CN101205198A - Multilevel method for continuously producing cycloaliphatic diisocyanates - Google Patents
Multilevel method for continuously producing cycloaliphatic diisocyanates Download PDFInfo
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- CN101205198A CN101205198A CNA200710152720XA CN200710152720A CN101205198A CN 101205198 A CN101205198 A CN 101205198A CN A200710152720X A CNA200710152720X A CN A200710152720XA CN 200710152720 A CN200710152720 A CN 200710152720A CN 101205198 A CN101205198 A CN 101205198A
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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
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Abstract
The present invention relates to a multistage method for preparing alicyclic vulcabond on the continuous and phosgene-free conditions.
Description
Technical field
The present invention relates to a kind of continuously and prepare the multi-stage process of cycloaliphatic diisocyanates under the no phosgene condition.
Background technology
The synthetic of isocyanic ester can obtain by a series of different routes.The scale operation pattern variant of the most ancient also is present dominant isocyanic ester is so-called phosgene route.The basis of this method is that amine and phosgene are reacted.The shortcoming of phosgene method is to use phosgene, because its toxicity and corrodibility processing to it in industrial standards have higher requirements.
Other many methods of using phosgene to prepare isocyanic ester are included in the technical grade.The idea of no phosgene method is used usually amine is converted into the relevant alternative carbonylation agent of isocyanic ester, for example urea or dialkyl carbonate (EP 0 018 586, and EP 0 355 443, and US 4 268 683, and EP 0 990 644).
The basis of said here urea route is by relevant with urea diamines to be converted into vulcabond in the second order reaction process.In the first step, a kind of diamines and alcohols are at urea or urea ketone thing (alkyl carbonate for example, alkyl carbamate) is converted into the diamino acid ethyl ester under the existence, usually its through intermediate purification step and then second step in vulcabond and alcohols thermo-cracking (EP 0 355 443, and US 4,713,476, US5,386,053).Alternative plan can be: by targetedly independent preparation two ureas of diamines and urea reaction being prepended to original diamino acid ethyl ester synthetic (EP 0 568 782).Optimal two orders by urea in the first step and the partial reaction of alcohol and next in second goes on foot diamines be metered into that esterification constitutes (EP 0 657 420) with ammonia.
Corresponding isocyanate and ammonia ester thermo-cracking in the alcohols be exactly for a long time known and can gas phase high temperature with in relative cryogenic liquid phase, carry out.Problem is, in these two kinds of ways and means, can produce the side reaction of non-expectation in essence by heat load, it has reduced output on the one hand and has produced resinification by product on the other hand, and this by product is by distributing and block the carrying out that further hinders technical process in reactor and processing units.
In addition, measure productive rate that is improved and the scheme that the by product that limits non-expectation produces by chemistry and Technology is absolutely necessary.Therefore, a series of document description quicken the use (DE 10 22 222, and US 3,919,279, and DE 26 35 490) of the catalyzer of ammonia ester scission reaction.In fact, under the appropriate catalyst condition-here about the thorough raising isocyanic ester output of a large amount of alkalescence, acidity and organometallics-compare with the catalyst-free pattern.Yet still can not avoid the production of by-products of non-expectation by using catalyzer.Equally, distribute uniformly at reaction medium, additionally use inert solvent in order to ensure the heat and the catalyzer that drop into, as it at US 3,919,279 with DE 26 35 490 in recommend the same.In principle, use backflow ebullient solvent causes the minimizing of isocyanic ester space/time output, has the shortcoming of extra high energy expenditure in addition.
In the monoamine ester thermocatalysis cracked example that EP 0 054 817 provides, described and partly taken out reaction mixture to be separated in the resinification by product that produces in the ammonia ester cracking process.This process has been avoided distributing and blocking in reactor and processing units.Prompting is not represented the part taking-up with the value that output rises.EP 0,061 013 has described a kind of similar dissolution mechanism, and it is directly better to absorb difficult evaporable by product by realize pyrolysis, the task of this solvent in this case in the presence of solvent.In addition, part is taken out and in fact is not used for output optimization.
