CN103553969A - Preparation method of 4,4'-dicyclohexylmethane diisocyanate - Google Patents
Preparation method of 4,4'-dicyclohexylmethane diisocyanate Download PDFInfo
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- CN103553969A CN103553969A CN201310543640.2A CN201310543640A CN103553969A CN 103553969 A CN103553969 A CN 103553969A CN 201310543640 A CN201310543640 A CN 201310543640A CN 103553969 A CN103553969 A CN 103553969A
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Abstract
The invention belongs to the technical field of an organic compound, and particularly relates to a method for preparing 4,4'-dicyclohexylmethane diisocyanate by utilizing a non-phosgene process. The method comprises the following step: reacting 4,4'-dicyclohexylmethane diisocyanate or an isomer mixture or salt thereof, or a mixture of amine and salt thereof which are as raw materials with bis(trichloromethyl) carbonate or trichloromethyl chlorocarbonate or a mixture thereof in an inert solvent. By adopting the method disclosed by the invention, the defects that preparation of the 4,4'-dicyclohexylmethane diisocyanate by utilizing the traditional phosgene process is long in process route, complicated in technique, poor in safety and the like are overcome. The method disclosed by the invention has the advantages of being convenient to operate, high in safety, environment-friendly, and accurate in reactant feeding and metering, and the feeding ratio is reduced, so that the safety coefficient of production is improved. In addition, exhaust treatment is simple; high-purity hydrochloric acid can be prepared from a hydrogen chloride gas generated by water absorption reaction; chloridion can be fully utilized; environmental conservation is facilitated.
Description
The application is to be dividing an application of December 23, application number in 2010 are 201010602661.3, denomination of invention is < < HMDI preparation method > > the applying date.
Technical field
The invention belongs to organic compound technical field, be specifically related to a kind of method that non-phosgene is prepared HMDI.
Background technology
Dicyclohexyl methane diisocyanate, also referred to as hydrogenation MDI, or H
12mDI is a kind of aliphatic category isocyanic ester.The polyurethane products that made by it, have the not excellent specific property such as xanthochromia, light stability, weathering resistance and high-mechanical property.At present conventional aliphatic category isocyanic ester is isophorone two isocyanide esters (IPDI) and hexamethylene diisocyanate (HDI).Although the former performance is good, due to main, by import, its price height is difficult to generally promote always; And the latter is also because its performance, not as the former, is difficult to be applied in high performance polyurethane product.H
12the appearance of MDI can make up the weak point of IPDI and HDI.Dicyclohexyl methane diisocyanate be take HMDI as main, include anti-anti-, along anti-, along along waiting isomer.H
12the raw material diamino-dicyclohexyl methane of MDI can be prepared by hydrogenation diaminodiphenyl-methane, and by H
12the polyurethane material excellent combination property that MDI makes, can be for the synthesis of top grade, resistance to xanthochromia, high temperature resistant products, polyurethane elastomer, aqueous polyurethane, coating, leather etc.In a word, its goods are better than the urethane of the isocyanic ester such as HDI at aspect of performance, and price is lower than the product of IPDI.
HMDI is to be synthesized by phosgenation at present.Phosgene is hypertoxicity gas, and boiling point is low, volatility is large, exists great danger in use, transportation and storage process.In production, use phosgene must have complicated conversion unit, refrigeration system, multiple strict security measures and working specification.Reaction is carried out conventionally under High Temperature High Pressure in addition, the solubleness of phosgene in solvent is limited, in use, be difficult to metering, often need greatly excessive phosgene and prolongation reaction times to guarantee fully carrying out of reaction, this not only easily causes side reaction, the consumption and the cost that increase phosgene, also bring larger danger to production.
Described in the Chinese invention patent application that is CN101429139A at publication number, during with the synthetic HMDI of phosgenation, the usage quantity of phosgene surpasses 250%-2000% of amino mole number; Secondly, also need to use specific installation, as injection stream type mixing tank centered by mixing device, smoothly to spray mixing nozzle or hole jet mixer reactor be tubular reactor etc.; Again, temperature of reaction is high, pressure is large, diamino-dicyclohexyl methane isomer mixture and phosgene are heated to respectively 300-500 ℃ and gasify, then send in the reactor with mixing device and mix, the absolute pressure in the feed-pipe of tubular reactor is 200-3000 mbar.
