CN101205200A - Multi-step method for continuously producing toluene diisocyanate - Google Patents
Multi-step method for continuously producing toluene diisocyanate Download PDFInfo
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- CN101205200A CN101205200A CNA2007101621790A CN200710162179A CN101205200A CN 101205200 A CN101205200 A CN 101205200A CN A2007101621790 A CNA2007101621790 A CN A2007101621790A CN 200710162179 A CN200710162179 A CN 200710162179A CN 101205200 A CN101205200 A CN 101205200A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/06—Preparation of derivatives of isocyanic acid from or via ureas
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention provides a multi-step method for continuously producing alicyclic vulcabond on the condition of non light and non-air, by the reaction of the alicyclic diamine and the carboxylic acid derivatives with alcohol producing alicyclic diurethane and subsequently decomposed into alicyclic vulcabond, characterized in that diurethane is formed by two steps, thermo-decomposing via removing diurethane of the easier boiler and the medium boiler to release desirable vulcabond, and continuously draining the product on the bottom of the part degradable tower of the degradable equipment, proceeding re-urethane by alcohol, then separating the high boiler, and then making the re-urethane product circle in the process, wherein using the unprocessed carbamide and/or carbamide equivalent made of un-precessed carbamide.
Description
Technical field
The present invention relates to a kind of multistep method for preparing alicyclic diisocyanate continuously with no phosgene ground.
Background technology
The route of synthesis of isocyanic ester can be realized via a series of different paths.The earliest and so far the scheme that still occupies leading big industrial preparation isocyanic ester is so-called phosgenation.The basis of this method is the reaction of amine and phosgene.The defective of phosgenation has been to use phosgene, and phosgene is because its toxicity and corrodibility and the operation on the technical scale has been proposed high requirement.
Now also exist multiple walk around use phosgene prepare the method for isocyanic ester with technical scale.Term " method of no phosgene " makes the process that amine changes isocyanic ester into interrelate (EP18586, EP355443, US4268683, EP990644) usually with under the condition of using alternate carbonylation agent such as urea or dialkyl carbonate.
The basis in described urea path is to make diamines change vulcabond into by two step process via urea.In the first step, make diamines and alcohol reaction under the condition that has urea or urea Equivalent (as alkyl carbonate, alkyl carbamate) generate two urethanes, two urethanes usually again through an intermediate purification step and then in second step thermolysis be vulcabond and alcohol (EP355443, US4713476, US5386053).Alternatively, also can insert independent passing through before real urethane forming process expressly makes diamines and urea reaction prepare the process (EP568782) of two ureas.Also can consider to follow the two steps orders (EP657420) of measuring interpolation and urethane diamines by the partial reaction and second step of the first step urea and alcohol.
The urethane thermolysis is that the process of corresponding isocyanate and alcohol is just known for a long time, and this process both can also can be carried out in lesser temps in liquid phase in comparatively high temps in gas phase.But the problem of these two kinds of methods is because heat load basically unfavorable side reaction can take place, and this side reaction can reduce yield on the one hand, also can cause forming resinification by product on the other hand, this by product can obviously be upset the technical process in reactor and the equipment for purifying owing to applying (Belegung) and obstruction.
Therefore also just be no lack of some of the recommendations are arranged, obtain the formation that yield improves and suppress unfavorable by product by the measure on chemistry and the operative technique.For example in a series of document, put down in writing and used the catalyzer (DE1022222, US3919279, DE2635490) that can quicken the urethane decomposition reaction.In fact, can fully successfully improve the yield of isocyanic ester under the have suitable catalyst condition of---referring to the organic compound of many alkalescence, acidity and metal here---with respect to uncatalyzed scheme.So but also owing to exist the formation that catalyzer can not be avoided unfavorable by product.For heat and catalyzer in reaction medium the equally distributed situation of inert solvent that other use is for example recommended in US3919279 and DE2635490, equally also be like this to guarantee to import.But in principle, use that the ebullient solvent can bring isocyanic ester volume/time under the reflux conditions-result that yield descends and can attach the too high shortcoming of energy consumption.
The embodiment of the single urethane of the thermal induction catalytic decomposition described in the EP54817 has described reaction mixture has partly been discharged the resinification by product that is produced in the urethane decomposition course to be separated in.This operation plays the effect that applies and block avoided in reactor and the processing unit (plant).But wherein do not exist hint can utilize this part to eject the enlightenment that improves yield.Put down in writing similar solution among the EP61013, pyrolytic process is to carry out existing under the condition of solvent in this scheme, and its task obviously is to absorb better difficult evaporable by product.Here do not utilize part discharge measure from the optimized angle of yield yet.
Known from EP355443, if the by product higher molecular weight that will produce in decomposition reactor in two urethane decomposition coursees, that can utilize and can not utilize is discharged from reactor as far as possible continuously to guarantee without interruption and optionally reaction, and then under the condition that has alcohol, make its most of reaction and be recycled in the two urethane preparation process, then just can improve yield.Described method is accompanied by higher energy consumption, because will separate from the discharge material of two urethanes preparation by the by product that distillation can not utilize, must evaporate two all urethanes simultaneously.Different with EP355443, be that discharge material with the urethane reaction is assigned as two part logistics in the method for EP566925, therefrom having only a part logistics is to remove its high boiling and can not utilize by product by distillation, then two urethane logistics of merger is imported in the decomposition reaction in the decomposition reactor.In addition, be that the successive decomposition reactor is discharged material directly, promptly turn the step of usefulness into and be recycled in the building-up process of two urethanes without urethane again in EP566925.
In the one kettle way reaction, are practical situation of using always and are documented in a series of patent documentation (EP18568, EP355443, EP566925) by preparation two urethanes under the condition of urea, diamines and pure separation of ammonia at the same time.Shortcoming is that owing to urea, pure and mild diamines react inevitable simultaneously and can form by product in large quantities, this by product is unfavorable for the selectivity of reacting and must be removed before two urethane thermolysiss.Therefore; claimed a kind of method for preparing fat (ring) (cyclo) aliphatic diisocyanates continuously among the EP568782; this method consists essentially of three key steps; wherein the first step is to form two ureas, and second step formed two urethanes by two ureas and the 3rd step was in liquid phase two urethanes to be decomposed into the ideal vulcabond---i.e. the preparation of two urethanes will be finished in two separation steps.Instruction according to EP568782, at first by distillation from the discharge material of the two urethane building-up reactions sequences that form and follow by two ureas, remove easily boil thing and in boil thing as alcohol, carbaminate/ester and carbonic ether, and then evaporate the high boiling material of removing in two urethanes by short distance.Two urethanes are understood thermolysis and the bottom product that a part is decomposed are discharged continuously, carry out urethaneization again and be recycled in the two urethane synthesis steps with alcohol going.
