CN108484447A - The synthetic method of m-xylylene diisocyanate - Google Patents
The synthetic method of m-xylylene diisocyanate Download PDFInfo
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- CN108484447A CN108484447A CN201810522661.9A CN201810522661A CN108484447A CN 108484447 A CN108484447 A CN 108484447A CN 201810522661 A CN201810522661 A CN 201810522661A CN 108484447 A CN108484447 A CN 108484447A
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- Prior art keywords
- synthetic method
- added dropwise
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- solid phosgene
- atent solvent
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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
-
- 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
Abstract
The present invention relates to chemical products and chemical technology field, and in particular to a kind of improved m-xylylene diisocyanate synthetic method.It is described to include the following steps：M-xylene diamine solution is added dropwise in solid phosgene solution, other solid phosgene solution is added dropwise after back flow reaction again, and the reaction was continued at reflux, product is down to room temperature, removed under reduced pressure solvent and rectifying, obtains MXDI.Method provided by the invention need not be reduced reaction step process, greatly reduce investment of production cost using photosynthesis is directly consolidated at salt；Equipment requirement is reduced by the tower tower diameter ratio of raising using boundling rectifying mode, without manufacturing prodigious rectifying column, greatly investment is reduced for public works such as steam conduction oils, while also can guarantee throughput requirements.The MXDI purity that this method is prepared is 99.5% or more, and appearance is in colourless transparent liquid, and product yield is higher, has the stronger market competitiveness.
Description
Technical field
The present invention relates to chemical products and chemical technology field, and in particular to a kind of two isocyanide of improved m-phenylenedimethylim-
Acid esters synthetic method.
Background technology
M-xylylene diisocyanate (MXDI) is a kind of important aromatic polyisocyanate product, extensive use
In polyurethane industrial.
In the prior art, MXDI generally with m-xylene diamine (MXDA) be starting material, by after its salinization with phosgene reaction
It is prepared (JPH037253A).The synthetic route has used the phosgene of severe toxicity, it is desirable that and consersion unit has good leakproofness,
Also because resulting in the soaring of totle drilling cost due to the cost of staff's protection and waste gas and liquids treatment input；Simultaneously as phosgene
With high reactivity, therefore the reaction controllability of the synthetic route is not good enough, and production process has higher risk, and is easy
Lead to the undesirable polymerization of product.
To solve the above problems, prior art discloses the synthetic routes for using solid phosgene to substitute gaseous phosgene
(CN106748887A).Compared with aforementioned synthetic route, the prior art is improved still using the MXDA of salinization as reaction raw materials
Place is, using solid phosgene as phosgene source, reaction is completed under the action of the trialkyl phosphine catalyst of specific structure.The conjunction
The use of phosgene is avoided at route, reduces the requirement for consersion unit leakproofness to a certain extent, but it is equally with salt
Change MXDA as reactant, needs to use additional hydrochloric acid, increase cost of material；Reaction process with it is inflammable, corrode and have
The trialkyl phosphine of poison proposes MXDI product purifications high requirement as catalyst.
Invention content
To solve problems of the prior art, the present invention provides a kind of improved m-xylylene diisocyanate
(MXDI) synthetic method, this method eliminate m-xylene diamine and are operated at salt, avoid the use of gaseous phosgene and catalyst,
Procedure is simple, product purity is high, is suitble to the large-scale production of MXDI.
Specifically, the synthetic method of benzene dimethylene diisocyanate (MXDI) provided by the present invention includes following step
Suddenly：
(1) solid phosgene is dissolved in atent solvent, obtains the first solid phosgene solution, heating is spare；
(2) m-xylene diamine (MXDA) is dissolved in atent solvent, obtains m-xylene diamine solution；
(3) the m-xylene diamine solution of step (2) is added dropwise among the solution of the first solid phosgene of step (1)；
(4) after being added dropwise to complete, it is warming up to 80-100 DEG C and insulation reaction 2-3h, then raises temperature to reflux temperature；
(5) solid phosgene is dissolved in atent solvent, obtains the second solid phosgene solution, and the second solid phosgene is molten
Liquid is added dropwise at reflux in the reaction system of step (4)；
(6) after being added dropwise to complete, the reaction was continued at a reflux temperature 4-6h；
(7) product of step (6) is down to room temperature, removed under reduced pressure solvent and rectifying, obtains MXDI.
