis (cyclohexylisocyanate) |
| US3697570A (en) * | 1969-07-30 | 1972-10-10 | Upjohn Co | Method of preparing organic isocyanates in the presence of molecular sieves |
| CN103319372A (en) * | 2012-03-19 | 2013-09-25 | 万华化学集团股份有限公司 | Method for producing light colored dicyclohexyl methane diisocyanate |
| CN106554293A (en) * | 2015-09-24 | 2017-04-05 | 万华化学集团股份有限公司 | A kind of method for preparing colourless or light polyisocyanates |
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