CN101234997A - Multi-stage method for continuously preparing alicyclic diisocyanate - Google Patents
Multi-stage method for continuously preparing alicyclic diisocyanate Download PDFInfo
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- CN101234997A CN101234997A CNA2007101600629A CN200710160062A CN101234997A CN 101234997 A CN101234997 A CN 101234997A CN A2007101600629 A CNA2007101600629 A CN A2007101600629A CN 200710160062 A CN200710160062 A CN 200710160062A CN 101234997 A CN101234997 A CN 101234997A
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
Multistep process for continuously preparing cycloaliphatic diisocyanates, comprises reacting a cycloaliphatic diamine with a carbonic acid derivative and an alcohol to produce a cycloaliphatic diurethane, separating the cycloaliphatic diurethane from low, middle and high boilers, and then thermally cleaving the cycloaliphatic diurethane to produce a cycloaliphatic diisocyanate, and continuously discharging a portion of the cleavage residue and reurethanizing the portion with an alcohol, and recycling the reurethanization product directly into the low-boiler separation. Multistep process for continuously preparing cycloaliphatic diisocyanates, comprises reacting a cycloaliphatic diamine with a carbonic acid derivative and an alcohol to produce a cycloaliphatic diurethane, separating the cycloaliphatic diurethane from low, middle and high boilers, and then thermally cleaving the cycloaliphatic diurethane to produce a cycloaliphatic diisocyanate, and continuously discharging a portion of the cleavage residue and reurethanizing the portion with an alcohol, and recycling the reurethanization product directly into the low-boiler separation; where the unconditioned urea and/or unconditioned urea produced from urea material are used equivalently.
Description
Technical field
The present invention relates to a kind of multi-stage method for preparing alicyclic diisocyanate continuously with no phosgene ground.
Background technology
The synthetic inlet of isocyanic ester can be realized via a series of different paths.The earliest and so far the scheme that still occupies leading industrial preparation isocyanic ester is so-called phosgene approach.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.
Exist also now that phosgene are used in many avoidances and the method that can prepare isocyanic ester with technical scale.Term " method of no phosgene " is commonly used to refer under the condition of using alternate carbonylation agent such as urea or dialkyl carbonate and makes amine change the process (EP18586, EP355443, US4268683, EP990644) of isocyanic ester into.
The mechanism of described urea route is to make diamines change vulcabond into by a two stage process via urea.In the first step, make diamines and alcohol reaction under urea or urea Equivalent (as alkyl carbonate, alkyl carbamate) existence condition generate two urea alkane (Diurethan), two urea alkane usually again through an intermediate purification stage and then in second goes on foot thermolysis be vulcabond and alcohol (EP355443, US4713476, US5386053).Another replacement scheme is also can insert one individually by expressly making the reaction of diamines and urea prepare the process (EP568782) of two ureas before original urea alkane forming process.Can consider that also a partial reaction and second by the first step urea and alcohol goes on foot the two stages orders (EP657420) that then are metered into urea alkanisation diamines.
The thermolysis of urea alkane 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 liquid phase under high temperature in gas phase at a lower temperature.But the problem of these two kinds of methods is generally also unfavorable side reaction will take place owing to be heated, and this side reaction can reduce productive rate on the one hand, also can cause forming resinification byproduct on the other hand, this byproduct can be because fouling and obstruction and obviously upset technical process in reactor and the equipment for purifying.
Therefore also just be no lack of some of the recommendations are arranged, obtain the improvement of productivity and suppress the formation of unfavorable by product by the measure on chemistry and the Technology.For example in a series of document, put down in writing and used the catalyzer (DE1022222, US3919279, DE2635490) that can quicken the decomposition reaction of urea alkane.In fact, can fully successfully improve the productive rate 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 productive rate descends and can attach the too high shortcoming of energy consumption.
The embodiment of the single urea alkane of the heat conduction catalytic decomposition described in the EP54817 has described reaction mixture has partly been discharged to be separated in formed resinoid by product in the urea alkane decomposition course.This process can play the effect of avoiding fouling and obstruction in reactor and the processing unit (plant).But wherein do not exist hint can utilize this part to eject the enlightenment that improves productive rate.Put down in writing a kind of similar solution among the EP061013, wherein 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 productive rate yet.
Existing known from EP0355443, if the by product higher molecular weight that will form in decomposition reactor in two urea alkane decomposition coursees, that can utilize and can not utilize is discharged from reactor as far as possible continuously to guarantee the interference-free and tool selectivity of reaction, and then under pure existence condition, make its most of reaction and return then and lead in the two urea alkane preparation process, then just can improve productive rate.Described method need have higher energy consumption, because will separate from the discharge material of two urea alkane preparation by the by product that distillation can not utilize, must evaporate two all urea alkane simultaneously.Different with EP0355443, be that discharge material with the urea alkylation reaction is assigned as two strands of part streams in the method for EP0566925, therefrom having only one is to remove its high boiling and can not utilize by product by distillation, and the two urea alkane liquid streams that will merge then import in the decomposition reaction in the decomposition reactor.In addition, be that the successive decomposition reactor is discharged material directly, promptly return in the building-up process that imports two urea alkane without the step of urea alkanisation again in EP566925.
The process of EP566925 can cause, and becomes branch to return via catabolic phase in the two urea alkane preparation process from two urea alkane synthetic part high boiling point and also arrives in the two urea alkane purification process again.