Known at present by EP 0 355 443, if being used for of producing during cracking diamines urethanum (Diurethanen) guarantees not have the valuable and unworthy by product of polymer of upsetting alternative reaction and take out and and then reacted and send back to afterwards most of in the presence of the alcohols from reactor as far as possible continuously, can improve output so the preparation of diamino acid ethyl ester in cracking reactor.The technological process of its description has high energy, because will be by distillation by isolating unworthy by product in the ejecta of producing the diamino acid ethyl ester, this moment, all diamino acid ethyl esters must be evaporated.The ejecta of diamino acid ethyl esterization in the method for EP 0,566 925 that different with EP 0 355 443 is is divided into two strands of part streams, before wherein one diamino acid ethyl ester in the associating of decomposition reaction flows to cracking reactor, only distill out the unworthy by product of high boiling point.In addition, direct by EP 0 566 925 continuous cracking reactor extracts, promptly need not urethane esterification process once more, send the diamino acid ethyl ester back to and synthesize.
The operator scheme of EP 0 566 925 causes part to get back in the production of diamino acid ethyl ester from diamino acid ethyl ester synthetic high boiling component once more by decomposition course and continues to enter diamino acid ethyl ester process.
The processing mode of present dominant scale operation urea is a bead, and promptly diameter is the bead of 1-3mm.Crystallized urea is also tended to be baked to strongly under less than 0.1% ten minutes low water content it and is unsuitable for a large amount of loose storages.The improvement of urea bead storing property, for example show as a large amount of circular tower shape bunker storages in case of necessity, can handle the realization of bead surface with flour as required by a kind of, for example talcum powder, wilkinite, diatomite, Diatomacae or other silicates material, or realize by sulphur with by spraying a small amount of oil.
Formaldehyde before the urea industry preferred little nodularization at present increases at the most 0.6wt% (industrial chemistry encyclopaedia of Ullmann, 2006 the 7th edition) in the urea melts, to increase the stability of bead.This measure is used for prevention in transportation decay and baking and be used to improve storage stability.
By the urea melts of usefulness formaldehyde (and Paraformaldehyde 96) processing before spherical or granulating and the urea that constitutes with the surface-treated urea of formaldehyde (and Paraformaldehyde 96); also be a kind of for improving the industrial practical step of spheroid storing property, this urea is by one-level, secondary and alternatively prepare the cyclic aliphatic diurethanes and be that the by product that cycloaliphatic diisocyanates produces non-expectation carries out by thermo-cracking cyclic aliphatic diurethanes next according to multi-stage process.
The by product that produces synthesizes by processed continuously one or more levels diurethanes and not only causes after short working time because the scavenging process of the follow-up costliness followed of short relatively production time the sticking of non-expectation in equipment, and makes the distillation procedure of processing of thick diurethanes of the different steps described in detail in known and document inadequately to separate.
In cyclic aliphatic diurethanes thermo-cracking is in a whole set of process of cycloaliphatic diisocyanates, additionally toast by the isolated by product of diurethanes step non-quantitation and a kind of new thus by product scope that produces separately, reduce the operability of equipment in addition by expensive scavenging process.
Summary of the invention
Be that this task can solve by the following method surprisingly, promptly in order to prepare cycloaliphatic diisocyanates, by (for example encircling fat family diamines and urea and/or urea equivalent, alkyl carbonate, alkyl carbamate) and alcohols reaction to obtain the cyclic aliphatic diurethanes, next the cyclic aliphatic diurethanes is thermally cracked to cycloaliphatic diisocyanates, in order to generate the cyclic aliphatic diurethanes, use the urea of unconditional restriction, irrelevant with input form (bead, particle, crystal, molten mass, solution).The urea of unconditional restriction can be with surface-treated or added in the molten mass before bead or granulating substance and/or formaldehyde.