Now, the primary commercial form of the urea of big industrial preparation is a bead, that is to say that diameter is the pellet of 1-3mm.Crystalline urea also can tend to lump consumingly (Verbacken) when water-content very low (＜0.1%), thereby makes it be not suitable for a large amount of storages.For the urea bead that for example as if must deposit in a large number in the silo, can adopt powder mass such as talcum, wilkinite, silica gel, diatomite or other silicates materials by subsequently bead being carried out surface treatment or improves its storing performance by sulphur with by spraying a spot of oil.
Now, urea industry all preferably will be no more than 0.6 weight % formaldehyde (Ullmann ' sEncyclopedia of Industrial Chemistry, 2006 the 7th edition) before granulation, add in the urea melt and go, to improve the stability of bead.This measure is used for preventing that transportation from taking place to decompose and lump also also in order to improve storage stability.
By make before pearl or the granulation through add urea that urea melt that formaldehyde (also having paraformaldehyde) handled makes and with formaldehyde (also having paraformaldehyde) no matter surface-treated urea---it is the measure that improves bead storage property of industrial practicality equally---in step of the alicyclic double carbamate of preparation, two steps and alternative multistep method or following when alicyclic double carbamate thermolysis is alicyclic diisocyanate, all can cause the unfavorable by product of formation.
Formed by product promptly not only can cause forming unfavorable caking in equipment after very short time in the double carbamate building-up process of step of carrying out continuously or multistep, the result make to produce the time length and shortens and need expensive cleaning process thereafter, and all can't satisfactorily it be separated in the step of the rough double carbamate of being recorded and narrated in known and document of each distillation purification.
In order to be in the equipment of alicyclic diisocyanate with alicyclic double carbamate thermolysis, that can't quantitatively remove all can cause caking and therefore and because the cleaning process of costliness has reduced the use properties of equipment extraly from the by product in double carbamate stage itself and the new therefrom a series of by products that produce.
Surprisingly, this task can be solved by following scheme, promptly in order to make alicyclic vulcabond, by making alicyclic diamines and urea and/or urea Equivalent (for example alkyl carbonate, alkyl carbamate) and alcohol reaction generate alicyclic double carbamate and being that alicyclic vulcabond carries out then with alicyclic double carbamate thermolysis, wherein for forming alicyclic double carbamate, adopt not rely on that dosage form is (bead, particle, crystal, melt, solution), undressed urea.Undressed urea both is meant without surface treatment and did not also add additive in melt before making pearl or granulation and/or formaldehyde goes.
The used urea and be preparation urea Equivalent (alkyl carbonate for example according to the present invention, alkyl carbamate) urea that conduct is used for the possible precursor of synthesis of alicyclic double carbamate is undressed, be that it need not to carry out surface treatment with inorganic substance, as adopt talcum, wilkinite, silica gel, diatomite, kaolin or other also can carry out surface treatment as the silicates material of anti-caking agent, and/or needn't derive from the urea melt after handling with formaldehyde (also can be paraformaldehyde) and/or needn't carry out surface treatment with formaldehyde (also can be paraformaldehyde).Usually, the maximum concentration of formaldehyde of used urea or used urea Equivalent (also can be paraformaldehyde) is 0.01 to 0.10 weight %, preferred 0.001 to 0.01 weight % and extremely preferably less than 0.001 weight %.
The advantage of the inventive method is; can quantitatively remove a series of by products that can produce usually vulcabond with described distillation and rectifier unit, and make the application performance of vulcabond quality can realize need not extra purification step promptly to be used for further refinement step with purification fat (ring) family.
By formaldehyde and/or by containing the formaldehyde composition and make in the stage of double carbamate in the used undressed urea, do not need to remove a series of by products that when under pure existence condition, reacting, generated, and do not need to use other equipment yet with alicyclic diamine.Owing to avoided by product at double carbamate in the stage, so also just in the process that ensuing alicyclic double carbamate thermolysis is an alicyclic diisocyanate, avoided the generation of other by products.In this stage, extra use has also just become unnecessary in order to the equipment that obtains ideal vulcabond purity at distillation purification vulcabond.
Can avoid fully astoundingly because the diamines loss makes whole process yield significantly reduce the ancillary cost that causes by undressed urea used according to the invention, described diamines loss phenomenon is owing to formed by product, thereby and this by product also can need to use the cleaning process of costliness reduce the equipment use properties owing in each equipment unit, producing caking; And also can therefore improve the economy of this method.
Also have been found that, if use alicyclic diamines, then preferably by two stage and therefore also be that the alicyclic diamine that carries out via two ureas and the reaction of pure and mild urea prepare alicyclic two urethanes, therefrom remove easily boil thing and in the thing that boils, with the alicyclic two urethane thermolysiss after so purifying, discharge the ideal alicyclic diisocyanate, from resolving device, discharge the decomposition tower substrate of a part continuously and therefrom remove the high boiling material composition, make ejecta after the purification like this and alcohol carry out urethaneization once more then and be recycled in the technology.Can be sure of, on the one hand, synthetic via whole two urethanes in this way, two urethanes are purified can realize the static concentration of relative low high boiling material composition with two urethane elaborative sequences, thereby make that the alluvial phenomenon particularly impel owing to the person's character of high viscosity high boiling material composition can be avoided to the full extent, and the equipment use properties that also can guarantee for a long time process recovery ratio of becoming reconciled.On the other hand, the sepn process of the high boiling material that carries out after the pyrolysis has following advantage, promptly compare with the common process of wherein removing high boiling material before two urethanes decompose, the amount that be transferred to two urethanes that go in the gas phase significantly reduces, and can save cost and energy thus.