So far, 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.The crystalline urea water-content very low＜also can tend to self-adhesion consumingly at 0.1% o'clock, thereby make 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, diatomite, Bacillariophyta (Diatomeen) or other silicate materials by subsequently surface of beads being handled or being improved its storing performance by sulphur with by spraying a spot of oil.
Now, urea industry all preferably will be at the most the formaldehyde of 0.6 weight % (Ullmann ' sEncyclopedia of Industrial Chemistry, Release 2006 the 7th edition) before granulation, add to and go in the urea melt, to improve the stability of bead.This measure is used for placing that disintegration and self-adhesion take place transportation and also in order to improve storage stability.
By before granulation or the granulating through add urea that urea melt that formaldehyde (also having Paraformaldehyde 96) handled makes and with formaldehyde (also having each polyoxymethylene) no matter surface-treated urea---it is a kind of measure that improves bead storage property of industrial practicality equally---in fs, subordinate phase and the alternate multi-stage method of the alicyclic diurethanes of preparation or following when alicyclic diurethanes thermolysis is alicyclic diisocyanate, all can cause the unfavorable by product of formation.
Formed by product promptly not only can cause forming unfavorable coherent mass in equipment after very short time in stage of carrying out continuously or multistage diurethanes building-up process, the result make to produce the time length and becomes relatively short and need expensive purification process thereafter, and all can't satisfactorily it be separated in the stage of the rough diurethanes of being recorded and narrated in known and document of each distillation purification.
In order to be in the suite of equipment of alicyclic diisocyanate with alicyclic diurethanes thermolysis, that can't quantitatively remove all can cause bonding and therefore and because the purification process of costliness has reduced usage ratio of equipment extraly from the by product in diurethanes stage itself and the new therefrom a series of by products that produce.
Summary of the invention
Surprisingly, this task can be solved by following scheme, promptly for by making alicyclic diamines and urea and/or urea Equivalent (for example alkyl carbonate, alkyl carbamate) thereby and alcohol reaction generates alicyclic diurethanes and be that alicyclic vulcabond makes alicyclic vulcabond with alicyclic diurethanes thermolysis then, adopt do not rely on delivery form (bead, particle, crystal, melt, solution), undressed urea forms alicyclic diurethanes.Undressed urea both was meant and did not also add additive and/or formaldehyde before granulation or granulating in melt without surface treatment.
The used urea and be used for preparing urea Equivalent (alkyl carbonate for example according to the present invention, alkyl carbamate) as possible precursor with the urea of synthesis of alicyclic diurethanes without conditioning (unkonditioniert), be that it can carry out surface treatment without inorganic substance, as adopt talcum, wilkinite, diatomite, Bacillariophyta, kaolin or other also can be as the silicate materials of antisticking agent, and/or needn't derive from the urea melt after handling with formaldehyde (also can be Paraformaldehyde 96) and/or needn't carry out surface treatment with formaldehyde (also can be Paraformaldehyde 96).Usually, the maximum concentration of formaldehyde of used urea or used urea Equivalent (also can be Paraformaldehyde 96) 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 with described distillation-and rectifier unit quantitatively remove a series of by products that can produce usually vulcabond with purification fat (ring) family, and make the applicability power spectrum of vulcabond quality can realize need not extra purification step promptly to be used for further refining stage.
By formaldehyde and/or by used without containing the formaldehyde composition and make in the stage of diurethanes in the urea of conditioning, 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 diurethanes in the stage, so also just in the process that ensuing alicyclic diurethanes thermolysis is an alicyclic diisocyanate, avoided the generation of other a series of by products.In this stage, additionally use equipment also just to become unnecessary at distillation purification vulcabond to obtain the ideal diisocyanate unit.
Can avoid extra astoundingly fully because the diamines loss makes whole process productive rate significantly reduce cost that causes and the economy that also can therefore improve this method by the urea without conditioning 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 plant factor owing in each equipment unit, producing self-adhesion.
Now also find, if use alicyclic diamines, then preferably after it is synthetic, from alicyclic two urea alkane, remove by alicyclic diamine and pure and mild urea and/or urea derivative are reacted easily boil thing with in the thing that boils, alicyclic two urea alkane thermolysiss after so purifying are discharged required alicyclic diisocyanate simultaneously, from resolving device, discharge the decomposition tower substrate of a part continuously and carry out again the urea alkanisation removing the high boiling material composition, and the logistics after will so purifying reclaims in the importing process with alcohol.Can be sure of, on the one hand, synthetic via whole order two urea alkane in this way, two urea alkane are purified and two urea alkane decompose the high boiling material composition that can realize low static concentration, thereby make that the alluvial phenomenon of particularly impelling owing to the person's character of high viscosity high boiling material composition can be avoided to the full extent, and also can guarantee good plant factor and good process yield for a long time.On the other hand, the order of the alkanisation of urea again of carrying out after the pyrolysis and the sepn process of high boiling material has following advantage, promptly compare with the conventional process that high boiling material was wherein removed before two urea alkane decompose, the amount that is transferred to the two urea alkane that go in the gas phase significantly reduces, and can save the cost of cost and energy thus.