Further, in the synthetic method：
In step (1), the mass ratio of the solid phosgene and atent solvent is 1:2-5；In step (5), the solid light
The mass ratio of gas and atent solvent is 1：5-10.
In step (2), the mass ratio of the MXDA and atent solvent is 1:2-5.
One or more mixtures of the atent solvent in chlorobenzene, dichloro benzene,toluene,xylene.
Further, step (1) is warming up to 55-70 DEG C, and m-xylene diamine solution is added dropwise in step (3) at 55-70 DEG C.
Further, in step (3), the m-xylene diamine solution is added dropwise in 2-3h.
Further, in step (4), the rate of the heating is 15-20 DEG C/h.
Further, in step (5), the second solid phosgene solution is added dropwise in 4-5h.
Further, in step (7), before the product of step (6) is down to room temperature, inert gas is passed through into reaction kettle
To purge phosgene and HCl.
Further, it is passed through inert gas at 90-100 DEG C.
Further, in step (7)：
The removed under reduced pressure solvent is carried out under conditions of 0.09MPa pressure, 70-120 DEG C.
In the rectifying, use tower diameter ratio for 15-30:1 rectifying column, control vacuum degree is 100Pa to exist hereinafter, collecting tower top
150-151 DEG C of fraction, i.e., MXDI.
Further, in the rectifying, first with 5-10:1 reflux ratio produces front-end volatiles, with complete after extraction front-end volatiles 5~6h
The mode of extraction collects fraction of the tower top at 150-151 DEG C.
Further, the front-end volatiles are mixed with MXDI crude products, as the raw material of rectifying, to further increase whole receipts
Rate.
The beneficial effects of the present invention are：
1, using photosynthesis is directly consolidated, it need not reduce reaction step process at salt, greatly reduce investment of production cost；
2, equipment requirement is reduced by the tower tower diameter ratio of raising using boundling rectifying mode, it is prodigious without manufacturing
Rectifying column reduces greatly investment for public works such as steam conduction oils, while also can guarantee throughput requirements；
3, reaction process does not use gas light, and safety greatly improves, advantageous to environmental protection yet；
4, the MXDI purity that this method is prepared is 99.5% or more, and appearance is in colourless transparent liquid, and product yield is higher,
With the stronger market competitiveness.
Specific implementation mode
Below in conjunction with the embodiment of the present invention, technical scheme of the present invention is clearly and completely described.Based on this
Embodiment in invention, the every other reality that those of ordinary skill in the art are obtained without creative efforts
Example is applied, shall fall within the protection scope of the present invention.
Embodiment 1
(1) 150g solid phosgenes are weighed to be dissolved in 300g chlorobenzenes, obtain the first solid phosgene solution, be warming up to 55 DEG C it is standby
With；
(2) 100g m-xylene diamines (MXDA) are weighed to be dissolved in 200g chlorobenzenes, obtain m-xylene diamine solution；
(3) by the m-xylene diamine solution of step (2) at 55 DEG C in the first solid phosgene for being added drop-wise to step (1) in 2h
Among solution, during dropwise addition, sediment increasingly generates under stirring；
(4) after being added dropwise to complete, 80 DEG C and insulation reaction 2h is warming up to the heating rate of 15 DEG C/h, is then heated up in 2h
To reflux temperature, so that reaction system is in reflux state.
(5) 100g solid phosgenes are dissolved in 500g chlorobenzenes, obtain the second solid phosgene solution, and by the second solid light
Gasoloid is at reflux in the reaction system for being added dropwise to step (4) in 4h；
(6) after being added dropwise to complete, the reaction was continued at a reflux temperature 4h；
(7) to purge phosgene and HCl, then the product of step (6) is passed through inert gas at 90 DEG C into reaction kettle
It is cooled to room temperature, micro insoluble matter, and removed under reduced pressure solvent under conditions of 0.09MPa pressure, 70 DEG C is filtered, it is thick to obtain yellow
Product；
(8) it is 15 by crude product input tower diameter ratio:In 1 rectifying column, in control tower vacuum degree be 100Pa hereinafter,
Heating is to flow back, then with reflux ratio=5:1 extraction front-end volatiles, subsequent 5h is interior to collect tower top at 150 DEG C in a manner of producing entirely
Fraction, as refined MDXI；Front-end volatiles are mixed with crude product, are used again as rectifying raw material.
