CN118005537A - Preparation method of 1, 4-cyclohexane diisocyanate - Google Patents
Preparation method of 1, 4-cyclohexane diisocyanate Download PDFInfo
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- CN118005537A CN118005537A CN202410137448.1A CN202410137448A CN118005537A CN 118005537 A CN118005537 A CN 118005537A CN 202410137448 A CN202410137448 A CN 202410137448A CN 118005537 A CN118005537 A CN 118005537A
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- cyclohexane diisocyanate
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- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- PXQANZCLKWEAHJ-UHFFFAOYSA-N 4-(hydrazinecarbonyl)cyclohexane-1-carboxylic acid Chemical compound NNC(=O)C1CCC(C(O)=O)CC1 PXQANZCLKWEAHJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 38
- 239000012074 organic phase Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 33
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 235000010288 sodium nitrite Nutrition 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 238000006462 rearrangement reaction Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000012267 brine Substances 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000006193 diazotization reaction Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 11
- 239000002360 explosive Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 abstract description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002341 toxic gas Substances 0.000 abstract description 3
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- -1 1, 4-cyclohexanedicarboxylic acid azide Chemical compound 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HXTYZWJVMWWWDK-IZLXSQMJSA-N ClC(=O)[C@H]1CC[C@@H](CC1)C(Cl)=O Chemical compound ClC(=O)[C@H]1CC[C@@H](CC1)C(Cl)=O HXTYZWJVMWWWDK-IZLXSQMJSA-N 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- HXTYZWJVMWWWDK-UHFFFAOYSA-N cyclohexane-1,4-dicarbonyl chloride Chemical compound ClC(=O)C1CCC(C(Cl)=O)CC1 HXTYZWJVMWWWDK-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- POVXOWVFLAAVBH-UHFFFAOYSA-N n-formamidoformamide Chemical compound O=CNNC=O POVXOWVFLAAVBH-UHFFFAOYSA-N 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 1, 4-cyclohexane diisocyanate, and belongs to the technical field of synthesis of diisocyanate. The preparation method is a one-step method for completing the whole reaction, has the advantages of simple reaction route, easily obtained raw materials and mild conditions, avoids the use of highly toxic gas phosgene and explosive sodium azide, has good safety, ensures that the product purity is not lower than 98.5 percent, has 75 percent of yield calculated by 1, 4-cyclohexanedicarboxylic acid hydrazide, and is suitable for large-scale production and application of medical auxiliary materials. The synthetic route aims at adopting conventional and easily available chemical materials to produce cyclohexane diisocyanate under milder conditions. The process has good production prospect and is easy for large-scale industrialized popularization.
Description
Technical Field
The invention belongs to the technical field of synthesis of diisocyanate, and particularly relates to a preparation method of 1, 4-cyclohexane diisocyanate.
Background
The existing synthesis generally adopts triphosgene technology, has larger material toxicity, more environmental protection and potential safety hazard, and is not easy to obtain materials, such as CN102827035, and the technology discloses a synthesis method of 1, 4-cyclohexane diisocyanate, which comprises the following steps: dissolving solid triphosgene in chloroform, cooling the solution to-5-0 deg.c, and dropping 1, 4-cyclohexane diamine slowly; and heating the reaction solution to 40-70 ℃ for reaction for 6 hours, cooling to 10-20 ℃ after the reaction is finished, washing with alkali until the reaction solution is slightly alkaline and neutral, recovering chloroform, and rectifying under reduced pressure to obtain light yellow waxy solid 1, 4-cyclohexane diisocyanate.