Summary of the invention
Theme of the present invention is a kind of multistep method of continuous preparation alicyclic diisocyanate, it is that alicyclic vulcabond carries out by making alicyclic diamines and carboxylic acid derivative and alcohol reaction generate alicyclic two urethanes and then make two urethane thermolysiss, it is characterized in that, two urethanes are to form in two stages, thermolysis removed easily boil thing and in boil two urethanes of thing to discharge the ideal vulcabond, and continuously the decomposition tower bottom product of a part of resolving device is discharged, therefrom remove the high boiling material composition and make ejecta after the purification like this and alcohol carry out once more urethane turn into and be recycled in the technology urea Equivalent that wherein uses undressed urea and/or make by undressed urea.
Theme of the present invention is to be used for the multistep method that preparation continuously has the alicyclic diisocyanate of formula (I),
OCN-R-NCO (I)
R wherein represents to have 4 to 18, the divalence alicyclic alkyl of preferred 5 to 15 carbon atoms, prerequisite is that two isocyanate groups directly are connected on the hydrocarbon ring and at least 3 carbon atoms of arrangement between them, this method is carried out with alcohol reaction generation two urethanes and with its thermolysis by alicyclic diamine and carboxylic acid derivative, in the method
A) make the alicyclic diamine of formula (II) and urea at the alcohol that has formula (III) and do not exist or exist under the condition of catalyzer and react ring alkylidene group two ureas of production (IV), and remove the ammonia that is produced simultaneously continuously,
H
2N-R-NH
2 (II)
R wherein represents to have 4 to 18, the divalence alicyclic alkyl of preferred 5 to 15 carbon atoms, and wherein two nitrogen-atoms directly are connected at least one hydrocarbon ring and are arranged with at least 3 carbon atoms between them,
R
1-OH (III)
R wherein
1Expression by the uncle with 3 to 8 carbon atoms or secondary fat (ring) alcohol remove after the hydroxyl remaining residue,
H
2N-OC-HN-R-NH-CO-NH
2 (IV)
R wherein represents to have 4 to 18, the divalence alicyclic alkyl of preferred 5 to 15 carbon atoms, and prerequisite is that the nitrogen-atoms of R both sides directly is connected in and is arranged with at least 3 carbon atoms on the hydrocarbon ring and between them;
B) in second reactor, make rough ring alkylidene group two ureas that produced and a) in be used as the formula (III) of solvent alcohol under the condition of discharging the ammonia that is discharged continuously, be converted into ring alkylidene group two urethanes of formula V;
R
1O-OC-HN-R-NH-CO-OR
1 (V)
C) from the reaction mixture of gained, separate alcohol, dialkyl carbonate and/or alkyl carbamate and with alcohol turn back to reactions steps a) in;
D) completely or partially give up and separate the boil step of residue of the optional height that is contained in the gained reaction mixture;
E) exist under the condition of catalyzer, continuously and solvent-freely contain via step c) and d at 180 to 280 ℃, preferred 200 to 260 ℃ temperature with at 0.1 to 200 millibar, preferred 0.2 to 100 millibar pressure thermolysis) reaction mixture of two urethanes that obtain of purifying, thus constantly will be, preferably discharge in the partial reaction mixture of feeding material 15 to 45 weight % in feeding material 10 to 60 weight %;
F) by rectifying degradation production is divided into rough vulcabond and alcohol;
G) also separate the product cut of purifying by the rough alicyclic diisocyanate of distillation purification;
H) will be from e) tower at the bottom of ejecta be divided into useful logistics and waste streams and from technology, discharge and give up the waste streams that is rich in the high boiling material composition;
I) make from h) useful logistics with from f) alcohol exist or do not exist under the condition of catalyzer, in 1 to 150min, in preferred 3 to 60min time, stress reaction at 20 to 200 ℃, preferred 50 to 170 ℃ temperature and 0.5 to 20 crust, preferred 1 to 15 crust, and the mol ratio of NCO group and OH group is 1: 100 at the most, preferred 1: 20 and preferred especially 1: 10;
J) the tower bottom distillate purification of a discharge part continuously distillation g) also imports to decomposition reaction e), and/or the urethane step I) in;
K) overhead fraction that randomly will be produced when purifying the rough alicyclic diisocyanate of distillation is recycled to the urethane step I equally) in;
L) will be from i) the logistics of urethaneization again be recycled to step b) and/or c) in,
Wherein adopt undressed urea and/or by the prepared urea Equivalent of untreated urea.
Embodiment
The method according to this invention can make alicyclic diisocyanate with very good yield without a doubt under non-stop run.Particularly advantageous in multistep processes of the present invention is the following fact, promptly when the alicyclic diamine of use formula (II) is used for synthesizing vulcabond continuously as original material, also can avoid largely particularly because the alluvial phenomenon that the person's character of high viscosity high boiling material composition is impelled, and the equipment use properties that also can guarantee for a long time process recovery ratio of becoming reconciled.In addition, another advantage of multistep processes of the present invention is that the amount that can allow will to be transferred to two urethanes that go in the vapor phase reduces to minimum value and limits required energy consumption with this.
A) be reactions steps a) in ring alkylidene group two ureas of preparation formula (IV), make the alicyclic diamine of formula (II) and urea under the condition of the alcohol that has formula (III) (optionally also can be the mixture of this alcohol), in 100 to 145 ℃ of temperature and 0.7 to 1.8 bar pressure react in reactor, simultaneously formed ammonia are discharged continuously.Reaction is preferably carried out in distillation reactor, wherein, with diamines: urea: the mol ratio of alcohol is that 1: 2.0～2.4: 3～10 charging thing is fed on the uppermost column plate continuously, and by the alcohol vapor in importing at the bottom of the distillation reactor tower ammonia that discharges is discharged.The required residence time is 4 to 10 hours, preferred 5 to 9 hours.Be 0.05 to 3kg/kg for discharging amount that ammonia imports to the alcohol that goes at the bottom of the tower, preferred 0.1 to 1kg/kg two urea, and so the alcohol amount of input is taken away at cat head with formed ammonia, at the bottom of removing remaining ammonia after the part condensation and be recycled into tower in pure recovery tower.