Summary of the invention
The present invention is directed to traditional phosgenation and prepare 4,4 '-dicyclohexyl methane diisocyanate exists operational path long, the defects such as technical sophistication and security are poor, provide a kind of non-phosgene preparation method of dicyclohexyl methane diisocyanate, the method has easy to operate, safe, advantages of environment protection.
In the present invention, above-mentioned technical problem is solved by the following technical programs:
A kind of 4, the non-phosgene preparation method of 4 '-dicyclohexyl methane diisocyanate, with 4, the miscellany of 4 '-diamino-dicyclohexyl methane or its isomer miscellany or its salt or its amine and salt is raw material, reacts in inert solvent with two (trichloromethyl) carbonic ethers or superpalite or the mixture of the two.The present invention is with 4, and 4 '-diamino-dicyclohexyl methane is raw material, with two (trichloromethyl) carbonic ether; or superpalite; or the mixture of the two and described raw material carry out acylation reaction, then dehydrochlorination generates HMDI (H
12mDI).Its reaction mechanism and phosgene reaction are similar, with two (trichloromethyl) carbonic ethers or superpalite, prepare H
12total chemical equation of MDI is as follows:
Two (trichloromethyl) carbonic ether is compared with stabilization of solid, its toxicity, volatility etc. are far smaller than phosgene, superpalite is liquid, be easy to reinforced operation, in view of phosgenation, prepare number of drawbacks and the great danger that HMDI exists, therefore two (trichloromethyl) carbonic ethers and superpalite become desirable substitute, be more suitable for suitability for industrialized production HMDI.
The present invention is utilizing two (trichloromethyl) carbonic ether, or superpalite, or the mixture of the two and 4, when HMDI is prepared in the reaction of 4 '-diamino-dicyclohexyl methane, by drip 4 in reactor, the solution of 4 '-diamino-dicyclohexyl methane or its salt and two (trichloromethyl) carbonic ether, or superpalite, or the method for the mixture solution of the two, thus the input amount of controlling reactant reaches the process of controlling reaction.Reactant can drip simultaneously, or alternately drips, or a reactant is dripped toward another reactant.
The present invention is in preparation 4; during 4 '-dicyclohexyl methane diisocyanate; can react by still two steps; in same reactor, first carry out the acylation reaction of lower temperature; carry out again the dehydrochlorination reaction of higher temperatures, or in same reactor under higher temperatures acylations and dehydrochlorination two-step reaction carry out simultaneously.The present invention is when preparing HMDI, and reaction also can be undertaken by a minute still, as first carried out the acylation reaction of lower temperature in a reactor, then at another reactor, carries out the dehydrochlorination reaction of higher temperatures.The present invention, when preparing HMDI, also can carry out in flow reactor in segmentation.
The present invention, when preparing HMDI, can use the inertia solution of two (trichloromethyl) carbonic ether or superpalite inertia solution or the mixture inertia solution of the two as a kind of reactant.Also can use solid two (trichloromethyl) carbonic ether, or liquid chlorine diphosgene, or the mixture solution of the two is as reactant.Use liquid superpalite or with the use that mixes of two (trichloromethyl) carbonic ether, can reduce the usage quantity of inert solvent and not affect the accurate-metering that feeds intake.
The present invention is using two (trichloromethyl) carbonic ether, or superpalite, or the mixture of the two prepares 4, during 4 '-dicyclohexyl methane diisocyanate, can use two (trichloromethyl) carbonic ether, superpalite or the mixture of the two by accurate-metering, control ingredient proportion.
The present invention is steaming except after reclaiming solvent, and directly vacuum fractionation obtains highly purified HMDI product.
As preferably, two described (trichloromethyl) carbonic ethers or superpalite or the mixture of the two are dissolved in inert solvent in advance, then react.Inert solvent in the present invention refers to and is difficult for and two (trichloromethyl) carbonic ether, superpalite and 4, the kind solvent that 4 '-diamino-dicyclohexyl methane or its hydrochloride react.Inert solvent Main Function is diluting reaction thing, realizes homogeneous reaction, is conducive to the generation of main reaction and controls the generation of side reaction.As preferably, described inert solvent is aromatic hydrocarbon, halogenated aryl hydrocarbon, halogenated aliphatic hydrocarbon, aliphatic ester compounds or aromatic ester compounds, aliphatics nitrile or aromatic series nitrile organic solvent, can be but be not limited to toluene, dimethylbenzene, chlorobenzene, dichlorobenzene, cyanobenzene, acetonitrile, ethyl acetate, butylacetate, methyl benzoate etc., can be even that the two is with the mixture of arbitrary proportion, as toluene and cyanobenzene 1:1(mass ratio) mixture.