In addition, the technology of synthesizing sodium azide belongs to explosive materials, and industrial large-scale production is not easy to realize, such as CN101735111, and the technology discloses a synthesis method of trans-1, 4-cyclohexane diisocyanate, which comprises the following steps: (1) Mixing trans-1, 4-cyclohexanedicarboxylic acid with thionyl chloride, heating and refluxing, and recovering excess thionyl chloride under reduced pressure to obtain trans-1, 4-cyclohexanedicarboxylic acid chloride; (2) Toluene, benzene or xylene are added into trans-1, 4-cyclohexanedicarboxylic acid chloride, the mixture is heated to 45 to 75 ℃, and sodium azide is added to obtain a mixture; (3) The mixture is kept at the temperature of 45-75 ℃ for 0.5-1.5 hours; filtering to remove insoluble substances, recovering toluene under reduced pressure, and rectifying to obtain trans-1, 4-cyclohexane diisocyanate. CN115850117, the technology discloses a preparation method of aliphatic diisocyanate, namely 1, 4-cyclohexane diisocyanate, mainly comprising the following steps: (1) Respectively adding oxalyl chloride and toluene into a three-neck flask, heating an oil bath to 50 ℃, gradually adding the prepared toluene slurry of 1, 4-cyclohexanedicarboxylic acid into the three-neck flask, cooling after the reaction is finished, and removing impurities through reduced pressure distillation to obtain 1, 4-cyclohexanedicarboxylic acid chloride; (2) Adding sodium azide, a small amount of catalyst and deionized water into a three-neck flask, and cooling to below 5 ℃ in an ice water bath; dripping toluene of 1, 4-cyclohexanedicarboxylic acid chloride into a three-neck flask, controlling the bath temperature below 5 ℃, carrying out phase separation after the reaction is finished, adding anhydrous magnesium sulfate into the toluene phase, and drying to obtain a toluene solution of the 1, 4-cyclohexanedicarboxylic acid azide; (3) And (3) dropwise adding the toluene solution of the 1, 4-cyclohexanediformylazide compound into the toluene solution at the temperature of 80-110 ℃, and evaporating the solvent under reduced pressure to obtain the target product.
Disclosure of Invention
The first aim of the invention is to provide a preparation method of 1, 4-cyclohexane diisocyanate, which is a one-step method for completing the whole reaction, has the advantages of simple reaction route, easily obtained raw materials, mild conditions, no use of highly toxic gas phosgene and explosive sodium azide, good safety, product purity not lower than 98.5 percent and yield of 75 percent calculated by 1, 4-cyclohexane dihydrazide, suitability for large-scale production and suitability for application of medical auxiliary materials.
The second object of the present invention is to provide a process for the preparation of 1, 4-cyclohexanediisocyanate, which aims at producing cyclohexanediisocyanate under milder conditions using conventional readily available and inexpensive chemical materials. The process has good production prospect and is easy for large-scale industrialized popularization.
The invention is realized by the following technical scheme:
A preparation method of 1, 4-cyclohexane diisocyanate comprises the following steps:
s1, diazotization reaction:
adding 1, 4-cyclohexanedicarboxylic acid hydrazide into water and acid liquor, adding an organic phase, stirring until the organic phase is dissolved, reducing the reaction temperature to-5-20 ℃, dropwise adding an aqueous solution of sodium nitrite, standing, and washing and drying the organic phase layer by using brine;
S2, rearrangement reaction:
Carrying out rearrangement reaction at 50-60 ℃ and releasing nitrogen, and recovering an organic phase under reduced pressure to obtain yellow turbid liquid;
The yellow turbid liquid is a crude product of 1, 4-cyclohexane diisocyanate;
Adding an extractant into the crude product of the 1, 4-cyclohexane diisocyanate, heating and refluxing for extraction at 50-60 ℃, recovering the extractant under reduced pressure, and rectifying under reduced pressure to obtain colorless to pale yellow liquid;
the colorless to pale yellow liquid is 1, 4-cyclohexane diisocyanate finished product.
The following is a reaction scheme:
the reaction process is a continuous feeding reaction and is carried out in the same reaction system.
Preferably, in the step S1, the acid solution includes any one of a hydrochloric acid solution, a sulfuric acid solution, a phosphoric acid solution, and an acetic acid solution;
The organic phase comprises any one of toluene, chloroform, dichloromethane and dichloroethane;
the mass ratio of the 1, 4-cyclohexanedicarboxylic acid hydrazide to the water to the acid liquor to the organic phase is 1:1-2:1-2:10-12 respectively.
Preferably, the acid solution is hydrochloric acid solution;
the organic phase is chloroform;
The temperature of the reaction is reduced to-5 to 0 ℃.
The water is used as a carrier for dissolving the diformyl hydrazine, and the hydrochloric acid solution is used as an acidic cosolvent to provide an acidic environment.
The pH value of the 1, 4-cyclohexanedicarboxylic acid hydrazide which is added into water and acid liquor to be mixed evenly is less than 1.
Preferably, in the step S1, the mass concentration of the sodium nitrite aqueous solution is 20-50 wt%;
the mass ratio of the sodium nitrite aqueous solution to the 1, 4-cyclohexanedicarboxylic acid hydrazide is 1:1.
Preferably, the mass concentration of the brine is 10-20wt%;
The mass ratio of the brine to the 1, 4-cyclohexanedicarboxylic acid hydrazide is 5-6:1.
Preferably, the mass concentration of the sodium nitrite aqueous solution is 40wt%.
