CN103553969B - Preparation method of 4,4'-dicyclohexylmethane diisocyanate - Google Patents
Preparation method of 4,4'-dicyclohexylmethane diisocyanate Download PDFInfo
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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 divisional application that the application is the applying date is on December 23rd, 2010, application number is 201010602661.3, denomination of invention is " preparation method of HMDI ".
Technical field
The invention belongs to organic compound technical field, be specifically related to a kind of method that non-phosgene prepares 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 obtained by it, have the excellent specific properties such as non yellowing, light stability, weathering resistance and high-mechanical property.Conventional aliphatic category isocyanic ester is isophorone two isocyanide ester (IPDI) and hexamethylene diisocyanate (HDI) at present.Although the former performance is good, owing to mainly leaning on import, its price height is difficult to popularity 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, based on HMDI, includes anti-, along anti-, waits isomer along suitable.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 is obtained, may be used for synthesizing top grade, color inhibition, 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 synthesized by phosgenation at present.Phosgene is hypertoxicity gas, and boiling point is low, volatility is large, in use, transport and storage process, there is great danger.Use phosgene must have complicated conversion unit, refrigeration system, multiple strict security measures and working specification in production.Reaction is carried out usually at high temperature under high pressure in addition, phosgene solubleness is in a solvent limited, metering is difficult in using, greatly excessive phosgene and prolongation reaction times is often needed to guarantee fully carrying out of reaction, this not only easily causes side reaction, increase consumption and the cost of phosgene, also bring larger danger to production.
As at publication number for described in the Chinese invention patent application of CN101429139A, with phosgenation synthesis HMDI time, the usage quantity of phosgene exceedes 250%-2000% of amino mole number; Secondly, also need to use specific installation, as centered by mixing device, injection stream type mixing tank, level and smooth injection mixing nozzle or hole jet mixer reactor are tubular reactor etc.; Again, temperature of reaction is high, pressure is large, diamino-dicyclohexyl methane isomer mixture and phosgene are heated to 300-500 DEG C respectively 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, it is long to there is operational path in 4 '-dicyclohexyl methane diisocyanate, technical sophistication and the defect such as security is poor, a kind of non-phosgene preparation method of dicyclohexyl methane diisocyanate is provided, the method have easy to operate, security is high, 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 with 4,4 '-diamino-dicyclohexyl methane for 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 similar, prepare H with two (trichloromethyl) carbonic ethers or superpalite
12total chemical equation of MDI is as follows:
Two (trichloromethyl) carbonic ether is comparatively stabilization of solid, its toxicity, volatility etc. are far smaller than phosgene, superpalite is then liquid, be easy to feeding operation, in view of phosgenation prepares the number of drawbacks of HMDI existence and great danger, 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 dripping 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, control the input amount of reactant thus reach the process controlling reaction.Reactant can drip simultaneously, or alternate dropwise addition, or is dripped toward another reactant by a reactant.
The present invention is in preparation 4; during 4 '-dicyclohexyl methane diisocyanate; can by a still two step reaction; namely in same reactor, first carry out the acylation reaction compared with low temperature; carry out the dehydrochlorination reaction of higher temperatures again, or acylations and dehydrochlorination two-step reaction carry out simultaneously at higher temperatures in same reactor.The present invention is when preparing HMDI, and reaction also can be undertaken by a point still, as first carried out the acylation reaction compared with low temperature in a reactor, then carries out the dehydrochlorination reaction of higher temperatures at another reactor.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 solid two (trichloromethyl) carbonic ether can be used, or liquid chlorine diphosgene, or the mixture solution of the two is as reactant.Use the superpalite of liquid or used in combination with two (trichloromethyl) carbonic ether, the usage quantity of inert solvent can be reduced and do not affect the accurate-metering that feeds intake.
The present invention is at use two (trichloromethyl) carbonic ether, or superpalite, or the mixture of the two prepares 4, during 4 '-dicyclohexyl methane diisocyanate, two (trichloromethyl) carbonic ether, superpalite or the mixture of the two can be used by accurate-metering, control ingredient proportion.
The present invention is after steaming is except recycling design, and direct 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 refer to not easily with 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 the two 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 controls between-10 – 100 DEG C; more preferably, between 0 – 50 DEG C, thus reaction process is controlled.During second step dehydrochlorination, temperature of reaction controls between 100 – 200 DEG C, more preferably, between 140 – 160 DEG C.If described preparation technology selects acylations and dehydrochlorination two-step reaction to carry out simultaneously, as preferably, temperature of reaction controls between 100 – 200 DEG C, more preferably, between 140 – 160 DEG C.
Two described (trichloromethyl) carbonic ethers or superpalite or the mixture of the two all can be used as phosgenation reagent.Superpalite is active in two (trichloromethyl) carbonic ether, more easily reacts under low temperature, and adds suitable catalyzer and can promote that two (trichloromethyl) carbonic ether decomposes, the carrying out of acceleration acylation reaction.At high temperature, two (trichloromethyl) carbonic ether stability is relatively high, not easily decomposes effusion 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 containing 2, the miscellany of 4 '-diamino-dicyclohexyl methane or other higher homologue, or 4,4 '-diamino-dicyclohexyl methane salt, e.g., 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 '-two cyclohexyl methane diisocyanate, 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, is more preferably 1:1 – 1:4.The mole ratio of diamino-dicyclohexyl methane and superpalite is 1:1 – 1:10, is more preferably 1:1.5 – 1:5.