If described preparation technology selects low temperature and high temperature two-step reaction to carry out respectively, as preferably, during initial acylation reaction; during dropwise reaction thing, temperature of reaction is controlled between 100 ℃ of-10 –; more preferably, between 50 ℃ of 0 –, thereby control reaction process.During second step dehydrochlorination, temperature of reaction is controlled between 200 ℃ of 100 –, more preferably, and between 160 ℃ of 140 –.If described preparation technology selects acylations and dehydrochlorination two-step reaction to carry out simultaneously, as preferably, temperature of reaction is controlled between 200 ℃ of 100 –, more preferably, and between 160 ℃ of 140 –.
Two described (trichloromethyl) carbonic ethers or superpalite or the mixture of the two all can be used as phosgenation reagent.Superpalite activity, higher than two (trichloromethyl) carbonic ether, is more easily reacted under low temperature, and adds suitable catalyzer can promote two (trichloromethyl) carbonic ether to decompose, and accelerates the carrying out of acylation reaction.At high temperature, two (trichloromethyl) carbonic ether stability is relatively high, is difficult for decomposing and overflowing very soon, is more conducive to reaction and carries out.
Described preparation 4, the raw material of 4 '-dicyclohexyl methane diisocyanate can be 4, the various isomer of 4 '-diamino-dicyclohexyl methane, isomer miscellany or contain 2, the miscellany of 4 '-diamino-dicyclohexyl methane or other higher homologue, or 4,4 '-diamino-dicyclohexyl methane salt, as, its hydrochloride, carbonate etc., or the miscellany of its salt and amine.
Two described (trichloromethyl) carbonic ethers or superpalite or the mixture of the two are as phosgenation reagent and 4,4 '-diamino-dicyclohexyl methane reaction preparation 4, during 4 '-bis-cyclohexyl methane diisocyanates, per molecule two (trichloromethyl) carbonic ether is equivalent to three molecule phosgene, per molecule superpalite is equivalent to two molecule phosgene, as preferably, 4, the mole ratio of 4 '-diamino-dicyclohexyl methane and two (trichloromethyl) carbonic ether is 1:0.67 – 1:10, more preferably 1:1 – 1:4.The mole ratio of diamino-dicyclohexyl methane and superpalite is 1:1 – 1:10, more preferably 1:1.5 – 1:5.
Described reaction product can a step isolation and purification, and after steaming solvent, directly vacuum fractionation obtains highly purified HMDI product.As preferably, the cut of 163-174 ℃/1.5 mmHg is collected in rectifying, and in this cut, the purity of dicyclohexyl methane diisocyanate meets or exceeds 98.6%, and isocyanate value is determined as 31.5 wt% or close to theoretical value 32.1 wt%.
The inventive method has been used two (trichloromethyl) carbonic ethers or superpalite or the mixture replacing phosgene of the two, and with 4,4 '-diamino-dicyclohexyl methane or its reactant salt are prepared HMDI.Compare with traditional phosgenation, the inventive method is easy to operate, safe, environmental friendliness, has very large advantage aspect industrial application.During with the synthetic HMDI of phosgenation, reaction is carried out at 300-500 ℃, and pressure is up to 200-3000 mbar, and phosgene is greatly excessive, equipment very complex, and operational danger is very large.And reaction conditions of the present invention is gentle, reinforced and reaction is carried out under normal pressure, thereby requires to reduce for production unit, and makes work simplification.Meanwhile, the inventive method is used two (trichloromethyl) carbonic ethers or superpalite or the mixture replacing phosgene of the two, makes this reactant accurate measurement that feeds intake, and feed ratio reduces, thereby production safety coefficient is improved.Vent gas treatment is also simple in addition, and the hydrogen chloride gas that water absorption reaction produces, can prepare high-purity hydrochloric acid, fully uses chlorion, is beneficial to environmental protection.