Theme of the present invention is a kind of multi-stage method of continuous preparation alicyclic diisocyanate, it is that to make alicyclic diamines and carbonic acid derivatives and alcohol reaction generate alicyclic two urea alkane and then make two urea alkane thermolysiss be alicyclic vulcabond, it is characterized in that, after it is synthetic, from alicyclic two urea alkane, remove by alicyclic diamine and pure and mild urea and/or urea derivatives are reacted easily boil thing with in the thing that boils, alicyclic two urea alkane thermolysiss after so purifying are discharged required vulcabond simultaneously, from resolving device, discharge the decomposition tower substrate of a part continuously and carry out again the urea alkanisation and then remove the high boiling material composition with alcohol, and the logistics after will so purifying is recycled in the process, wherein uses without the urea of conditioning and/or the urea Equivalent that is made by the urea without conditioning.
Theme of the present invention also is the multi-stage method of the alicyclic diisocyanate of a kind of continuous preparation formula (I),
OCN-R-NCO
Wherein R represent divalence have 4 to 18, the alicyclic alkyl of preferred 5 to 15 carbon atoms, prerequisite is that two nitrogen-atoms directly are connected on the hydrocarbon ring and at least 3 carbon atoms of arrangement between them, this method generates alicyclic two urea alkane by alicyclic diamine and urea and/or urea derivatives and alcohol reaction and is undertaken by its thermolysis, wherein
A) make the alicyclic diamine of formula (II) and the alcohol of urea and/or urea derivatives and formula (III) not have or exist dialkyl carbonate, carboxylamine (carbamids ure) alkyl ester or dialkyl carbonate and urea acid esters mixture and not exist or exist under the condition of catalyzer, reaction generates alicyclic two urea alkane and removes formed ammonia simultaneously
H
2N-R-NH
2 (II)
R wherein represent divalence have 4 to 18, the alicyclic alkyl of preferred 5 to 15 carbon atoms, prerequisite is that two nitrogen-atoms directly are connected and are arranged with at least 3 carbon atoms on the hydrocarbon ring and between them,
R
1-OH (III)
R wherein
1Be illustrated in removed from after the hydroxyl of uncle with 3 to 8 carbon atoms or secondary fat (ring) family alcohol remaining residue;
B) from the reaction mixture of gained, separate alcohol, dialkyl carbonate and/or alkyl carbamate and with alcohol and optional dialkyl carbonate in addition and/or alkyl carbamate return lead step of reaction a) in;
C) completely or partially give up and separate the boil step of residue of the optional height that is contained in the gained reaction mixture;
D) under the catalyzer existence condition, continuously and solvent-freely under 180 to 280 ℃, preferred 200 to 260 ℃ temperature and 0.1 to 200mbar, under preferred 0.2 to 100mbar the pressure Continuous Heat decompose contain via step b) and optional c) reaction mixture of the two urea alkane that obtain of purifying, thereby will be benchmark 10 to 60 weight %, preferably be that the partial reaction mixture of benchmark 15 to 45 weight % is discharged in the feeding material constantly in the feeding material;
E) by rectifying decomposed product is divided into thick alicyclic diisocyanate and alcohol;
F) also separate the product cut of purifying by the thick alicyclic diisocyanate of distillation purification;
G) will be from d) tower at the bottom of ejecta partially or completely with from e) alcohol under the condition that has or do not exist catalyzer in 1 to 150min, in preferred 3 to 60min time, under 20 to 200 ℃, preferred 50 to 170 ℃ temperature and 0.5 to 20bar, react under preferred 1 to 15bar the pressure, wherein the mol ratio of NCO-group and OH-group is for being at most 1: 100, preferred 1: 20 and extremely preferred 1: 10;
H) will be from g) the alkylated product of urea again stream be divided into useful logistics and waste streams and from process, discharge and give up the waste streams that is rich in the high boiling point composition;
I) discharge a part of purification still-process f continuously) tower bottom distillate and import to the decomposition reaction step d) or import in the urea alkanisation stage g);
J) optional will be at the distillation f that purifies) overhead fraction that produced during thick alicyclic diisocyanate returns equally and leads in the urea alkanisation stage g);
K) will be from h) useful logistics return the stage of leading a), b) or d) in,
Wherein adopt without the urea of conditioning and/or by the prepared urea Equivalent of urea without conditioning.
The method according to this invention can make alicyclic diisocyanate with extraordinary productive rate without a doubt under operate continuously.In multistage method of the present invention, have the following advantages especially, 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 also can guarantee good plant factor and good process yield for a long time.In addition, another advantage of multistage method of the present invention is that the amount that can allow will to be transferred to the two urea alkane that go in the vapor phase reduces to minimum value and limits required energy consumption in this way.
A) for step of reaction a) in the preparation monomeric alicyclic two urea alkane, will make the alicyclic diamine of formula (II) and the alcohol of urea and/or urea derivatives and formula (III), optional also can with these pure mixture reactions, its mol ratio is 1: 2.01: 4.0 to 1: 2.2: 10, preferred 1: 2.02: 6 to 1: 2.12: 9, but also optional can not be the dialkyl carbonate that benchmark is 1-10Mol% in the diamines there being consumption preferably, react under the condition of the mixture of alkyl carbamate or dialkyl carbonate and carbamate, do not exist or exist under the catalyzer situation and at 140-270 ℃, preferred 160-250 ℃ temperature and according to used alcohol and at 2-80bar, the pressure of preferred 7-15bar reacted 2 to 20 hours down, preferred 4-9 hour.Reaction can be in the stirring tank cascade unit of operate continuously, but also preferably carries out in the pressure distillation reactor.