In S1, it is required to control the reaction temperature to-5 to 20℃because the reaction is exothermic, and if the reaction temperature is not controlled, the reaction temperature will rise rapidly, causing a risk. The temperature is controlled to ensure the stability of the material.
The sodium nitrite aqueous solution adopts a dripping mode, and the dripping mode can ensure that the whole reaction temperature is controllable, so that the reaction is more uniform.
Preferably, in the step S2, the rearrangement reaction temperature is 50 to 60 ℃ and the reaction time is 0.5 to 3 hours.
Preferably, in the step S2, the extractant includes any one of toluene, n-hexane, cyclohexane, petroleum ether and n-heptane;
The mass ratio of the crude 1, 4-cyclohexane diisocyanate to the extractant is 1:4-5.
Preferably, in S2, the heating reflux extraction period is 2 to 2.5 hours.
Compared with the prior art, the invention has at least the following technical effects:
The invention provides a preparation method of 1, 4-cyclohexane diisocyanate, which is characterized by one-step method for completing the whole reaction, simple reaction route, easily obtained raw materials, mild condition, no use of highly toxic gas phosgene and explosive sodium azide, good safety, product purity not less than 98.5%, and yield of 75% calculated by 1, 4-cyclohexane diformylhydrazine, and suitability for large-scale production and application of medical auxiliary materials.
The synthetic route aims at adopting conventional and easily available chemical materials to produce cyclohexane diisocyanate under milder conditions. The process has good production prospect and is easy for large-scale industrialized popularization.
Drawings
FIG. 1 is a nuclear magnetic (1 H NMR) detection chart of a1, 4-cyclohexanediisocyanate product.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the following examples, which are to be construed as merely illustrative and not limitative of the scope of the invention, but are not intended to limit the scope of the invention to the specific conditions set forth in the examples, either as conventional or manufacturer-suggested, nor are reagents or apparatus employed to identify manufacturers as conventional products available for commercial purchase.
The technical scheme of a specific implementation mode of the invention is as follows:
A preparation method of 1, 4-cyclohexane diisocyanate comprises the following steps:
s1, diazotization reaction:
adding 1, 4-cyclohexanedicarboxylic acid hydrazide into water and acid liquor, adding an organic phase, stirring until the organic phase is dissolved, reducing the reaction temperature to-5-20 ℃, dropwise adding an aqueous solution of sodium nitrite, standing, and washing and drying the organic phase layer by using brine;
S2, rearrangement reaction:
Carrying out rearrangement reaction at 50-60 ℃ and releasing nitrogen, and recovering an organic phase under reduced pressure to obtain yellow turbid liquid;
The yellow turbid liquid is a crude product of 1, 4-cyclohexane diisocyanate;
Adding an extractant into the crude product of the 1, 4-cyclohexane diisocyanate, heating and refluxing for extraction at 50-60 ℃, recovering the extractant under reduced pressure, and rectifying under reduced pressure to obtain colorless to pale yellow liquid;
the colorless to pale yellow liquid is 1, 4-cyclohexane diisocyanate finished product.
The following is a reaction scheme:
in the step S1, the acid solution comprises any one of hydrochloric acid solution, sulfuric acid solution, phosphoric acid solution and acetic acid solution;
The organic phase comprises any one of toluene, chloroform, dichloromethane and dichloroethane;
the mass ratio of the 1, 4-cyclohexanedicarboxylic acid hydrazide to the water to the acid liquor to the organic phase is 1:1-2:1-2:10-12 respectively.
The acid liquor is hydrochloric acid solution;
the organic phase is chloroform;
The temperature of the reaction is reduced to-5 to 0 ℃.
In the step S1, the mass concentration of the sodium nitrite aqueous solution is 20-50wt%;
the mass ratio of the sodium nitrite aqueous solution to the 1, 4-cyclohexanedicarboxylic acid hydrazide is 1:1.
The mass concentration of the brine is 10-20wt%;
The mass ratio of the brine to the 1, 4-cyclohexanedicarboxylic acid hydrazide is 5-6:1.
The mass concentration of the sodium nitrite aqueous solution is 40wt%.
In the step S2, the rearrangement reaction temperature is 50-60 ℃ and the reaction time is 0.5-3 h.
In the step S2, the extractant comprises any one of toluene, n-hexane, cyclohexane, petroleum ether and n-heptane;
The mass ratio of the crude 1, 4-cyclohexane diisocyanate to the extractant is 1:4-5.
In the step S2, the heating reflux extraction time is 2-2.5 h.