Urea and in order (for example to prepare the urea equivalent used according to the present invention, alkyl carbonate, alkyl carbamate) there is not condition restriction as the urea in the stage use before the possibility of synthetic cyclic aliphatic diurethanes, be that it can be surface-treated with inorganic substance, for example use talcum powder, wilkinite, diatomite, Diatomacae, kaolin or other silicates material, it can also use as anti-caking agent, and/or is constituted and/or be that usefulness formaldehyde (reaching Paraformaldehyde 96) is surface-treated by the urea molten mass of handling with formaldehyde (and Paraformaldehyde 96).Usually, the maximum concentration of formaldehyde of the urea of use or used urea equivalent (and Paraformaldehyde 96) is 0.01% to 0.10wt%, and preferred 0.001% to 0.01wt%, especially preferably less than 0.001wt%.
Be according to method advantage of the present invention, can stop the Quantitative Separation of less usually by product scope with purifying (ring) aliphatic diisocyanate by described distillation and rectifying device, and make the quality of the vulcabond that the utilisation technology performance is composed to be used for further extractive process and to need not to use procedure of processing.
Diurethanes in the stage by formaldehyde and/or by the component that contains formaldehyde of the urea of used unconditional restriction with the cycloaliphatic diamine reaction in alcohols exist separating of the little by product scope that produces be there is no need and also there is no need to use extra equipment.Owing to avoided by product next can also avoid with cyclic aliphatic diurethanes thermo-cracking being further by product scope in the cycloaliphatic diisocyanates in the stage at diurethanes.In addition, in this vulcabond distillation purifying stage, the vulcabond purity of using extra equipment to obtain to expect is unnecessary.
The relevant extra investment of the obvious decline of the holistic approach output that causes with diamines loss can be wonderful by use the urea of unconditional restriction to avoid fully according to the present invention, therefore improved the economy of present method.Wherein the diamines loss is brought by production of by-products, and it is owing to reduce the operability of equipment by expensive purge process in the baking of equipment different piece.
In addition, find that also it is favourable using cycloaliphatic diamine, cyclic aliphatic diamino acid ethyl ester discharges by cycloaliphatic diamine and alcohols and urea and/or urea derivatives reaction and by in low and the mid-boiling point material in its synthetic back, so the cyclic aliphatic diamino acid ethyl ester of purifying is discharging thermo-cracking under the cyclic aliphatic isocyanic ester of expecting, take out and isolate thus high boiling component from the part cracking substrate successive of cracking apparatus, and so the extract of purifying with alcohols urethane esterification and recycle in this process once more.Realized on the one hand the relative low steady concentration of high boiling component in, diamino acid ethyl ester purifying synthetic and the diamino acid ethyl ester cracking process in this way at whole diamino acid ethyl ester, so that formation throw out, this especially helps from natural high viscosity high boiling component, equipment availability and the good process output that can avoid to a great extent and keep for a long time getting well.Make the high boiling component separation in heat scission reaction downstream have advantage on the other hand, compare with the general method of carrying out, be separated before the cracking of diamino acid ethyl ester with this method high boiling substance, its diamino acid ethyl ester amount that is used to transport in vapor phase obviously reduces, and so just can reduce investment outlay and energy expenditure.
Target of the present invention is a multi-stage process of preparation cycloaliphatic diisocyanates continuously, it passes through cycloaliphatic diamine and carbonic acid derivatives and alcohols reaction generation cyclic aliphatic diamino acid ethyl ester, next thermo-cracking diamino acid ethyl ester is a cycloaliphatic diisocyanates, it is characterized in that, cyclic aliphatic diamino acid ethyl ester after it is synthetic by with cycloaliphatic diamine and alcohols and urea and/or urea derivatives reaction and by hang down with the mid-boiling point material in discharge, so the cyclic aliphatic diamino acid ethyl ester of purifying is discharging thermo-cracking under the vulcabond of expecting, part cracking substrate is by taking out continuously in the cracking apparatus, isolate high boiling component thus, and so the extract of purifying is with alcohols urethane esterification and recycle in this process once more, at this moment, use the urea of unconditional restriction or/and the urea equivalent of producing by unconditional restriction urea.