For improving speed of reaction, can under the catalyzer existence condition, prepare alicyclic two urea alkane.What be suitable as catalyzer is inorganic or organic compound, and it comprises IA in one or more, the preferred cycle table, 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, and Chemical Rubber Publishing Co. press publishes, 2310Superior Ave.N.E.Cleveland, the 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 sulfo-or dithiocar-bamate.The example that can mention 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 can mention 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, acetopyruvic acid vanadium, manganese acetate (II), iron acetate (II), iron acetate (III), ironic oxalate, cobalt chloride, cobalt naphthenate, nickelous chloride, nickel naphthenate and their mixture.Catalyzer is optional also can its hydrate or the use of amide (Ammoniakate) form.
Under the condition of the mixture that does not have or exist dialkyl carbonate, alkyl carbamate or dialkyl carbonate and alkyl carbamate, the starting compound that is used for the inventive method is to have had the alicyclic diamine of above-mentioned formula (II), have the alcohol and a urea of above-mentioned formula (III) and/or be suitable as the urea derivatives (carbonic acid derivatives) of carboxylic acid reagent.
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) since preparation condition limit can be with 4,4 '-, 2,4-and 2, the form appearance (referring to for example DE10127273) of the isomer mixture that 2 '-MDA forms.All hydrogenated methylenediphenyl diamines obtains by complete hydrogenation MDA and so but a kind of methylene radical dicyclohexyl diamines (H by 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 these isomer.Obviously, also can use and the different diamines of formula (II).For example have 1,3-and 1,4-diaminomethyl hexanaphthene, hexamethylene diamine, 6,2,2,4-or 2,4,4-trimethylammonium hexylamine-1,6 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 aliphatic series arbitrarily or the alicyclic alcohol that is lower than 190 ℃ of boiling points.The example that can mention is that C1-C6 alcohol is as methyl alcohol, ethanol, 1-propyl alcohol, 1-butanols, 2-butanols, 1-hexanol or hexalin.Preferably use the 1-butanols as alcohol.
In the reaction mixture reaction process, can discharge ammonia, consider with its removal it is more favourable for molecular balance.When being discharged from reactor, ammonia to note, the wall temperature of reactor and vent pipe will be higher than 60 ℃, can avoid thus by the formed fouling of ammonium carbamate (Ammoniumcarbaminat), and ammonium carbamate is to be formed by the ammonia and the carbonic acid gas that obtain by the decomposition urea with minimum.For example verified effective way is to make to be reflected in the pressure distillation reactor to carry out, and wherein makes reaction mixture import in the pure steam that penetrates at the bottom of the tower with the adverse current form and liquid is all met on the column plate of cascade structure actually to carry out intense mixing.The vapour mixture that ammonia that extract out from cat head, pure and mild constitutes can preferably import to the distillation tower under the pressure of pressure distillation reactor and under the condition of not condensation in advance, to obtain not ammoniated alcohol, then alcohol is gone back to the bottom of leading pressure distillation reactor and tower.For avoiding ammonium carbamate to form fouling in reflux exchanger, the alcohol that will import respective amount therein arrives at least 60 ℃ with the temperature regulation with cat head.
B) with excessive alcohol, as long as that form or be present in dialkyl carbonate in the reaction mixture or alkyl carbamate or these compositions at least two kinds mixture and preferably separate with two stages.The first step with the reaction mixture on step of reaction stress level a) be decompressed to 1 to 500mbar, preferred 2 to 150mbar pressure, and be divided into the alcohol that contains main amount and the optional dialkyl carbonate and/or the steam and the liquid ejecta of alkyl carbamate in this way.In second step by thin film evaporation 180 to 250 ℃, preferred 200 to 230 ℃ remove from liquid ejecta down and 0.1 to 20mbar, under preferred 1 to 10mbar the pressure the optional remaining alcohol that exists and boil thing such as dialkyl carbonate and/or alkyl carbamate, thereby make resistates form by preferred two urea alkane of monomeric urethane and the optional height oligopolymer that boils in fact.
Steam can be preferably after distillation is purified, randomly return lead step of reaction a) in.
C) preferably save the optional high boiling material that contains in the reaction mixture that at every turn is separated in stage b).If but just adopt a part stream, promptly partly carry out h) described in stage g) gastral cavity alkylated product stream separating process again, then can advantageously take a kind of isolating approach of high boiling material that is used for of the following stated:
Choose wantonly, can preferably utilize thin layer or quick (Kurzweg) vaporizer, at 180 to 270 ℃, preferred 200 to 250 ℃ temperature with 0.01 to 10mbar, under preferred 0.02 to 5mbar the pressure, to come from step b), separated easily boil thing and in boil resulting liquid state after the thing and logistics that contain monomeric two urea alkane and optional high boiling point oligopolymer, fractionation by distillation becomes to contain the useful logistics and the not distillable byproduct stream of the monomeric two urea alkane and the by product that easily boils.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.
Choose wantonly, also can will also be divided into two strands of part streams before carrying out its above-mentioned distillation purification process from the boil logistics of oligopolymer of optional height of containing of stage b), wherein one directly imports to decomposition reaction (Deblockierungsreaktion) (referring to d)) in go another strand then at first to go through above-mentioned high boiling material sepn process.