Embodiment
Below specific embodiments of the invention; These embodiment can do further to supplement and explanation to the present invention; But the present invention is not limited to these embodiment.
The technology of using in following examples, unless stated otherwise, is oneself routine techniques of knowing of those skilled in the art; The plant and instrument using, reagent etc., this specification sheets special instruction only, is that the research of this area and technician can obtain by public approach.In the present embodiment, the not special content of indicating is mass content.
Embodiment 1:
400 ml are contained to 210.4 g (1 mole) 4, the o-dichlorobenzene solution that the o-dichlorobenzene solution of 4 '-diamino-dicyclohexyl methane isomer mixture and 300 ml contain 396 g (1.34 moles) two (trichloromethyl) carbonic ether slowly joins respectively in 2000 ml there-necked flasks, in dropping process, the temperature of reaction system is controlled at below 50 ℃.After dropwising, be warming up to and reflux 3 hours.Remove under reduced pressure after solvent, the cut product of 163-174 ℃/1.5 mmHg is collected in rectifying.The content that detects analysis HMDI isomer mixture through GC is 97.5%, and isocyanate value is determined as 31.1 wt% (theoretical value 32.1 wt%).
Embodiment 2:
400 ml are contained to 210.4 g (1 mole) 4, and the cyanobenzene solution of 4 '-diamino-dicyclohexyl methane isomer mixture slowly joins the cyanobenzene solution that 300 ml contain 396 g (1.34 moles) two (trichloromethyl) carbonic ether.In dropping process, the temperature of reaction system is controlled at below 50 ℃.After dropwising, be warming up to backflow, and the insulation 3 hours that refluxes at this temperature.After steaming desolventizes, the cut product of 160-176 ℃/1.5 mmHg is collected in rectifying.The content that GC analyzes HMDI isomer mixture is 83.2%.Isocyanate value is determined as 26.7 wt% (theoretical value 32.1 wt%).
Embodiment 3:
In reaction flask, add 100 ml cyanobenzenes, be warming up to 140 ℃, 400 ml are contained to 210.4 g (1 mole) 4, and the cyanobenzene cyanobenzene solution molten and that 250 ml contain 148.6 g (0.5 mole) two (trichloromethyl) carbonic ether of 4 '-diamino-dicyclohexyl methane isomer mixture adds in reaction flask simultaneously.In the time of 140 ℃, in 4 hours, dropwise, at uniform temp, drip again the cyanobenzene solution that 250 ml contain 148.6 g (0.5 mole) two (trichloromethyl) carbonic ether afterwards, add rear insulation 3 hours.After steaming desolventizes, the cut product of 163-175 ℃/1.5 mmHg is collected in rectifying.The content that GC analyzes HMDI isomer mixture is 98.5%, and isocyanate value is determined as 31.5 wt% (theoretical value 32.1 wt%).
Embodiment 4:
By 281.3 g(1 mole) 4,4 '-diamino-dicyclohexyl methane isomer mixture hydrochloride and 300 ml cyanobenzene solvents add in reaction flask, be warming up to 150 ℃, the cyanobenzene solution that again 200 ml is contained to 395.7 g (2 moles) superpalite is slowly added drop-wise in reaction flask, after dropwising, and be incubated 6 hours at this temperature.Remove under reduced pressure after solvent, the cut product of 163-174 ℃/1.5 mmHg is collected in rectifying.The content that detects analysis HMDI isomer mixture through GC is 98.6%, and isocyanate value is determined as 31.5 wt% (theoretical value 32.1 wt%).
Embodiment 5:
400 ml are contained to 210.4 g (1 mole) 4, and the o-dichlorobenzene solution of 4 '-diamino-dicyclohexyl methane isomer mixture slowly joins the o-dichlorobenzene solution that 100 ml contain 397.0 g (2 moles) superpalite.In dropping process, the temperature of reaction system is controlled at below 50 ℃.After dropwising, be warming up to backflow, and the insulation 3 hours that refluxes at this temperature.After steaming desolventizes, the cut product of 163-175 ℃/1.5 mmHg is collected in rectifying.The content that GC analyzes HMDI isomer mixture is 98.1%, and isocyanate value is determined as 31.4 wt% (theoretical value 32.1 wt%).