Theme of the present invention still is the multi-stage process of a continuous preparation formula (I) cycloaliphatic diisocyanates
OCN-R-NCO
Wherein, the R representative has 4 to 18, the divalence cycloaliphatic hydrocarbon residue of preferred 5 to 15 carbon atoms, prerequisite is, two nitrogen-atoms directly are connected with the hydrocarbon ring, have arranged three carbon atoms therebetween at least, obtain cyclic aliphatic diamino acid ethyl ester by cycloaliphatic diamine and urea and/or urea derivatives and alcohols reaction, and cyclic aliphatic diamino acid ethyl ester thermo-cracking, wherein
A) cycloaliphatic diamine of formula (II)
H
2N-R-NH
2
Wherein, the R representative has 4 to 18, the divalence cycloaliphatic hydrocarbon residue of preferred 5 to 15 carbon atoms, and prerequisite is that two nitrogen-atoms directly are connected with the hydrocarbon ring, have arranged three carbon atoms therebetween at least, with the alcohols of urea and/or urea derivatives and formula (III)
R
1-OH
Wherein, R
1Represent residue, as its by the uncle who contains 3 to 8 carbon atoms or kept after the second month in a season, (ring) aliphatics alcohols removed hydroxyl, it does not exist or exists under dialkyl carbonate, urea acid alkyl ester or the condition by the mixture of dialkyl carbonate and urea acid esters, and reaction generates cyclic aliphatic diamino acid ethyl ester under the condition that does not have or exist catalyzer, isolates the ammonia of generation simultaneously:
B) isolate dialkyl carbonate and/or urea acid alkyl ester by the reaction mixture of the alcohols that makes, step of reaction a) send back to alcohols, optional also have dialkyl carbonate and/or urea acid alkyl ester;
C) the optional waste material that contains high boiling substance in all or part of reaction mixture that is discarded in acquisition in separation;
D) superincumbent step b) and optional c) in, the reaction mixture that contains the diamino acid ethyl ester of purifying is 180-280 ℃ in temperature in the presence of catalyzer continuously and solvent-freely, preferred 200-260 ℃, under 0.1-200mbar pressure, Continuous Heat cracking under the preferred 0.2-100mbar pressure, so that with reaction mixture based on the mark of charging at 10%-60wt%, the mark that is preferably based on charging is that the part of 15%-45wt% is progressively taken out;
E) in thick cycloaliphatic diisocyanates and methyl alcohol, go out split product by rectifying separation;
F) thick cycloaliphatic diisocyanates is by distillation purifying and isolate pure product fractions;
G) will be in recyclable materials stream and overflow from d) the bottom extract separate, the overflow of enrichment high boiling component is by this process taking-up and abandon;
H) from g) recyclable materials stream with from e) alcohols under the condition that has or do not exist catalyzer in 1-150min, in the preferred 3-60min, in temperature is 20-200 ℃, preferred 50-170 ℃, pressure is 0.5-20bar, reacts under the condition of preferred 1-15bar, at this moment, the mol ratio of NCO-group and OH-group is at most 1: 100, and preferred 1: 20, preferred especially 1: 10;
I) purify distillation f) part of bottom fraction takes out and feeds scission reaction d continuously) or urethane esterification stage h) in;
J) optionally will purify distillation f) in the subsidiary overhead fraction that generates of thick cycloaliphatic diisocyanates be fed back to urethane esterification stage h) equally;
K) will be from h) the esterification of urethane once more flow back to and transport to stage b);
Or
L) will be from h) the esterification of urethane once more flow back to and transport to step of reaction a), prerequisite is, stage h) carries out down for the halogenide that is selected from Fe (III) and/or Cu (I) at catalyzer, the urea equivalent that wherein uses the urea that unconditionally limits and/or prepared by the urea of unconditional restriction.