D) make from stage b) and optional phase c) the useful logistics that contains the monomer two urea alkane and the by product that easily boils in suitable device partly, solvent-freely in liquid phase and thermolysis continuously under in 180 to 280 ℃, preferred 200 to 260 ℃ temperature and 0.1 to 200mbar, preferred 0.2 to 100mbar pressure under the catalyzer existence condition.In thermal decomposer, two urea alkane generate the transformation efficiency of vulcabond and can freely select to a great extent according to two used urea alkane, and normally in the scope of the two urea alkane amounts (feeding material) that 10 to 95 weight %, preferred 35 to 85 weight % are imported.Discharge on the undecomposed partial continuous ground of reaction mixture, and this part comprises by product and other byproducts that can utilize and can not utilize that unreacted two urea alkane, height boil.The amount of ejecta is decided on for example decomposition reaction desired transformation efficiency and desired production capacity, and can determine by test simply.This value is generally 10 to 60 weight %, preferred 15 to 45 weight %, is benchmark in the feeding material.
As the catalyzer of decomposition two urea alkane, the inorganic and organic compound that can use for example aforesaid catalysis urea alkane to form.Preferred zinc or the muriate of tin and the oxide compound of zinc, manganese, iron or cobalt of using, wherein catalyzer with 5 to 400ppm, preferred 10 to 100ppm amount add metering be added to import to before going in the decomposition course and from purification order b) and optional c) the logistics that contains two urea alkane basically in, this logistics is the solution or the form of suspension that also can be used for the preferred alcohols of urea alkane in preparing of 0.01 to 25 weight %, preferred 0.05 to 10 weight %.
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.
Basic problem is that the isocyanate groups that will inevitably discharge when alcohol decomposes will keep very little as far as possible at the average retention time of resolver, and the side reaction that will not expect 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 following 1/3rd places that are connected with the device that is used for extra intake or is used for recovered energy, import to last 1/3rd places that are connected with the device that is used to extract out thick vulcabond and import to and be connected with the top of tower that is used to reflux and extracts the condenser of pure alcohol out.
E) under 95 to 260 ℃, preferred 110 to 245 ℃ temperature and 0.5 to 250mbar, preferred 1 to 100mbar pressure, by the degradation production that the two urea alkane that form in the thermal decomposition process and at first decomposed by alcohol, vulcabond and part are formed in rectifying, be separated into the pure and mild thick mixtures of diisocyanates of preferably forming by alicyclic diisocyanate, the alicyclic diisocyanate that partly decomposes and optional a small amount of alicyclic two urea alkane.This separation can for example be carried out in above-mentioned built-up type decomposition and the decomposition tower in the rectifying tower.
F) under 95 to 260 ℃, preferred 110 to 245 ℃ temperature and 0.5 to 150mbar, preferred 1 to 75mbar pressure, the thick mixture that will preferably obtain by rectifying by distillation and alicyclic two urea alkane that decomposed by alicyclic diisocyanate, part and optional a small amount of alicyclic two urea alkane are formed is purified, and returns simultaneously to lead formed fraction or isolate as clean product.
G) ejecta is partially or completely with from stage of rectification e at the bottom of tower catabolic phase d)) alcohol import, wherein the mol ratio of NCO-group and OH-group is paramount 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 under 20 to 200 ℃, preferred 50 to 170 ℃ temperature and 0.5 to 20bar, preferred 1 to 15bar pressure.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 and triethylamine are for example arranged.Again the urea alkanisation also can exist Fe (III)-or the condition of Cu (I)-halogenide or their mixtures under carry out.Fe (III)-muriate, Fe (III)-bromide, Cu (I)-muriate and Cu (I)-bromide are for example arranged.The effect of using other catalyzer, the latter to play acceleration urea alkylation reaction is not simultaneously got rid of in the adding of these catalyzer in principle.Preferred halogenide that uses Fe (III) or Cu (I) or their mixture and additionally do not use other catalyst.
H) will become useful logistics and waste streams from the alkylated product of the urea again flow point of stage g) and from process, 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 distillation by means of thin layer or flash evaporator, carry out at 180 to 270 ℃, preferred 200 to 250 ℃ temperature with 0.01 to 10mbar, under preferred 0.02 to 5mbar the pressure.The useful logistics that contains the monomer two urea alkane and the by product that easily boils produces as overhead product.The waste streams that is rich in the high boiling point composition then forms as residue and discharges from preparation process 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.
Choose wantonly, also can incite somebody to action urea alkylated product stream again and be separated into two strands of part streams before above-mentioned purification, wherein one directly imports in the urea alkanisation stage b) again.The distribution of two strands of part streams can be carried out according to 99: 1 to 1: 99, preferred 95: 5 to 5: 95 mode.Remove excessive alcohol partially or completely in the optional at first alkylated product of urea again from import the high boiling material sepn process stream.This process is preferably carried out in the distillation mode.Isolating alcohol can choose wantonly back the stage of leading a) or b) in.
I) discharge continuously a part from purification still-process f) tower bottom distillate and back choose importing catabolic phase d) or urea alkanisation stage g) in.Preferred returning imports the urea alkanisation in the stage.The amount of ejecta is 0.1 to 50 weight %, preferred 0.2 to the 25 weight % of polyisocyanates import volume thick in the purification distillation stage.
J) overhead fraction of purification distillation stage f) can be given up or preferably return in the importing urea alkanisation stage g).The amount of the overhead fraction that each time unit discharged is 0.1 to 3 weight %, preferred 0.3 to the 1 weight % of polyisocyanates import volume thick in the purification still-process.