B) will result from distillation reactor bottom and rough ring alkylidene group two ureas that are dissolved in the alcohol import in second reactor continuously, and react generation two urethanes in comparatively high temps and elevated pressures therein, wherein emit ammonia again, these ammonia must be removed from reaction mixture according to chemical equilibrium mechanism.Then preferably be to carry out under 1: 5～12 the molar ratio in the pressure distillation reactor and at two ureas from the further reaction of a) rough ring alkylidene group urea than alcohol.In this process, will preferably be incorporated into continuously on the top column plate of pressure distillation reactor from a) logistics.Under the condition that does not have or exist catalyzer, in 140 to 270 ℃, preferred 160 to 250 ℃ temperature and under the pressure of 5 to 20 crust, preferred 7 to 15 crust reacted in 2 to 20 hours, preferred 8 to 15 hours.The continuous discharge of the ammonia that is discharged can be undertaken by alcohol vapor, and described alcohol vapor is introduced into the bottom of pressure distillation reactor and results from suitably in the vaporizer at the bottom of being placed in tower.
For improving speed of reaction, preparation two urethanes under the condition of catalyzer can be had.What be suitable as catalyzer is inorganic or organic compound, and it comprises one or more, IA in preferred a kind of periodictable, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIB, the positively charged ion of VIIB and VIIIB family metal, and it is according to content-defined among the Handbook of Chemistry and Physics the 14th edition, the Chemical Rubber Publishing Co. 2310Superior Ave.N.E.Cleveland of press, Ohio; For example can be halogenide such as muriate and bromide, vitriol, phosphoric acid salt, nitrate, borate, alkoxide, phenates, sulfonate, oxide compound, oxide hydrate, oxyhydroxide, carboxylate salt, inner complex, carbonate and thiocarbamate or dithiocar-bamate.The example of being worth mentioning is the positively charged ion of following metal: lithium, sodium, potassium, magnesium, calcium, aluminium, gallium, tin, lead, bismuth, antimony, copper, silver, gold, zinc, mercury, cerium, titanium, vanadium, chromium, molybdenum, manganese, iron, cobalt and nickel.As typical catalyzer, that is worth mentioning has a for example following compound: lithium ethoxide, butanols lithium, sodium methylate, potassium tert.-butoxide, magnesium ethylate, calcium methylate, tin chloride (II), tin chloride (IV), plumbic acetate, aluminum chloride, Trichlorobismuthine, neutralized verdigris (II), cupric chloride (II), zinc chloride, zinc octoate, four butanols titaniums, vanadium trichloride, vanadium acetylacetonate, manganese acetate (II), iron acetate (II), iron acetate (III), ironic oxalate, cobalt chloride, cobalt naphthenate, nickelous chloride, nickel naphthenate and their mixture.Catalyzer also can optionally use with its hydrate or ammonate form.
The starting compound that is used for the inventive method is the diamines with above-mentioned formula (II), alcohol and the urea with above-mentioned formula (III).The diamines of suitable formula (II) is for example 1,4-diamino-cyclohexane, 4,4 '-methylene radical dicyclohexyl diamines, 2,4-methylene radical dicyclohexyl diamines, 2, the alicyclic diamine of 2 '-methylene radical dicyclohexyl diamines and isomery and all hydrogenated methylenediphenyl diamines.Methylenediphenyl diamines (MDA) is understood with 4,4 ', 2 4-and 2, the form appearance (referring to for example DE10127273) of the isomer mixture that 2 '-MDA forms because preparation condition is limit.Therefore all hydrogenated methylenediphenyl diamines obtains by complete hydrogenation MDA and but by the methylene radical dicyclohexyl diamines (H of isomery
12MDA), promptly 4,4 ', 2,4-and 2,2 '-H
12The mixture that (part) aromatics MDA of MDA and possible a small amount of not complete reaction forms.As the diamines of formula (II), preferably use 4,4 '-methylene radical dicyclohexyl diamines, 2,4-methylene radical dicyclohexyl diamines and 2,2 '-methylene radical dicyclohexyl diamines and any mixture that also has at least two kinds of compositions in these isomer.Obviously, also can use and the different diamines of formula (II).For example have 1,3-and 1,4-diaminomethyl hexanaphthene, 1,6-hexanediamine, 2,2,4-or 2,4,4-trimethylammonium-1,6-hexanediamine and 3-aminomethyl-3,5,5-trimethylcyclohexyl amine.But preferably do not use those to be different from the amine of formula (II).
Be suitable as formula (III) alcohol be under normal pressure, to have any aliphatic series or the alicyclic alcohol that is lower than 190 ℃ of boiling points.The example of being worth mentioning is alcohol such as methyl alcohol, ethanol, 1-propyl alcohol, 1-butanols, 2-butanols, 1-hexanol or the hexalin of C1-C6.Preferably use the 1-butanols as alcohol.
In the reaction mixture reaction process, can discharge ammonia, consider that for molecular balance it is useful removing it verified.The wall temperature that is noted that reactor and vent pipe from reactor when ammonia is discharged will be higher than 60 ℃, can avoid thus being covered by ammonium carbamate, and wherein ammonium carbamate is formed by the carbonic acid gas that ammonia and urea decomposition obtain by minute quantity.For example verified effective way is to make to be reflected in the pressure distillation reactor to carry out, and makes reaction mixture with respect to carrying out intense mixing on the column plate that imports and make in this way liquid at the alcohol vapor of introducing at the bottom of the tower with the adverse current form and all meet actually cascade structure (Kaskadenstuf).The vapour mixture of extracting out from cat head, forms by pure and mild ammonia can be preferably at the pressure of pressure distillation reactor and under the condition of not prior condensation, import to the distillation tower, to obtain not ammoniated alcohol, then alcohol is recycled to the bottom of pressure distillation reactor and tower.For avoiding ammonium carbamate to form coating in reflux exchanger, the alcohol that will import respective amount therein arrives at least 60 ℃ with the temperature regulation with cat head.