Example 1:
S1, adding 100kg of water and 100kg of industrial hydrochloric acid into a reaction kettle (1), and stirring to dissolve 50kg of 1, 4-cyclohexanedicarboxylic acid hydrazide.
After the dissolution is completed, the feed liquid is transferred to a reaction kettle (2), 300kg of chloroform is added, the temperature is reduced, and when the internal temperature reaches-5 ℃, the feed liquid is ready for use.
Adding 40kg of sodium nitrite and 160kg of water into a high-level preparation tank, stirring and dissolving, and then dropwise adding the sodium nitrite solution into a reaction kettle (2), controlling the reaction temperature to be between-5 and 0 ℃, and continuing to react for half an hour after the addition is completed.
The mixture was allowed to stand to separate an organic phase, the organic phase was washed with 300kg of a 10% sodium chloride solution, the separated organic phase was dried over 50kg of anhydrous magnesium sulfate for 2 hours.
S2, filtering to remove the drying agent, transferring the organic phase into another drying reaction kettle (3), and gradually heating to 50 ℃ to perform rearrangement reaction to generate 1, 4-cyclohexane diisocyanate.
After 2h of reaction, chloroform was recovered under reduced pressure to give a yellow turbid liquid.
200Kg of petroleum ether was added to the yellow turbid liquid, and the mixture was extracted at 60℃under reflux for 2 hours. Recovering petroleum ether under reduced pressure to obtain crude 1, 4-cyclohexane diisocyanate.
And (3) after the crude product is decompressed and rectified, collecting 140-150 ℃/30mmHg fractions to obtain 31.1kg of colorless transparent liquid 1,4 cyclohexane diisocyanate.
The yield calculated by 1, 4-cyclohexanedicarboxylic acid hydrazide is 74.9 percent and the purity of the product is 99.3 percent.
Example 2:
S1, adding 200kg of water and 200kg of industrial hydrochloric acid into a reaction kettle (1), and stirring to dissolve 50kg of 1, 4-cyclohexanedicarboxylic acid hydrazide.
After the dissolution is completed, the feed liquid is transferred to a reaction kettle (2), 600kg of chloroform is added, the temperature is reduced, and when the internal temperature reaches-5 ℃, the material liquid is ready for use.
Adding 40kg of sodium nitrite and 40kg of water into a high-level preparation tank, stirring and dissolving, and then dropwise adding the sodium nitrite solution into a reaction kettle (2), controlling the reaction temperature to be between-5 and 0 ℃, and continuing to react for half an hour after the addition is completed.
The mixture was allowed to stand to separate an organic phase, the organic phase was washed with 300kg of a 10% sodium chloride solution, the separated organic phase was dried over 50kg of anhydrous magnesium sulfate for 2 hours.
S2, filtering to remove the drying agent, transferring the organic phase into another drying reaction kettle (3), and gradually heating to 60 ℃ to perform rearrangement reaction to generate 1, 4-cyclohexane diisocyanate.
After 2h of reaction, chloroform was recovered under reduced pressure to give a yellow turbid liquid.
200Kg of petroleum ether was added to the yellow turbid liquid, and the mixture was extracted at 60℃under reflux with heating for 2 hours. Recovering petroleum ether under reduced pressure to obtain crude 1, 4-cyclohexane diisocyanate.
After the crude product is decompressed and rectified, 140-150 ℃/30mmHg fractions are collected, and 32.5kg of colorless transparent liquid 1,4 cyclohexane diisocyanate is obtained.
The yield of the 1, 4-cyclohexanedicarboxylic acid hydrazide is 78.3 percent and the purity of the product is 99.2 percent.
Example 3:
S1, adding 100kg of water and 100kg of industrial hydrochloric acid into a reaction kettle (1), and stirring to dissolve 50kg of 1, 4-cyclohexanedicarboxylic acid hydrazide.
After the dissolution is completed, the feed liquid is transferred to a reaction kettle (2), 400kg of chloroform is added, the temperature is reduced, and when the internal temperature reaches 10 ℃, the feed liquid is ready for use.
40Kg of sodium nitrite and 40kg of water are added into a high-level preparation tank, after stirring and dissolving, sodium nitrite solution is dripped into a reaction kettle (2), the reaction temperature is controlled at 10 ℃, and the continuous reaction is carried out for half an hour after the addition is completed.
The mixture was allowed to stand to separate an organic phase, the organic phase was washed with 300kg of a 20% sodium chloride solution, the separated organic phase was dried over 50kg of anhydrous magnesium sulfate for 2 hours.