K) will from the useful logistics of stage h) return import two urea alkane preparation process a), easily boil thing and in the thing sepn process b that boils) or two urea alkane decomposition course d) in.Equally also can return lead-in stage c) in, but not preferred.
Utilize multistage method of the present invention to prepare alicyclic diisocyanate continuously and return and lead and discharge by product, for distillable alicyclic vulcabond, can guarantee to be reflected in the long time and carry out without barrier so that higher selectivity is smooth and easy.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 mixture of the methylene radical dicyclohexyl vulcabond of above-mentioned isomery, for example their can be converted into H at perhydro-MDA according to its character
12Produce in the MDI process.
Prepared alicyclic vulcabond is suitable for being equipped with according to polymeric polyisocyanate-addition polymerization legal system the plastics of urea-alkyl containing base, isocyanuric acid ester group, amide group and/or urea groups most.In addition, they also can be used for preparing the mixture of polyisocyanates with urea alkyl, biuret groups and/or the modification of tricarbimide 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 (52)
1. continuous multi-stage method of preparation alicyclic diisocyanate, it is alicyclic vulcabond by making alicyclic diamines and carbonic acid derivatives and alcohol reaction generate alicyclic two urea alkane and then make two urea alkane thermolysiss, it is characterized in that, after it is synthetic, from alicyclic two urea alkane, remove by alicyclic diamine and pure and mild urea and/or urea derivatives are reacted easily boil thing with in the thing that boils, alicyclic two urea alkane thermolysiss after so purifying are discharged required vulcabond simultaneously, from resolving device, discharge the decomposition tower substrate of a part continuously and carry out again the urea alkanisation and remove the high boiling material composition afterwards with alcohol, and the logistics after will so purifying is recycled in the process, wherein uses without the urea of conditioning and/or the urea Equivalent that is made by the urea without conditioning.
2. the multi-stage method of the alicyclic diisocyanate of a continuous preparation formula (I),
OCN-R-NCO
R wherein represent divalence have 4 to 18, the alicyclic alkyl of preferred 5 to 15 carbon atoms, prerequisite is that two nitrogen-atoms directly are connected on the hydrocarbon ring and at least 3 carbon atoms of arrangement between them, generate alicyclic two urea alkane by alicyclic diamine and urea and/or urea derivatives and alcohol reaction in the method and undertaken, wherein by its thermolysis
A) make the alicyclic diamine of formula (II) and the alcohol of urea and/or urea derivatives and formula (III) not have or exist dialkyl carbonate, alkyl carbamate or dialkyl carbonate and carboxylamine ester mixture and not exist or exist under the condition of catalyzer, reaction generates alicyclic two urea alkane and removes formed ammonia simultaneously
H
2N-R-NH
2 (II)
R wherein represent divalence have 4 to 18, the alicyclic alkyl of preferred 5 to 15 carbon atoms, prerequisite is that two nitrogen-atoms directly are connected and are arranged with at least 3 carbon atoms on the hydrocarbon ring and between them,
R
1-OH (III)
R wherein
1Be illustrated in removed from after the hydroxyl of the uncle with 3 to 8 carbon atoms or secondary fat (ring) alcohol remaining residue;
B) from the reaction mixture of gained, separate alcohol, dialkyl carbonate and/or alkyl carbamate and with alcohol and optional dialkyl carbonate in addition and/or alkyl carbamate return lead reactions steps a) in;
C) completely or partially give up and separate the boil step of residue of the optional height that is contained in the gained reaction mixture;
D) under the catalyzer existence condition, continuously and solvent-freely under 180 to 280 ℃, preferred 200 to 260 ℃ temperature and 0.1 to 200mbar, Continuous Heat is decomposed via step b) and optional c under preferred 0.2 to 100mbar the pressure) the resulting reaction mixture of two urea alkane of purifying, thus will be benchmark 10 to 60 weight %, preferably be that the partial reaction mixture of benchmark 15 to 45 weight % is discharged in the feeding material constantly in the feeding material;
E) by rectifying decomposed product is divided into thick alicyclic diisocyanate and alcohol;
F) purify thick alicyclic diisocyanate and separate pure product fraction by distilling;
G) will be from d) tower at the bottom of ejecta partially or completely with from e) 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 0.5 to 20bar, react under preferred 1 to 15bar the pressure, wherein the mol ratio of NCO-group and OH-group is 1: 100 at the most, preferred 1: 20 and extremely preferred 1: 10;
H) will be from g) the alkylated product of urea again stream be divided into useful logistics and waste streams and from process, discharge and give up the waste streams that is rich in the high boiling point composition;
I) the tower bottom distillate purification of a discharge part continuously distillation f) also imports to decomposition reaction d) or import in the urea alkanisation stage g);
J) optional will be at the distillation f that purifies) overhead fraction that produced during thick alicyclic diisocyanate returns equally and leads in the urea alkanisation stage g);
K) with h) useful logistics return the stage of leading a), b) or d) in,
Wherein adopt without the urea of conditioning and/or by the prepared urea Equivalent of not nursing one's health of urea.
3. multi-stage method as claimed in claim 1 or 2 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.
4. multi-stage method as claimed in claim 1 or 2 is characterized in that, as alicyclic diamines, uses 4, the alicyclic diamine of 4 '-methylene radical dicyclohexyl diamines and/or isomery.
5. multi-stage method as claimed in claim 1 or 2 is characterized in that, uses 1 as alicyclic diamine, the 4-diamino-cyclohexane.