C) with at least two kinds mixture in excessive alcohol, the dialkyl carbonate that may form or alkyl carbamate or these compositions with a step, or the isolated in form in two steps advantageously.The first step is with reactions steps b) the reaction mixture of stress level be decompressed to 1 to 500 millibar, preferred 2 to 150 millibars force value, and be divided into liquid ejecta in this way and contain the alcohol of main amount and the steam of dialkyl carbonate optionally and/or alkyl carbamate.In second step by thin layer evaporator 180 to 250 ℃, preferred 200 to 230 ℃ and 0.1 to 20 millibar, preferred 1 to 10 millibar pressure remove from liquid ejecta the residue butanols that may exist and boil thing such as dialkyl carbonate and/or alkyl carbamate, thereby make resistates form by monomeric two urethanes and the height optionally oligopolymer that boils basically.Steam can after further distillation is purified, be recycled to reactions steps a) in.But dialkyl carbonate and/or alkyl carbamate also can be recycled to reactions steps b) in.
D) preferably remove the high boiling material that optionally contains in the reaction mixture that at every turn is separated in step c) from.If but just adopt a part logistics, promptly partly carry out h) described in separation from e) process of step bottom ejecta, that then can take the following stated is used for the isolating approach of high boiling material:
Randomly, can preferably utilize thin layer evaporator or short-path evaporator, at 180 to 260 ℃, preferred 200 to 240 ℃ temperature with at 0.01 to 10 millibar, preferred 0.02 to 5 millibar pressure, to come from step c), separated easily boil thing and in the resulting logistics that contains monomer two urethanes and high boiling point oligopolymer optionally after the thing of boiling, fractionation by distillation becomes to contain the useful logistics and the not distillable byproduct stream of monomer two urethanes and low hubble-bubble point by product.The not distillable byproduct stream that contains the high boiling point composition is discharged from preparation process and is given up as the residue that can not use on the material usually.
Randomly, also the logistics that contains high boiling point oligopolymer optionally from step c) can carried out being divided into two part logistics before its above-mentioned distillation purification process, one of them part logistics directly imports to decomposition reaction (referring to e)) in go another part logistics then at first to experience above-mentioned high boiling material sepn process.
E) make from step c) and the optional useful logistics that contains monomer two urethanes and low-boiling by-products from step d) in suitable device partly, solvent-freely in liquid phase and have under the condition of catalyzer in 180 to 280 ℃, preferred 200 to 260 ℃ temperature and 0.1 to 200 millibar, preferred 0.2 to 100 a millibar pressure thermolysis continuously.In thermal decomposer, transformation efficiency from two urethanes to vulcabond can freely be selected to a great extent according to two used urethanes, and normally in the scope of 10 to 95 weight %, preferred 35 to 85 weight % that import two urethanes (infeeding material) are measured.Discharge on the undecomposed partial continuous ground of reaction mixture, and this part comprises unreacted two urethanes, high boiling point by-products produced and other by products that can utilize and can not utilize.The amount of ejecta is especially decided according to the transformation efficiency and the throughput of decomposition reaction, and can determine by test simply.This value is generally 10 to 60 weight %, preferred 15 to 45 weight %, for the pan feeding meter.
As the catalyzer of decomposition two urethanes, the inorganic and organic compound that can use for example aforesaid catalysis urethane to form.The preferred muriate of zinc, tin or copper and the oxide compound of zinc, manganese, iron or cobalt of using, and before catalyzer enters in the decomposition step with its with 5 to 400ppm, preferred 10 to 100ppm amount adds to from purification step c) and optional d) logistics in, this catalyzer uses as the solution or the form of suspension of the alcohol of 0.01 to 25 weight %, preferred 0.05 to 10 weight %, and described alcohol is the alcohol that is used for the urethane preparation equally.
What be suitable as decomposer is for example columniform decomposition reactor, for example tube furnace or preferably vaporizer, as falling liquid film-, thin layer-or Bulk vaporizer, as Robert vaporizer, Herbert vaporizer, caddle type vaporizer, Oskar vaporizer and heating candle formula vaporizer.
In principle, the isocyanates material that will inevitably discharge when alcohol decomposes will keep little as far as possible at the mean residence time of resolver, thereby unfavorable side reaction is limited in minimum value.
Preferably in decomposition of making up and rectifying tower, decompose, and their structure will be suitable for energy is imported to the tower bottom that has falling-film evaporator, import to and be connected with following 1/3rd places that are used for extra intake or are used for recovered energy, import to be connected with last 1/3rd places that are used to extract out the device of rough vulcabond preferably and to import to and be connected with the top of tower that is used to reflux and extracts the condenser of pure alcohol out.
F) at 95 to 260 ℃, preferred 110 to 245 ℃ temperature and 0.5 to 250 millibar, preferred 1 to 100 millibar pressure, by the degradation production that two urethanes that especially decomposed by alcohol, vulcabond and part that form in the thermal decomposition process are formed in rectifying, be separated into pure and mild by the alicyclic diisocyanate of alicyclic diisocyanate, part decomposition and the rough mixtures of diisocyanates that a small amount of alicyclic two urethanes are optionally formed.This separation can for example be carried out in above-mentioned built-up type decomposition and the decomposition tower in the rectifying tower.
G) at 95 to 260 ℃, preferred 110 to 245 ℃ temperature and 0.5 to 150 millibar, preferred 1 to 75 millibar pressure, that to preferably obtain by rectifying by distillation and alicyclic two urethanes that decomposed by alicyclic diisocyanate, part and the crude mixture that alicyclic two urethanes form of seldom measuring are optionally purified, and the cut that produced or isolate as clean product simultaneously circulates.
H) will be from e) tower at the bottom of ejecta be divided into useful logistics and waste streams and from technology, discharge and give up the waste streams that is rich in the high boiling material composition.The separation of two kinds of logistics can be preferably by means of thin layer evaporator or short-path evaporator, carries out at 180 to 270 ℃, preferred 200 to 250 ℃ temperature with at 0.01 to 10 millibar, preferred 0.02 to 5 millibar pressure distillation ground.The useful logistics that contains monomer two urethanes and low-boiling by-products produces as overhead product.The waste streams that is rich in the high boiling point composition then forms as residue and discharges from preparation technology and gives up as the material that can not utilize on the material usually.Another substitutes but not preferred mode is also can become useful thing and refuse by extracting and separating.What be suitable as extraction agent is for example postcritical carbonic acid gas.