Embodiment 2
(1) atent solvent that 150g solid phosgenes are dissolved in chlorobenzene, dichloro-benzenes and the toluene composition that gross weight is 450g is weighed
In, obtain the first solid phosgene solution, be warming up to 60 DEG C it is spare；
(2) 100g m-xylene diamines (MXDA) are weighed to be dissolved in atent solvent described in 400g, it is molten to obtain m-xylene diamine
Liquid；
(3) by the m-xylene diamine solution of step (2) at 60 DEG C in the first solid phosgene for being added drop-wise to step (1) in 2.5h
Solution among, during dropwise addition, sediment increasingly generates under stirring；
(4) after being added dropwise to complete, 90 DEG C and insulation reaction 2.5h is warming up to the heating rate of 17 DEG C/h, is then risen in 2h
Temperature is to reflux temperature, so that reaction system is in reflux state.
(5) 100g solid phosgenes are dissolved in atent solvent described in 700g, obtain the second solid phosgene solution, and by
Two solid phosgene solution are at reflux in the reaction system for being added dropwise to step (4) in 4.5h；
(6) after being added dropwise to complete, the reaction was continued at a reflux temperature 5h；
(7) to purge phosgene and HCl, then the product of step (6) is passed through inert gas at 95 DEG C into reaction kettle
It is cooled to room temperature, micro insoluble matter, and removed under reduced pressure solvent under conditions of 0.09MPa pressure, 100 DEG C is filtered, obtains yellow
Crude product；
(8) it is 25 by crude product input tower diameter ratio:In 1 rectifying column, in control tower vacuum degree be 100Pa hereinafter,
Heating is to flow back, then with reflux ratio=7:1 extraction front-end volatiles, subsequent 5.5h is interior to collect tower top 150 in a manner of producing entirely
DEG C fraction, as refined MDXI；Front-end volatiles are mixed with crude product, are used again as rectifying raw material.
Embodiment 3
(1) inertia that 150g solid phosgenes are dissolved in the chlorobenzene of gross weight 750g, dichloro-benzenes, toluene and dimethylbenzene composition is weighed
In solvent, obtain the first solid phosgene solution, be warming up to 70 DEG C it is spare；
(2) 100g m-xylene diamines (MXDA) are weighed to be dissolved in atent solvent described in 500g, it is molten to obtain m-xylene diamine
Liquid；
(3) by the m-xylene diamine solution of step (2) at 70 DEG C in the first solid phosgene for being added drop-wise to step (1) in 3h
Among solution, during dropwise addition, sediment increasingly generates under stirring；
(4) after being added dropwise to complete, 100 DEG C and insulation reaction 3h is warming up to the heating rate of 20 DEG C/h, is then risen in 2h
Temperature is to reflux temperature, so that reaction system is in reflux state.
(5) 100g solid phosgenes are dissolved in atent solvent described in 1000g, obtain the second solid phosgene solution, and will
Second solid phosgene solution is at reflux in the reaction system for being added dropwise to step (4) in 5h；
(6) after being added dropwise to complete, the reaction was continued at a reflux temperature 6h；
(7) product of step (6) is passed through inert gas to purge phosgene and HCl into reaction kettle at 100 DEG C, then dropped
It warms to room temperature, filters micro insoluble matter, and removed under reduced pressure solvent under conditions of 0.09MPa pressure, 120 DEG C, it is thick to obtain yellow
Product；
(8) it is 30 by crude product input tower diameter ratio:In 1 rectifying column, in control tower vacuum degree be 100Pa hereinafter,
Heating is to flow back, then with reflux ratio=10:1 extraction front-end volatiles, subsequent 6h is interior to collect tower top at 151 DEG C in a manner of producing entirely
Fraction, as refined MDXI；Front-end volatiles are mixed with crude product, are used again as rectifying raw material.