6. at least one described multi-stage method in the claim as described above is characterized in that the stage a) carries out continuously in distillation reactor or stirring tank cascade device.
7. at least one described multi-stage method in the claim as described above is characterized in that, the stage is reflected at diamines in a): urea: the mol ratio of alcohol is to carry out for 1: 2.01: 4.0 to 1: 2.2: 10 time.
8. at least one described multi-stage method in the claim as described above, wherein, the raw material thing is 2 to 20 in the residence time of stage in a), preferred 4 to 9 hours.
9. at least one described multi-stage method in the claim as described above is characterized in that, the stage a) carries out under 140 to 270 ℃ and 2 to 80bar pressure in reactor.
10. at least one described multi-stage method in the claim as described above is characterized in that, the stage is reflected in a) under 160 to 250 ℃ temperature of reaction and 7 to 15bar the pressure carries out.
11. at least one described multi-stage method in the claim is characterized in that the stage a) carries out in the pressure distillation reactor as described above.
12. at least one described multi-stage method in the claim as described above wherein is assigned to the raw material thing on the column plate of going up most in a) and by the auxiliary ammonia that is discharged of discharging of the alcohol vapor that imports to the distillation reactor bottom in the stage continuously.
13. at least one described multi-stage method in the claim is characterized in that as described above, the stage is the middle alcohol with 1-6 carbon atom that uses a).
14. at least one described multi-stage method in the claim is characterized in that as described above, the stage is the middle butanols that uses a).
15. at least one described multi-stage method in the claim is characterized in that as described above, stage being reflected under the catalyzer existence condition in a) carried out.
16. at least one described multi-stage method in the claim is characterized in that stage b) carries out in two stages as described above.
17. multi-stage method as claimed in claim 16 is characterized in that, in the fs with step of reaction a) reaction mixture under the stress level reduce pressure 1 to 500mbar, preferred 2 to 150mbar pressure.
18. as claim 16 or 17 described multi-stage methods, it is characterized in that, in second step, under the pressure of 180 ℃ to 250 ℃, preferred 200 ℃ to 230 ℃ temperature and 0.1mbar to 20mbar, preferred 1mbar to 10mbar, from liquid ejecta, remove by thin film evaporation the optional remnants that exist alcohol and in boil thing such as dialkyl carbonate and/or alkyl carbamate.
19. as claim 16 or 17 described multi-stage methods, it is characterized in that, the steam of stage b) imported to step of reaction go in a) after further distillation is purified.
20. at least one described multi-stage method in the claim as described above, it is characterized in that, separation in stage c) if adopt, is carried out under 180 to 270 ℃, preferred 200 to 250 ℃ temperature and 0.01 to 10mbar, preferred 0.02 to 5mbar pressure.
21. at least one described multi-stage method in the claim is characterized in that stage c) if adopt, carries out by means of thin layer or flash evaporator as described above.
22. at least one described multi-stage method in the claim is characterized in that as described above, discharges and give up the by product of stage c), if adopt.
23. at least one described method in the claim as described above, it is characterized in that,, the logistics in the stage c) is handled if adopt, made before its distillation is purified it to be divided into two strands of part streams that wherein one part stream directly imports to decomposition reaction and (goes in the stage d).
24. at least one described method in the claim as described above, it is characterized in that, the thermoinducible two urea alkane decomposition coursees of stage d) carry out in tube furnace or preferred vaporizer, described vaporizer is for example falling-film evaporator, thin layer evaporator or Bulk vaporizer, is selected from Robert vaporizer, Herbert vaporizer, Caddle type vaporizer, Oskar vaporizer and heating candle formula vaporizer.
25. at least one described multi-stage method in the claim is characterized in that stage d) carries out in decomposition of making up and rectifying tower as described above.
26. at least one described multi-stage method in the claim is characterized in that as described above, in stage d), carries out thermolysis continuously under 180 to 280 ℃, preferred 200 to 260 ℃ temperature and 0.1 to 200mbar, preferred 0.2 to 100mbar pressure.
27. at least one described multi-stage method in the claim is characterized in that as described above, in the step d), decomposes in liquid phase under solvent-free condition.
28. at least one described multi-stage method in the claim is characterized in that stage d) carries out under the catalyzer existence condition as described above.
29. at least one described multi-stage method in the claim as described above, it is characterized in that, in the stage d), two urea alkane generate the transformation efficiency of vulcabond and freely select according to two used urea alkane, preferably at 10 to 95 weight % of the two urea alkane amounts that imported (feed and expect), more preferably in the scope of 35 to 85 weight %.
30. at least one described multi-stage method in the claim as described above, it is characterized in that, in stage d), discharge a part of reaction mixture continuously, described mixture comprises by product and other recycling and can not the utilize by products that unreacted two urea alkane, height boil.
31. multi-stage method as claimed in claim 30 is characterized in that, output is 10 to 60 weight %, preferred 15 to the 45 weight % of feeding material.
32. at least one described multi-stage method in the claim is characterized in that stage e) carries out in decomposition of making up and rectifying tower as described above.
33. at least one described multi-stage method in the claim is characterized in that as described above, carries out under 95 to 260 ℃, preferred 110 to 245 ℃ temperature and 0.5 to 250mbar, preferred 1 to 200mbar pressure.