Described reaction product can a step isolation and purification, and after steaming solvent, direct vacuum fractionation obtains highly purified HMDI product.As preferably, the cut of 163-174 DEG C/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 employs 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 prepare HMDI.Compared with traditional phosgenation, the inventive method is easy to operate, security is high, environmental friendliness, has very large advantage in industrial application.During with phosgenation synthesis HMDI, react and carry out at 300-500 DEG C, pressure is up to 200-3000 mbar, and phosgene is greatly excessive, and equipment is quite complicated, and operational danger is very large.And reaction conditions of the present invention is gentle, reinforced and reaction is carried out at ambient pressure, thus requires to reduce for production unit, and makes work simplification.Meanwhile, the inventive method uses two (trichloromethyl) carbonic ethers or superpalite or the mixture replacing phosgene of the two, this reactant is fed intake accurate measurement, and feed ratio reduces, and thus makes production safety coefficient improve.Vent gas treatment is also simple in addition, and the hydrogen chloride gas produced with water absorption reaction, can prepare high-purity hydrochloric acid, fully use chlorion, be beneficial to environmental protection.
Embodiment
Below specific embodiments of the invention; These embodiments can be done further to supplement and explanation to the present invention; But the present invention is not limited to these embodiments.
The technology used in following examples, unless stated otherwise, is oneself routine techniques of knowing of those skilled in the art; The plant and instrument used, reagent etc., only this specification sheets special instruction, be that the research of this area and technician can be obtained by public approach.In the present embodiment, the not special content indicated is mass content.
Embodiment 1:
400 ml are contained 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 in 2000 ml there-necked flasks respectively, the temperature of reaction system is controlled below 50 DEG C in dropping process.After dropwising, be warming up to backflow 3 hours.After removing solvent under reduced pressure, the cut product of 163-174 DEG C/1.5 mmHg is collected in rectifying.Detecting through GC the content analyzing HMDI isomer mixture is 97.5%, and isocyanate value is determined as 31.1 wt% (theoretical value 32.1 wt%).
Embodiment 2:
400 ml are contained 210.4 g (1 mole) 4, 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 below 50 DEG C.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 DEG C/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:
100 ml cyanobenzenes are added in reaction flask, be warming up to 140 DEG C, 400 ml are contained 210.4 g (1 mole) 4, the cyanobenzene solution that molten and 250 ml of the cyanobenzene of 4 '-diamino-dicyclohexyl methane isomer mixture contain 148.6 g (0.5 mole) two (trichloromethyl) carbonic ether adds in reaction flask simultaneously.Dropwise in 4 hours 140 DEG C time, drip at uniform temp the cyanobenzene solution that 250 ml contain 148.6 g (0.5 mole) two (trichloromethyl) carbonic ether more afterwards, add rear insulation 3 hours.After steaming desolventizes, the cut product of 163-175 DEG C/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 DEG C, the cyanobenzene solution again 200 ml being contained 395.7 g (2 moles) superpalite is slowly added drop-wise in reaction flask, after dropwising, and be incubated 6 hours at this temperature.After removing solvent under reduced pressure, the cut product of 163-174 DEG C/1.5 mmHg is collected in rectifying.Detecting through GC the content analyzing HMDI isomer mixture is 98.6%, and isocyanate value is determined as 31.5 wt% (theoretical value 32.1 wt%).
Embodiment 5:
400 ml are contained 210.4 g (1 mole) 4, 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 below 50 DEG C.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 DEG C/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 210.4 g (1 mole) 4, 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 ether and 197.85 g (1 mole) superpalite.In dropping process, the temperature of reaction system is controlled below 50 DEG C.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 DEG C/1.5 mmHg is collected in rectifying.Detecting through GC the content analyzing HMDI isomer mixture is 96.0%, and isocyanate value is determined as 30.8 wt% (theoretical value 32.1 wt%).
Embodiment 7:
100 ml chlorobenzene solvents are added in reaction flask, be warming up to backflow, 400 ml are contained 210.4 g (1 mole) 4, 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 DEG C/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 DEG C, the cyanobenzene solution again 200 ml being contained 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.After removing solvent under reduced pressure, the cut product of 163-173 DEG C/1.5 mmHg is collected in rectifying.Detecting through GC the content analyzing HMDI isomer mixture 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 DEG C, again 492.5 g (1.66 moles) two (trichloromethyl) carbonic ether (solid) is 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.After removing solvent under reduced pressure, the cut product of 161-173 DEG C/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 amendment or supplement or adopt similar mode to substitute to described specific embodiment, but can't depart from spirit of the present invention or surmount the scope that appended claims defines.Although oneself has made detailed description and has quoted some specific exampless as proof to the present invention, to those skilled in the art, only otherwise it is obvious for leaving that the spirit and scope of the present invention can make various changes or revise.
Claims (1)
1. one kind 4, the preparation method of 4 '-dicyclohexyl methane diisocyanate, it is characterized in that, by 281.3g 4,4 '-diamino-dicyclohexyl methane isomer mixture hydrochloride and 300ml cyanobenzene solvent add in reaction flask, are warming up to 150 DEG C, then cyanobenzene solution 200ml being contained 395.7g superpalite is slowly added drop-wise in reaction flask, after dropwising, and be incubated 6 hours at this temperature; After removing solvent under reduced pressure, the cut product of 163-174 DEG C/1.5mmHg is collected in rectifying; Detecting through GC the content analyzing HMDI isomer mixture is 98.6%, and isocyanate value is determined as 31.5wt%.
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| 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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| 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 |
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