Here is the performance parameter of the synthetic method of the m-xylylene diisocyanate described in 1-3 of the embodiment of the present invention
Table 1
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. the synthetic method of benzene dimethylene diisocyanate (MXDI), which is characterized in that include the following steps：
(1) solid phosgene is dissolved in atent solvent, obtains the first solid phosgene solution, heating is spare；
(2) m-xylene diamine (MXDA) is dissolved in atent solvent, obtains m-xylene diamine solution；
(3) the m-xylene diamine solution of step (2) is added dropwise among the solution of the first solid phosgene of step (1)；
(4) after being added dropwise to complete, it is warming up to 80-100 DEG C and insulation reaction 2-3h, then raises temperature to reflux temperature；
(5) solid phosgene is dissolved in atent solvent, obtains the second solid phosgene solution, and the second solid phosgene solution is existed
It is added dropwise under reflux state in the reaction system of step (4)；
(6) after being added dropwise to complete, the reaction was continued at a reflux temperature 4-6h；
(7) product of step (6) is down to room temperature, removed under reduced pressure solvent and rectifying, obtains MXDI.
2. synthetic method according to claim 1, which is characterized in that in step (1), the solid phosgene and atent solvent
Mass ratio be 1：2-5；In step (5), the mass ratio of the solid phosgene and atent solvent is 1：5-10.
3. synthetic method according to claim 1, which is characterized in that in step (2), the matter of the MXDA and atent solvent
Amount is than being 1:2-5.
4. according to claims 1 to 3 any one of them synthetic method, which is characterized in that the atent solvent is selected from chlorobenzene, two
One or more mixtures in chlorine benzene,toluene,xylene.
5. according to claims 1 to 3 any one of them synthetic method, which is characterized in that step (1) is warming up to 55-70 DEG C, step
Suddenly m-xylene diamine solution is added dropwise in (3) at 55-70 DEG C.
6. according to claims 1 to 3 any one of them synthetic method, which is characterized in that in step (3), the isophthalic diformazan
Amine aqueous solution is added dropwise in 2-3h.
7. according to claims 1 to 3 any one of them synthetic method, which is characterized in that in step (4), the speed of the heating
Rate is 15-20 DEG C/h.
8. according to claims 1 to 3 any one of them synthetic method, which is characterized in that in step (5), second solid
Phosgene solution is added dropwise in 4-5h.
9. synthetic method according to claim 1, which is characterized in that in the rectifying, use tower diameter ratio for 15-30:1 essence
Tower is evaporated, control vacuum degree is 100Pa hereinafter, collecting fraction of the tower top at 150~151 DEG C, i.e., MXDI.
10. synthetic method according to claim 9, which is characterized in that in the rectifying, first with 5-10:1 reflux ratio produces
Front-end volatiles then collect fraction of the tower top at 150~151 DEG C in a manner of producing entirely.
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| CN201810522661.9A CN108484447A (en) | 2018-05-28 | 2018-05-28 | The synthetic method of m-xylylene diisocyanate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217975A (en) * | 2018-11-27 | 2020-06-02 | 万华化学集团股份有限公司 | Method for producing resin for optical material |
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| JPH11310567A (en) * | 1998-04-28 | 1999-11-09 | Mitsui Chem Inc | Production of aliphatic isocyanate compound |
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2018
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| CN1045578A (en) * | 1989-02-23 | 1990-09-26 | 三井东压化学株式会社 | The preparation method of eylylene diisocyanate |
| JPH11310567A (en) * | 1998-04-28 | 1999-11-09 | Mitsui Chem Inc | Production of aliphatic isocyanate compound |
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| CN1827593A (en) * | 2005-02-28 | 2006-09-06 | 北京金源化学集团有限公司 | Process for preparing polyisocyanate by solid phosgene |
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| CN107325024A (en) * | 2017-08-11 | 2017-11-07 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of XDI |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217975A (en) * | 2018-11-27 | 2020-06-02 | 万华化学集团股份有限公司 | Method for producing resin for optical material |
| CN111217975B (en) * | 2018-11-27 | 2022-01-07 | 万华化学集团股份有限公司 | Method for producing resin for optical material |
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