According to preparing the very cycloaliphatic diisocyanates of high yield easily by continuous operation according to method of the present invention.According to the advantage of multi-stage process of the present invention particularly in such fact, the cycloaliphatic diamine that promptly uses formula (II) is as the synthetic sedimentary initiator of continuous vulcabond, it helps the high boiling component of high viscosity in nature source especially, largely can avoid and keeps good equipment availability and high process yield for a long time.The amount of the diamino acid ethyl ester that feeds in vapor phase can be reduced to minimum and can limit necessary energy dissipation in this way according to being also advantageous in that of multi-stage process of the present invention.A) in order to produce monomer cyclic aliphatic diamino acid ethyl ester in a) in step of reaction, with the cycloaliphatic diamine of formula (II) and the alcohols of urea and/or urea derivatives and formula (III), the mixture of optional these alcohols, with mol ratio is 1: 2.01: 4.0 to 1: 2.2: 10, preferred 1: 2.02: 6 to 1: 2.12: 9, optional is not preferably at dialkyl carbonate still, urea acid alkyl ester or the mixture that is made of dialkyl carbonate and urea acid esters are in the presence of according to each comfortable 1%-10mol% of diamines molar fraction, there is not or exists catalyzer, in temperature of reaction at 140-270 ℃, preferred 160-250 ℃, pressure is relevant to the alcohols of use 2-80bar, under the condition of preferred 7-15bar, in 2-20 hour, preferably react in 4-9 hour.Reaction can be carried out in the preferred pressure distillation reactor in the backflow cascade boiler of operate continuously.
Can in the presence of catalyzer, produce cyclic aliphatic diamino acid ethyl ester in order to improve speed of response.As catalyzer suitable be inorganic or organic compound, it contains one or more, IA in preferred a kind of periodic table of elements, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIB, VIIB and VIIIB family metallic cation, it defines according to 14 editions chemical physics handbooks, chemistry rubber publishing company publishes, the 2310Superior main road, N.E., the Cleveland, Ohio, for example 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.For example said positively charged ion 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.For example can mention as typical catalyzer and to be following compound: lithium ethoxide, the 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, the 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.Optional catalyst can also be used with the form of its hydrate or ammonate (Ammoniakate).
The urea derivatives (carbonic acid derivatives) that the initial compounds that is used for the inventive method is fit to for the alcohols of the cycloaliphatic diamine of the formula (II) said in the above, the formula (III) said in the above and urea and/or as carboxylating agent is under the condition of the mixture that does not have or exist dialkyl carbonate, urea acid alkyl ester or be made of dialkyl carbonate and urea acid alkyl ester.
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, 2,2 '-methylene radical dicyclohexyl diamines and isomery cycloaliphatic diamine such as all hydrogenated methylenediphenyl diamines.The working condition of methylenediphenyl diamines (MDA) is by 4,4 '-, 2,4-and 2, the heterogeneous mixture (for example DE10127273) that 2 '-MDA constitutes.All hydrogenated methylenediphenyl diamines obtains by the complete hydrogenation of MDA, is a kind of by isomery methylene radical dicyclohexyl diamines (H therefore
12MDA) mixture of Gou Chenging, promptly 4,4 '-, 2,4-and 2,2 '-H
12The mixture that MDA constitutes.Diamines as formula (II) preferably uses 4,4 '-methylene radical dicyclohexyl diamines, 2,4-methylene radical dicyclohexyl diamines, 2,2 '-methylene radical dicyclohexyl diamines and any mixture of two kinds of isomer at least wherein.Certainly can also use and the different diamines of formula (II).For example, 1,3-and 1,4-diamino methylcyclohexane, hexamethylene diamine, 6,2,2,4-or 2,4,4-trimethylammonium hexyl amine-1,6 and 3-amino methyl-3,5,5-trimethylcyclohexyl amine.But preferably do not use and the different amine of formula (II).
Having under normal pressure boiling point arbitrarily is lower than 190 ℃ aliphatic series or cyclic aliphatic alcohols and is suitable for alcohols as formula (III).For example C1-C6 alcohols, for example methyl alcohol, ethanol, 1-propyl alcohol, 1-butanols, 2-butanols, 1-hexanol or hexalin.The preferred 1-butanols that uses is as alcohols.