Randomly, also can be before above-mentioned distillation be purified with tower at the bottom of ejecta be separated into two part logistics, wherein a part logistics is directly imported in the urethane reaction again (referring to i)).The distribution of two logistics can be carried out with 99: 1 to 1: 99, preferred 99: 5 to 5: 95.
I) make from step h) useful logistics and from rectification step f) alcohol import together, wherein the mol ratio of NCO group and OH group be at most 1: 100, preferred 1: 20 and preferred especially 1: 10, and reaction mixture under the condition that has or do not exist catalyzer in 1 to 150min, react in preferred 3 to 60min time and at the pressure of 20 to 200 ℃, preferred 50 to 170 ℃ temperature and 0.5 to 20 crust, preferred 1 to 15 crust.Reaction can be carried out in the successive cascade unit or in tubular reactor.As catalyzer, can consider the catalyst that all can impel the NCO/OH reaction basically.Stannous octoate, dibutyl tin laurate, tindichloride, zinc dichloride, cupric chloride, dichloride copper, ferrous chloride, iron trichloride and tetraethyl-amine are for example arranged.
J) a part of g that distills from purifying of continuous discharge) tower bottom distillate and optional recycle are gone into decomposition step e) or the urethane step I) in.Preferred cycle is gone in the urethane step.The amount of ejecta is 0.1 to 50 weight % of rough vulcabond import volume in the purification distilation steps, preferred 0.2 to 25 weight %.
K) overhead fraction purification distilation steps g) can be rejected or preferred cycle is gone into the urethane step I) in.The amount of the overhead fraction that each time period discharges is 0.1 to 3 weight % of rough vulcabond import volume in the purification still-process, preferred 0.3 to 1 weight %.
L) will be from the urethane step I) logistics be recycled into easily boil thing and in the thing separating step c that boils) and/or two urethanes prepare b) in.
Utilize multistep processes of the present invention next, for distillable alicyclic vulcabond, can guarantee to react and carry out without barrier so that higher selectivity is smooth and easy circulating and discharging continuous preparation alicyclic diisocyanate under the by product situation.Method of the present invention be particularly suitable for preparing have 4 to 18, the alicyclic diisocyanate of preferred 5 to 15 carbon atoms, as 1,4-two isocyanato-hexanaphthenes, 4,4 '-methylene radical dicyclohexyl vulcabond (4,4 '-H
12MDI), 2,2 '-methylene radical dicyclohexyl vulcabond (2,2 '-H
12MDI), 2,4 '-methylene radical dicyclohexyl vulcabond (2,4 '-H
12MDI) or the methylene radical dicyclohexyl vulcabond (H of above-mentioned isomery
12MDI) mixture, for example they can be converted into H at perhydro-MDA according to its character
12Produce in the MDI process.Very particularly preferably prepare 4,4 '-methylene radical dicyclohexyl vulcabond and by 4,4 '-H
12MDI, 2,4-H
12MDI and 2,2 '-H
12Any mixture that MDI forms.
Prepared alicyclic vulcabond is suitable for containing the plastics of urethane groups, isocyanuric acid ester group, amide group and/or urea groups according to polymeric polyisocyanate-addition polymerization method preparation most.In addition, they also can be used for preparing the mixture of polyisocyanates with urethane groups, biuret groups and/or the modification of isocyanuric acid ester group.The mixture of polyisocyanates that this class is made up of alicyclic diisocyanate can be used in particular for preparing high price, fast to light polyurethane coating.
Claims (51)
1. multistep method that is used for preparing continuously alicyclic diisocyanate, it is that alicyclic vulcabond carries out by making alicyclic diamines and carboxylic acid derivative and alcohol reaction generate alicyclic two urethanes and then make two urethane thermolysiss, the method is characterized in that, two urethanes are to form in two steps, thermolysis removed easily boil thing and in boil two urethanes of thing to discharge the ideal vulcabond, and continuously the decomposition tower bottom product of a part of resolving device is discharged, therefrom remove the high boiling material composition and make ejecta after the purification like this and alcohol once more urethane turn into and be recycled in the technology urea Equivalent that wherein uses undressed urea and/or make by undressed urea.
2. one kind is used for the multistep method that preparation continuously has the alicyclic diisocyanate of formula (I),
OCN-R-NCO (I)
R wherein represents to have 4 to 18, the divalence alicyclic alkyl of preferred 5 to 15 carbon atoms, prerequisite is that two isocyanate groups directly are connected on the hydrocarbon ring and at least 3 carbon atoms of arrangement between them, this method is carried out with alcohol reaction generation two urethanes and with its thermolysis by alicyclic diamine and carboxylic acid derivative, in the method
A) make the alicyclic diamine of formula (II) and urea at the alcohol that has formula (III) and do not exist or exist under the condition of catalyzer and react ring alkylidene group two ureas of production (IV), and remove the ammonia that is produced simultaneously continuously,
H
2N-R-NH
2 (II)
R wherein represents to have 4 to 18, the divalence alicyclic alkyl of preferred 5 to 15 carbon atoms, and wherein two nitrogen-atoms directly are connected at least one hydrocarbon ring and are arranged with at least 3 carbon atoms between them,
R
1-OH (III)
R wherein
1Expression by the uncle with 3 to 8 carbon atoms or secondary fat (ring) alcohol remove after the hydroxyl remaining residue,
H
2N-OC-HN-R-NH-CO-NH
2 (IV)
R wherein represents to have 4 to 18, the divalence alicyclic alkyl of preferred 5 to 15 carbon atoms, and prerequisite is that the nitrogen-atoms of R both sides directly is connected in and is arranged with at least 3 carbon atoms on the hydrocarbon ring and between them;
B) in second reactor, make rough ring alkylidene group two ureas that produced and a) in be used as the formula (III) of solvent alcohol under the condition of discharging the ammonia that is discharged continuously, be converted into ring alkylidene group two urethanes of formula V;
R
1O-OC-HN-R-NH-CO-OR
1 (V)
C) from the reaction mixture of gained, separate alcohol, dialkyl carbonate and/or alkyl carbamate and with alcohol turn back to reactions steps a) in;
D) completely or partially remove from and separate the boil step of residue of the optional height that is contained in the gained reaction mixture;
E) exist under the condition of catalyzer, continuously and solvent-freely under 180 to 280 ℃, preferred 200 to 260 ℃ temperature and at 0.1 to 200 millibar, preferred 0.2 to 100 millibar pressure thermolysis, contain via step c) and d) reaction mixture of two urethanes that obtain of purifying, thus will discharge in the partial reaction mixture of feeding material 10 to 60 weight %, preferred 15 to 45 weight % constantly;
F) by rectifying degradation production is divided into rough vulcabond and alcohol;
G) purify rough alicyclic diisocyanate and separate pure product fractions by distilling;
H) will be from e) tower at the bottom of ejecta be divided into useful logistics and waste streams and from technology, discharge and give up the waste streams that is rich in the high boiling material composition;
I) make from h) useful logistics with from f) alcohol exist or do not exist under the condition of catalyzer, in 1 to 150min, in preferred 3 to 60min time, under 20 to 200 ℃, preferred 50 to 170 ℃ temperature and the stress reaction of 0.5 to 20 crust, preferred 1 to 15 crust, and the mol ratio of NCO group and OH group is 1: 100 at the most, preferred 1: 20 and preferred especially 1: 10;
J) the tower bottom distillate purification of a discharge part continuously distillation g) also imports to decomposition reaction e), and/or the urethane step I) in;
K) overhead fraction that randomly will be produced when purifying the rough alicyclic diisocyanate of distillation is recycled to the urethane step I equally) in;
L) will be from i) the logistics of urethaneization again be recycled to step b) and/or c) in,
Wherein adopt undressed urea and/or by the prepared urea Equivalent of untreated urea.