S2, filtering to remove the drying agent, transferring the organic phase into another drying reaction kettle (3), and gradually heating to 50-60 ℃ to perform rearrangement reaction to generate 1, 4-cyclohexane diisocyanate.
After 2h of reaction, chloroform was recovered under reduced pressure to give a yellow turbid liquid.
200Kg of petroleum ether was added to the yellow turbid liquid, and the mixture was extracted at 50℃under reflux with heating for 2 hours. Recovering petroleum ether under reduced pressure to obtain crude 1, 4-cyclohexane diisocyanate.
After the crude product is decompressed and rectified, 140-150 ℃/30mmHg fractions are collected, and 29.3kg of colorless transparent liquid 1,4 cyclohexane diisocyanate is obtained.
The yield calculated by 1, 4-cyclohexanedicarboxylic acid hydrazide is 70.6 percent and the purity of the product is 99.1 percent.
As shown in FIG. 1, the nuclear magnetic (1 H NMR) detection pattern (deuterated chloroform as the test solvent) of the 1, 4-cyclohexane diisocyanate product.
Product structure validation information:
1H NMR(500MHz,CDCl3)δ1.52-1.58(m,4H),2.02-2.05(m,4H),3.55(s,2H)。
Finally, it should be noted that: the foregoing description is only of the preferred embodiments of the invention and is not intended to limit the scope of the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the 1, 4-cyclohexane diisocyanate is characterized by comprising the following steps:
s1, diazotization reaction:
adding 1, 4-cyclohexanedicarboxylic acid hydrazide into water and acid liquor, adding an organic phase, stirring until the organic phase is dissolved, reducing the reaction temperature to-5-20 ℃, dropwise adding an aqueous solution of sodium nitrite, standing, and washing and drying the organic phase layer by using brine;
S2, rearrangement reaction:
Carrying out rearrangement reaction at 50-60 ℃ and releasing nitrogen, and recovering an organic phase under reduced pressure to obtain yellow turbid liquid;
The yellow turbid liquid is a crude product of 1, 4-cyclohexane diisocyanate;
Adding an extractant into the crude product of the 1, 4-cyclohexane diisocyanate, heating and refluxing for extraction at 50-60 ℃, recovering the extractant under reduced pressure, and rectifying under reduced pressure to obtain colorless to pale yellow liquid;
the colorless to pale yellow liquid is 1, 4-cyclohexane diisocyanate finished product.
2. The method for preparing 1, 4-cyclohexane diisocyanate according to claim 1, wherein in S1, the acid solution comprises any one of hydrochloric acid solution, sulfuric acid solution, phosphoric acid solution and acetic acid solution;
The organic phase comprises any one of toluene, chloroform, dichloromethane and dichloroethane;
the mass ratio of the 1, 4-cyclohexanedicarboxylic acid hydrazide to the water to the acid liquor to the organic phase is 1:1-2:1-2:10-12 respectively.
3. The method for preparing 1, 4-cyclohexane diisocyanate according to claim 2, wherein the acid solution is hydrochloric acid solution;
the organic phase is chloroform;
The temperature of the reaction is reduced to-5 to 0 ℃.
4. The method for preparing 1, 4-cyclohexane diisocyanate according to claim 1, wherein in S1, the mass concentration of the sodium nitrite aqueous solution is 20wt% to 50wt%;
the mass ratio of the sodium nitrite aqueous solution to the 1, 4-cyclohexanedicarboxylic acid hydrazide is 1:1.
5. The method for preparing 1, 4-cyclohexane diisocyanate according to claim 1, wherein the mass concentration of the brine is 10wt% to 20wt%;
The mass ratio of the brine to the 1, 4-cyclohexanedicarboxylic acid hydrazide is 5-6:1.
6. The method for producing 1, 4-cyclohexanediisocyanate according to claim 4, wherein the mass concentration of the aqueous solution of sodium nitrite is 40% by weight.
7. The method for preparing 1, 4-cyclohexane diisocyanate according to claim 1, wherein in the step S2, the rearrangement reaction temperature is 50 to 60 ℃ and the reaction time is 0.5 to 3 hours.
8. The method for preparing 1, 4-cyclohexane diisocyanate according to claim 1, wherein in S2, the extractant comprises any one of toluene, n-hexane, cyclohexane, petroleum ether and n-heptane;
The mass ratio of the crude 1, 4-cyclohexane diisocyanate to the extractant is 1:4-5.
9. The method for preparing 1, 4-cyclohexane diisocyanate according to claim 8, wherein in the step S2, the heating reflux extraction time is 2 to 2.5 hours.
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