Embodiment 6:
400 ml are contained to 210.4 g (1 mole) 4, and the chlorobenzene solution of 4 '-diamino-dicyclohexyl methane isomer mixture slowly joins the chlorobenzene solution that 250 ml contain 99 g (0.33 mole), two (trichloromethyl) carbonic ethers and 197.85 g (1 mole) superpalite.In dropping process, the temperature of reaction system is controlled at below 50 ℃.After dropwising, be warming up to backflow, and the insulation 3 hours that refluxes at this temperature.After steaming desolventizes, the cut product of 162-175 ℃/1.5 mmHg is collected in rectifying.The content that detects analysis HMDI isomer mixture through GC is 96.0%, and isocyanate value is determined as 30.8 wt% (theoretical value 32.1 wt%).
Embodiment 7:
In reaction flask, add 100 ml chlorobenzene solvents, be warming up to backflow, 400 ml are contained to 210.4 g (1 mole) 4, and the chlorobenzene solution that the chlorobenzene solution of 4 '-diamino-dicyclohexyl methane isomer mixture and 600 ml contain 594.8 g (2 moles) two (trichloromethyl) carbonic ether slowly drops in reaction flask simultaneously.After dropwising, and the insulation 3 hours that refluxes at this temperature.After steaming desolventizes, the cut product of 162-174 ℃/1.5 mmHg is collected in rectifying.The content that GC analyzes HMDI isomer mixture is 94.8%, and isocyanate value is determined as 30.4 wt% (theoretical value 32.1 wt%).
Embodiment 8:
By 282.1 g(1 mole) 4,4 '-diamino-dicyclohexyl methane isomer mixture hydrochloride and 300 ml cyanobenzene solvents add in reaction flask, be warming up to 150 ℃, the cyanobenzene solution that again 200 ml is contained to 195.7 g (1 mole) superpalite and 297.4 g (1 mole) two (trichloromethyl) carbonic ether is slowly added drop-wise in the solution of diamino-dicyclohexyl methane isomer mixture hydrochloride and cyanobenzene, after dropwising, and the insulation 5 hours that refluxes at this temperature.Remove under reduced pressure after solvent, the cut product of 163-173 ℃/1.5 mmHg is collected in rectifying.The content that detects analysis HMDI isomer mixture through GC is 97.4%, and isocyanate value is determined as 31.3 wt% (theoretical value 32.1 wt%).
Embodiment 9:
By 282.5 g(1 mole) 4,4 '-diamino-dicyclohexyl methane isomer mixture hydrochloride and 400 ml cyanobenzene solvents add in reaction flask, be warming up to 150 ℃, again 492.5 g (1.66 moles) two (trichloromethyl) carbonic ethers (solid) are slowly added in the solution of diamino-dicyclohexyl methane isomer mixture hydrochloride and cyanobenzene, after dropwising, and the insulation 5 hours that refluxes at this temperature.Remove under reduced pressure after solvent, the cut product of 161-173 ℃/1.5 mmHg is collected in rectifying.The content that GC analyzes HMDI isomer mixture is 93.8%, and isocyanate value is determined as 30.1 wt% (theoretical value 32.1 wt%).
Specific embodiment described in the present invention is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various modifications or supplement or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.Although oneself has made detailed explanation and has quoted some specific exampless as proof to the present invention, to those skilled in the art, only otherwise it is obvious leaving that the spirit and scope of the present invention can make various changes or revise.
Claims (10)
1. one kind 4, the preparation method of 4 '-dicyclohexyl methane diisocyanate, it is characterized in that: with 4, the miscellany of 4 '-diamino-dicyclohexyl methane or its isomer miscellany or its salt or its amine and salt is raw material, reacts in inert solvent with two (trichloromethyl) carbonic ethers or superpalite or the mixture of the two.
2. preparation method according to claim 1, it is characterized in that: in two (trichloromethyl) carbonic ethers or superpalite or the mixture of the two and 4, the miscellany reaction preparation 4 of 4 '-diamino-dicyclohexyl methane or its isomer miscellany or its salt or its amine and salt, during 4 '-dicyclohexyl methane diisocyanate, by the method for dropwise reaction thing in reactor, control the input amount of reactant and the process of reaction, reactant or simultaneously dropping, or alternately drip, or a reactant is dripped toward another reactant.