In the reaction mixture conversion process, ammonia is released out, and the discharge of ammonia is good for speed of response.The discharge of ammonia is noticeable from reactor, and the temperature of reactor-side wall temperature and discharge line is higher than 60 ℃, and to avoid the distribution by urea acid (carbaminate) ammonium, it is made of with minimum ammonia and carbonic acid gas by decomposing urea.For example this proves feasible, in the pressure distillation reactor, react, feed the reaction mixture adverse current in the alcohols waste gas of being introduced by the bottom this moment, realizes that by this method the reinforcement of bottom flow is even, and it is equivalent to cascaded stages in fact in all cases.The top isolate by alcohols and ammonia constitute the mixture of gaseous form can feed in the distillation tower, preferably under the pressure of pressure distillation reactor, need not condensation in advance, to obtain the pressure distillation reactor bottom alcohols by sky ammonia, it will be fed back in the tower.Distribution for fear of the reflux exchanger that contains urea acid ammonium allows correspondingly to set head temperature with alcohols content and is at least 60 ℃.
B) excessive alcohols, dialkyl carbonate, as long as its generation or exist in reaction mixture, or urea acid alkyl ester or the mixture that has at least two kinds of these components to constitute will preferentially be isolated in second step.In the first step, reaction mixture is 1-500mbar at the step of reaction stress level a) pressure that reduces pressure, preferred 2-150mbar, it and separates in the fluid waste liquid in this way in the refuse of the gas form that contains excessive alcohols and optional dialkyl carbonate and/or urea acid alkyl ester.In second step, the fluid waste liquid by thin film evaporation at 180-250 ℃, preferred 200-230 ℃, pressure is at 0.1-20mbar, preferred 1-10mbar, by discharging in the optional remaining alcohols that exists and mid-boiling point material such as dialkyl carbonate and/or the urea acid alkyl ester, so that resistates is basically by monomer urethane, and preferred diamino acid ethyl ester and optional high boiling point oligopolymer constitute.
Waste liquid can preferably optionally be fed back to step of reaction a) behind distillation purifying.
C) preferably at every turn will be in the stage 6) reaction mixture in the optional high boiling substance that contains separate and remove.If will be at g) in describe from the separation of the bottom ejecta of stage d) only with part stream, promptly the ejecta to part separates, it can be favourable, next Shuo Ming approach is used to illustrate the separation of high boiling substance:
Can choose wantonly by the isolated liquid that obtains by low and mid-boiling point material in the step b), it contains the logistics of monomer diamino acid ethyl ester and the high boiling point oligopolymer of choosing wantonly, preferably by means of thin layer or short-path evaporator, temperature is at 180-260 ℃, preferred 200-240 ℃, pressure is at 0.01-10mbar, distillation in recyclable stream (Wertstoff Strom) under the preferred 0.02-5mbar, this logistics contains monomer diamino acid ethyl ester and low-boiling by-products, and isolate can not the distillatory byproduct stream.Containing high boiling component can not the distillatory byproduct stream follow by taking out in the preparation flow and being dropped as unworthy waste liquid usually.
Can choose wantonly and will be divided into two strands of part streams before from the optional described in front distillation purification of logistics that contains the high boiling point oligopolymer of stage b), wherein a plume is directly used in and is separated decomposition reaction (referring to d)), another thigh at first separates by above-described high boiling point.
D) from stage b) and optional phase c) monomer diamino acid ethyl ester and the recyclable stream of low-boiling by-products in suitable device partly, solvent-freely exist under the catalyzer condition in liquid phase, temperature is 180-280 ℃, preferred 200-260 ℃, under 0.1-200mbar pressure, Continuous Heat cracking under the preferred 0.2-100mbar pressure.The diamino acid ethyl ester that is used for thermo-cracking in equipment is relevant with the diamino acid ethyl ester of use to the conversion of vulcabond, can freely select to a great extent, usually account for the 10%-95wt% of the diamino acid ethyl ester amount (charging) of input, preferred 35%-85%.The diamino acid ethyl ester that does not have cracking section, do not have to transform of reaction mixture, high boiling point by-products produced and other can utilize and can not utilize by product to be taken out continuously.In addition, the amount of ejecta is according to the conversion of expectation and the degree adjustment of the scission reaction of expectation, and can simply test definite.It counts 10%-60wt% based on charging usually, preferred 15%-45wt%.