3. claim 1 or 2 described multistep methods is characterized in that, as alicyclic diamines, use 4, the alicyclic diamine of 4 '-methylene radical dicyclohexyl diamines and/or isomery.
4. the described multistep method of claim 3 is characterized in that, as alicyclic diamine, use 4,4 '-methylene radical dicyclohexyl diamines, 2,4 '-methylene radical dicyclohexyl diamines and 2,2 '-methylene radical dicyclohexyl diamines and at least two kinds any mixture that also has above-mentioned isomer.
5. claim 1 or 2 described multistep methods is characterized in that, use 1 as alicyclic diamine, the 4-diamino-cyclohexane.
6. at least one described method is characterized in that in the aforementioned claim, and step a) is carried out in reactor and under 100 to 145 ℃ and 0.7 to 1.8 pressure condition that clings to.
7. at least one described method is characterized in that step a) is carried out in the aforementioned claim in distillation reactor.
8. at least one described method is characterized in that in the aforementioned claim, is reflected at diamines in the step a): urea: alcohol is that 1: 2.0～2.4: 3～10 molar ratio carries out.
9. at least one described method is characterized in that in the aforementioned claim, in step a) the raw material thing is fed on the column plate of going up most and by the alcohol vapor that imports to the distillation reactor bottom continuously and discharges the ammonia that is discharged.
10. at least one described method in the aforementioned claim, wherein, the residence time of raw material thing in step a) be 4 to 10, preferred 5 to 9 hours.
11. at least one described method is characterized in that step b) is carried out in the aforementioned claim in the pressure distillation reactor.
12. at least one described method is characterized in that in the aforementioned claim, step b) is to 12 condition to carry out at 1: 5 at two ureas to the mol ratio of alcohol.
13. at least one described method is characterized in that in the aforementioned claim, preferably imports to continuously from a) logistics on the column plate of the top of reactor of step b).
14. at least one described method is characterized in that in the aforementioned claim, in 140 to 270 ℃, preferred 160 to 250 ℃ temperature of reaction and react at the pressure of 5 to 20 crust, preferred 7 to 15 crust in step b).
15. at least one described method is characterized in that in the aforementioned claim, is reflected at 2 to 20 hours in the step b), carries out in preferred 8 to 15 hours.
16. at least one described method is characterized in that in the aforementioned claim, being reflected in step a) and/or the step b) exists under the condition of catalyzer carries out.
17. at least one described method is characterized in that step a) and b in the aforementioned claim) the middle alcohol that uses with 1 to 6 carbon atom.
18. at least one described method is characterized in that step a) and b in the aforementioned claim) the middle butanols that uses.
19. at least one described method is characterized in that in the aforementioned claim, step c) was carried out with two steps.
20. the described method of claim 19 is characterized in that, in the first step with reactions steps b) reaction mixture of stress level reduce pressure 1 to 500 millibar, preferred 2 to 150 millibars pressure.
21. claim 19 or 20 described methods, it is characterized in that, in second step by thin layer evaporator 180 ℃ to 250 ℃, preferred 200 ℃ to 230 ℃ temperature and 0.1 millibar to 20 millibars, preferred 1 millibar to 10 millibars pressure from liquid ejecta, remove the optional remnants that exist alcohol and in boil thing such as dialkyl carbonate and/or alkyl carbamate.
22. at least one described method is characterized in that in the claim 19 to 21, the steam of step c) after further distillation is purified, import to reactions steps a) in.
23. at least one described method is characterized in that in the aforementioned claim, the sepn process in the step d) if you are using, is carried out at 180 to 260 ℃, preferred 200 to 240 ℃ temperature and 0.01 to 10 millibar, preferred 0.02 to 5 millibar pressure.
24. at least one described method is characterized in that step d) if you are using, is carried out by means of thin layer evaporator or short-path evaporator in the aforementioned claim.
25. at least one described method is characterized in that in the aforementioned claim, if use step d), discharges and gives up by product from step d).
26. at least one described method in the aforementioned claim, it is characterized in that, before going in transferring to step d) from the logistics of step c), if you are using, it is handled, make before distillation is purified it to be divided into two part logistics, one of them part logistics is directly imported in the decomposition reaction goes, referring to e).
27. at least one described method is characterized in that in the aforementioned claim, step e) is carried out in decomposition of making up and rectifying tower.
28. at least one described method in the aforementioned claim, it is characterized in that, in step e), exist under the condition of catalyzer and carrying out thermolysis continuously at 180 to 280 ℃, preferred 200 to 260 ℃ temperature and 0.1 to 200 millibar, preferred 0.2 to 100 millibar pressure.