34. at least one described multi-stage method in the claim as described above, it is characterized in that purifying by distillation under in 95 to 260 ℃, preferred 110 to 245 ℃ temperature and 0.5 to 150mbar, preferred 1 to 75mbar pressure derives from the thick fraction that stage e) and alicyclic two urea alkane that decomposed by alicyclic diisocyanate, part and optional a spot of alicyclic two urea alkane are formed in stage f).
35. the multi-stage method described in claim 34 is characterized in that, the fraction that is produced in the stage f) obtains or leads and get back in the stage g) with the isolated in form of pure product.
36. at least one described multi-stage method in the claim is characterized in that as described above, in stage h), process is carried out under 180 ℃ to 270 ℃, preferred 200 to 250 ℃ temperature and 0.01 to 10mbar, preferred 0.02 to 5mbar pressure.
37. at least one described multi-stage method in the claim is characterized in that as described above, utilizes thin layer evaporator or flash evaporator to carry out in the distillatory mode in the stage h).
38. at least one described multi-stage method in the claim is characterized in that stage h) is undertaken by extraction as described above.
39. at least one described multi-stage method in the claim is characterized in that, with g as described above) the alkylated product of urea again stream optionally before distillation is purified be divided into two bursts of parts and flow, wherein one directly imports to purification phase b) in.
40. multi-stage method as claimed in claim 39 is characterized in that, two strands of part stream distributes according to 99: 1 to 1: 99, preferred 95: 5 to 5: 95 ratio.
41. at least one described multi-stage method in the claim is characterized in that stage g) is to carry out at the successive equipment cascading or in tubular reactor as described above.
42. at least one described multi-stage method in the claim as described above, it is characterized in that, being reflected in the stage g) exist be selected from Sn-and/or Zn-carboxylate salt or-halogenide, tertiary amine, Cu (I)-and/or the condition of Fe (III)-halid catalyzer under carry out.
43. at least one described multi-stage method in the claim is characterized in that as described above, returns to import in the urea alkanisation stage g) in stage i).
44. at least one described multi-stage method in the claim is characterized in that as described above, in stage i), output is 0.1 to 50 weight %, preferred 0.2 to the 25 weight % of polymeric polyisocyanate input thick in the purification distillation stage.
45. at least one described multi-stage method in the claim is characterized in that as described above, the amount of the overhead fraction that per time unit discharges in stage j) is 0.1 to 3 weight %, preferred 0.3 to the 1 weight % of vulcabond input thick in the distillation of purifying.
46. at least one described multi-stage method in the claim as described above, it is characterized in that, from from g) importing high boiling material sepn process h) the alkylated product of urea again stream remove excessive alcohol at first partially or completely and the alcohol that will remove choose wantonly back lead-in stage a) or b) in.
47. at least one described multi-stage method in the claim is characterized in that, from high boiling material sepn process h as described above) useful logistics return lead-in stage a), b) or d) in.
48. at least one described multi-stage method in the claim as described above, it is characterized in that, preparation 1,4-two isocyanato-hexanaphthenes, 4,4 '-methylene radical dicyclohexyl vulcabond, 2,2 '-methylene radical dicyclohexyl vulcabond, 2, any mixture of the methylene radical dicyclohexyl vulcabond of 4 '-methylene radical dicyclohexyl vulcabond or at least two kinds of isomeries.
49. at least one described multi-stage method in the claim is characterized in that used diamines is selected from 1,3-and 1,4-diaminomethyl hexanaphthene, hexamethylene diamine as described above, 6,2,2,4-or 2,4,4-trimethylammonium hexylamine-1,6 and 3-aminomethyl-3,5,5-trimethylcyclohexyl amine.
50. at least one described multi-stage method in the claim as described above, it is characterized in that the maximum concentration of formaldehyde of used urea or used urea Equivalent (also can be Paraformaldehyde 96) is 0.01 to 0.10 weight %, preferred 0.001 to 0.01 weight % and especially preferably less than 0.001 weight %.
51. at least one described multi-stage method in the claim is characterized in that as described above, without inorganic substance and/or formaldehyde urea carried out surface treatment.
52. at least one described multi-stage method in the claim is characterized in that urea does not contain talcum, wilkinite, diatomite, Bacillariophyta, kaolin or other silicate materials as described above.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006061471.2 | 2006-12-23 | ||
| DE102006061471A DE102006061471A1 (en) | 2006-12-23 | 2006-12-23 | Multistep process to prepare cycloaliphatic diisocyanates, useful to prepare e.g. urethane, comprises reacting cycloaliphatic diamine with carbonic acid derivative and alcohol and thermally cleaving the obtained cycloaliphatic diurethane |
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| Publication Number | Publication Date |
|---|---|
| CN101234997A true CN101234997A (en) | 2008-08-06 |
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| CNA2007101600629A Pending CN101234997A (en) | 2006-12-23 | 2007-12-21 | Multi-stage method for continuously preparing alicyclic diisocyanate |
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| DE (1) | DE102006061471A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102918024A (en) * | 2009-12-16 | 2013-02-06 | 赢创德固赛有限公司 | Compounds made of (cyclo)aliphatic diisocyannates and aromatic acid halides |
-
2006
- 2006-12-23 DE DE102006061471A patent/DE102006061471A1/en not_active Withdrawn
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102918024A (en) * | 2009-12-16 | 2013-02-06 | 赢创德固赛有限公司 | Compounds made of (cyclo)aliphatic diisocyannates and aromatic acid halides |
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