Use for example said inorganic and organic compound catalytic amino ethyl formate generation in front as the catalyzer that is used for diamino acid ethyl ester chemical cracking.Preferred zinc or the muriate of tin and the oxide compound of zinc, manganese, iron or cobalt of using, at this moment, catalyzer is joined from purifying series b by dosage) and optional c) the logistics that mainly contains the diamino acid ethyl ester before entering cracking, as 0.01%-25wt% concentration, the solution or the suspended substance of preferred 0.05%-10wt% concentration, preferably in alcohols, it also is used for the preparation of urethanum, consumption is 5-400ppm, preferred 10-100ppm.
As cracking apparatus suitable be as cylindric cracking reactor, for example tube furnace or preferably vaporizer, as hang a layer vaporizer, thin layer evaporator or vaporizer in bulk, for example Robert evaporator, Herbert vaporizer, drive younger brother's type vaporizer, Oscar vaporizer and hot candle vaporizer.
In principle, force the mean residence time of the isocyanate group discharge short as much as possible in the cracking zone by the alcohols deblocking, be restricted to minimum with side reaction with non-expectation.
Preferred cracking is carried out in the cracking of an associating and rectifying tower, it hangs a layer vaporizer at the bottom equipment and comes conveying capacity, equipment of 1/3 equipment is carried additional energy or recovered energy below, equipment of 1/3 equipment is discharged thick vulcabond in the above, and refluxes and discharge purified alcohols at condenser of top equipment.
E) split product that thermo-cracking produced, the split product of forming by alcohols, vulcabond and part cracked diamino acid ethyl ester particularly, by being 95-260 ℃ in temperature, preferred 110-245 ℃, pressure is 0.5-250mbar, and preferred 1-100mbar is at alcohols with in thick mixtures of diisocyanates, preferably constitute by cycloaliphatic diisocyanates, part cracking cycloaliphatic diisocyanates and optional small part cyclic aliphatic diamino acid ethyl ester, rectifying separation.This separation can for example said in the above joint cracking and the cleavage column of rectifying tower in carry out.
F) crude mixture that preferably obtains by rectifying, it is made of cycloaliphatic diisocyanates, part cracked cyclic aliphatic diamino acid ethyl ester and optional small part cyclic aliphatic diamino acid ethyl ester, with it by being 95-260 ℃ in temperature, preferred 110-245 ℃, under 0.5-150mbar pressure, preferred 1-75mbar pressure is down by distillation purifying, and at this moment, the subsidiary cut that produces is fed back to stage h) or isolates as pure products.
G) from cleavage stages d) the bottom extract be separated into recyclable logistics and waste liquid, and in this process, take out and abandon the waste liquid that is rich in high boiling component.Separating two kinds of logistics preferably by means of thin layer or short-path evaporator, is 180-270 ℃ in temperature, preferred 200-250 ℃, under 0.01-10mbar pressure, preferably distills under 0.02-5mbar pressure.The recyclable logistics that contains monomer diamino acid ethyl ester and low-boiling by-products produces as overhead product.The waste liquid that is rich in high boiling component is created among the preparation technology as waste material and is removed, and abandons as the material that has no value for use in fact usually.Alternatively be, but not preferred, by recyclable logistics of extracting and separating and waste material.For example supercritical co is appropriate to as extraction agent.
Before the optional distillation purifying of describing the bottom extract is divided into two strands of part streams in the above, wherein one directly carries out urethane esterification once more (seeing h)).The ratio that is divided into two strands part stream is 99: 1 to 1: 99, preferred 95: 5 to 5: 95.