29. at least one described method is characterized in that in the aforementioned claim, in the step e), decomposes in liquid phase under solvent-free condition.
30. at least one described method is characterized in that in the aforementioned claim, step e) is carried out existing under the condition of catalyzer.
31. at least one described method in the aforementioned claim, it is characterized in that, the thermoinducible two urethane decomposition reactions of step e) are carried out in tube furnace or preferred vaporizer, described vaporizer is for example falling-film evaporator, thin layer evaporator or Bulk vaporizer, as Robert vaporizer, Herbert vaporizer, caddle type vaporizer, Oskar vaporizer and heating candle formula vaporizer.
32. at least one described method in the aforementioned claim, it is characterized in that, in the step e), transformation efficiency from two urethanes to vulcabond freely selects according to two used urethanes, preferably expects 10 to 95 weight % of the amount of two urethanes, the more preferably scope of 35 to 85 weight % in the feeding that is imported.
33. at least one described method in the aforementioned claim, it is characterized in that, in step e), discharge a part of reaction mixture continuously, described mixture comprises unreacted two urethanes, high boiling by product and other recycling and can not utilize by products.
34. the described method of claim 33 is characterized in that, output is 10 to 60 weight %, preferred 15 to the 45 weight % of feeding material.
35. at least one described method is characterized in that in the aforementioned claim, step f) is carried out in decomposition of making up and rectifying tower.
36. at least one described method is characterized in that in the aforementioned claim, at 95 to 260 ℃, preferred 110 to 245 ℃ temperature and 0.5 millibar to 250 millibars, preferred 1 millibar to 200 millibars pressure operation.
37. at least one described method in the aforementioned claim, it is characterized in that, in step g) under in 95 to 260 ℃, preferred 110 to 245 ℃ temperature and 0.5 millibar to 150 millibars, preferred 1 millibar to the 75 millibars pressure condition, purifying by distillation derives from the rough cut that step f) and alicyclic two urethanes that decomposed by alicyclic diisocyanate, part and optionally a spot of alicyclic two urethanes are formed.
38. at least one described method is characterized in that in the aforementioned claim, the cut that is produced in the step g) is with the isolated in form of clean product or be recycled to step I) in.
39. at least one described method is characterized in that, at step h in the aforementioned claim) in, in 180 ℃ to 270 ℃, preferred 200 to 250 ℃ temperature and 0.01 millibar to 100 millibars, preferred 0.02 millibar to 5 millibars pressure condition operation down.
40. at least one described method is characterized in that step h in the aforementioned claim) undertaken by extraction.
41. at least one described method is characterized in that, at step h in the aforementioned claim) in, before distillation is purified with tower at the bottom of ejecta be divided into two part logistics, one of them part logistics is directly imported to the step I of urethaneization again) in.
42. at least one described method is characterized in that in the aforementioned claim, two part logistics distribute according to 99: 1 to 1: 99, preferred 95: 5 to 5: 95 ratio.
43. at least one described method is characterized in that step I in the aforementioned claim) be to carry out at the successive cascade device or in tubular reactor.
44. at least one described method is characterized in that step I in the aforementioned claim) in the condition that is reflected at the catalyzer that has the carboxylate salt that is selected from Sn and/or Zn and/or Cu or halogenide and/or tertiary amine under carry out.
45. at least one described method is characterized in that, at step j in the aforementioned claim) in be recycled into decomposition step e) or the urethane step I) in.
46. at least one described method is characterized in that, at step j in the aforementioned claim) in, the amount of ejecta is 0.1 to 50 weight % of rough polymeric polyisocyanate input in the purification distilation steps, preferred 0.2 to 25 weight %.
47. at least one described method in the aforementioned claim, it is characterized in that, preparation 1,4-two isocyanato-hexanaphthenes, 4,4 '-methylene radical dicyclohexyl vulcabond, 2,2 '-methylene radical dicyclohexyl vulcabond, 2, both mixtures at least in the methylene radical dicyclohexyl vulcabond of 4 '-methylene radical dicyclohexyl vulcabond or above-mentioned isomery.
48. at least one described method is characterized in that used diamines is selected from 1,3-and 1,4-diaminomethyl hexanaphthene, 1 in the aforementioned claim, the 6-hexanediamine, 2,2,4-or 2,4,4-trimethylammonium-1,6-hexanediamine and 3-aminomethyl-3,5,5-trimethylcyclohexyl amine.
49. at least one described method in the aforementioned claim, it is characterized in that, the maximum formaldehyde of used urea or used urea Equivalent also can be paraformaldehyde, and concentration is 0.01 to 0.10 weight %, preferred 0.001 to 0.01 weight % and especially preferably less than 0.001 weight %.
50. at least one described method is characterized in that in the aforementioned claim, without inorganics and/or formaldehyde urea carried out surface treatment.
51. at least one described method is characterized in that urea does not contain talcum, wilkinite, silica gel, diatomite, kaolin or other silicates materials in the aforementioned claim.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006061470A DE102006061470A1 (en) | 2006-12-23 | 2006-12-23 | Multistage preparation of cycloaliphatic diisocyanates, useful for forming e.g. polymers, comprises reacting cycloaliphatic diamines with carbonic acid derivatives and alcohols to give cycloaliphatic diurethane and thermally cleaving |
| DE102006061470.4 | 2006-12-23 |
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|---|---|
| CN101205200A true CN101205200A (en) | 2008-06-25 |
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|---|---|---|---|
| CNA2007101621790A Pending CN101205200A (en) | 2006-12-23 | 2007-12-21 | Multi-step method for continuously producing toluene diisocyanate |
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| CN (1) | CN101205200A (en) |
| DE (1) | DE102006061470A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256296A (en) * | 2019-05-20 | 2019-09-20 | 江苏蓝丰生物化工股份有限公司 | The synthetic method of 1,5- naphthalene diisocyanate |
-
2006
- 2006-12-23 DE DE102006061470A patent/DE102006061470A1/en not_active Withdrawn
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2007
- 2007-12-21 CN CNA2007101621790A patent/CN101205200A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256296A (en) * | 2019-05-20 | 2019-09-20 | 江苏蓝丰生物化工股份有限公司 | The synthetic method of 1,5- naphthalene diisocyanate |
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