3. preparation method according to claim 1, it is characterized in that: 4,4 '-dicyclohexyl methane diisocyanate makes respectively with low temperature and high temperature two-step reaction, and the first step temperature of reaction is between 100 ℃ of-10 –, and second step temperature of reaction is between 200 ℃ of 100 –.
4. preparation method according to claim 1, is characterized in that: HMDI makes with acylations and dehydrochlorination two-step reaction simultaneously, and temperature of reaction is between 200 ℃ of 100 –.
5. according to the preparation method described in any one in claim 1-4, it is characterized in that: two described (trichloromethyl) carbonic ethers or superpalite or the mixture of the two are dissolved in inert solvent in advance, then react; Or use solid two (trichloromethyl) carbonic ether, or liquid chlorine diphosgene, or the mixture solution of the two reacts as reactant.
6. according to the preparation method described in any one in claim 1-4, it is characterized in that: described inert solvent is aromatic hydrocarbon, halogenated aryl hydrocarbon, halogenated aliphatic hydrocarbon, aliphatic ester compounds or aromatic ester compounds, aliphatics nitrile or aromatic series nitrile organic solvent.
7. according to the preparation method described in any one in claim 1-4, it is characterized in that: prepare 4, the raw material of 4 '-dicyclohexyl methane diisocyanate comprises 4,4 '-diamino-dicyclohexyl methane, its isomer miscellany, 4, the salt of 4 '-diamino-dicyclohexyl methane or 4, the amine of 4 '-diamino-dicyclohexyl methane and the miscellany of salt, 4, the salt of 4 '-diamino-dicyclohexyl methane comprises its hydrochloride, carbonate, vitriol or phosphoric acid salt.
8. according to the preparation method described in any one in claim 1-4, it is characterized in that: two described (trichloromethyl) carbonic ethers or superpalite or the mixture of the two are as phosgenation reagent and 4,4 '-diamino-dicyclohexyl methane reaction preparation 4, during 4 '-dicyclohexyl methane diisocyanate, 4, the mole ratio of 4 '-diamino-dicyclohexyl methane and two (trichloromethyl) carbonic ether is 1:0.67 – 1:10; 4, the mole ratio of 4 '-diamino-dicyclohexyl methane and superpalite is 1:1 – 1:10.
9. according to the preparation method described in any one in claim 1-4, it is characterized in that: the product that described reaction obtains obtains HMDI or its isomer miscellany through vacuum fractionation.
10. preparation method according to claim 8, is characterized in that: the product that described reaction obtains obtains HMDI or its isomer miscellany through vacuum fractionation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106045882A (en) * | 2016-06-03 | 2016-10-26 | 山东崇舜化工有限公司 | Method for synthesizing pentamethylene diisocyanate |
| CN108912013A (en) * | 2018-05-16 | 2018-11-30 | 丽水学院 | A kind of synthetic method of aryl formyl based isocyanate |
| CN114380715A (en) * | 2022-01-24 | 2022-04-22 | 纳琳威纳米科技（上海）有限公司 | Preparation method of hydrogenated phenylmethane diisocyanate |
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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 |
| CN101429139A (en) * | 2008-12-18 | 2009-05-13 | 宁波万华聚氨酯有限公司 | Process for producing dicyclohexyl methyl hydride diisocyanate and its midbody |
| CN101805271A (en) * | 2010-03-31 | 2010-08-18 | 北京金方博源科技发展有限公司 | Alicyclic diisocyanate and preparation method and purposes thereof |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101429139A (en) * | 2008-12-18 | 2009-05-13 | 宁波万华聚氨酯有限公司 | Process for producing dicyclohexyl methyl hydride diisocyanate and its midbody |
| CN101805271A (en) * | 2010-03-31 | 2010-08-18 | 北京金方博源科技发展有限公司 | Alicyclic diisocyanate and preparation method and purposes thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106045882A (en) * | 2016-06-03 | 2016-10-26 | 山东崇舜化工有限公司 | Method for synthesizing pentamethylene diisocyanate |
| CN108912013A (en) * | 2018-05-16 | 2018-11-30 | 丽水学院 | A kind of synthetic method of aryl formyl based isocyanate |
| CN114380715A (en) * | 2022-01-24 | 2022-04-22 | 纳琳威纳米科技（上海）有限公司 | Preparation method of hydrogenated phenylmethane diisocyanate |
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