H) from purification phase g) recyclable logistics will with from stage of rectification e) alcohols converge, at this moment, the mol ratio of NCO-group and OH-group is at most 1: 100, and preferred 1: 20, especially preferred 1: 10, reaction mixture under the condition that has or do not exist catalyzer in 1-150min, preferred 3-60min, temperature is 20-200 ℃, preferred 50-170 ℃, under 0.5-20bar pressure, the reaction down of preferred 1-15bar pressure.Reaction can or be carried out in tubular reactor at continuous cascade boiler.Basically all promote the NCO/OH-catalyst for reaction all to be fit to as catalyzer.For example use stannous octoate, dibutyl tin laurate, tindichloride, zinc dichloride and triethylamine.
I) purifying distillation f) part of bottom fraction will be taken out continuously and can be chosen wantonly and is fed back to cleavage stages d) or urethane esterification stage h).Preferably be fed back to the urethane esterification stage.The amount of extract accounts for the 0.1%-50wt% of the thick polymeric polyisocyanate in ingress in the purifying distillation stage, preferred 0.2%-25wt%.
J) overhead fraction of purifying distillation stage f) can be dropped or preferably be fed back to urethane esterification stage h).The amount of the overhead fraction of time per unit output accounts for the 0.1%-3wt% of the thick polymeric polyisocyanate in ingress in the purifying distillation, preferred 0.3%-1wt%.
K) will be fed back to from the logistics of urethane esterification stage h) lowly separate b with mid-boiling point) in.
L) alternatively being, for k) backflow described also can be fed back to the logistics from the urethanum stage h) during the diamino acid ethyl ester produces a), as long as the urethane esterification is carried out in the presence of special lewis acid catalyst.Special catalyzer is relevant at this to be Fe (III) or Cu (I) halogenide or their mixture.For example use Fe (III)-muriate, Fe (III)-bromide, Cu (I)-muriate and Cu (I)-bromide.Do not get rid of simultaneously on the using priciple of dedicated catalyst and use other to quicken the catalyzer of urethane esterification.Preferred use special catalyzer, i.e. Fe (III) or Cu (I) halogenide or their mixture, and additionally do not use other catalyzer.
Use according to the multi-stage process of continuous preparation cycloaliphatic diisocyanates of the present invention refluxing and taking out under the by product condition, can keep reacting for the long-time highly selective interference-free of distillable cycloaliphatic diisocyanates.Be particularly useful for preparation according to method of the present invention and contain 4-18, preferably contain the cycloaliphatic diisocyanates of 5-15 carbon atom, 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 front said isomery methylene radical dicyclohexyl mixtures of diisocyanates, for example nature is being converted into H by perhydro-MDA
12Produce in the MDI process.
Prepared cycloaliphatic diisocyanates optimum according to the preparation of polymeric polyisocyanate-addition polymerization process contain urethanum-, chlorinated isocyanurates-, acid amides-and/or the plastics of urea groups.Discovery can with its produce with urethanum-, biuret-and/or the mixture of polyisocyanates of isocyanate groups modification.This mixture of polyisocyanates that is made of the cyclic aliphatic isocyanic ester is particularly useful for preparing the fast to light polyurethane coating of high value.
Claims (51)
1. the multi-stage process for preparing cycloaliphatic diisocyanates continuously, it passes through cycloaliphatic diamine and carbonic acid derivatives and alcohols reaction, generate cyclic aliphatic diamino acid ethyl ester, next thermo-cracking diamino acid ethyl ester is a cycloaliphatic diisocyanates, it is characterized in that, cyclic aliphatic diamino acid ethyl ester after it is synthetic by with cycloaliphatic diamine and alcohols and urea and/or urea derivatives reaction and by hang down with the mid-boiling point material in discharge, so the cyclic aliphatic diamino acid ethyl ester of purifying is discharging thermo-cracking under the vulcabond of expecting, part cracking substrate is by taking out continuously in the cracking apparatus, isolate high boiling component thus, so the extract of purifying is with alcohols urethane esterification and recycle in this process once more, at this moment, use the urea of unconditional restriction and/or the urea equivalent of producing by unconditional restriction urea.
2. the continuous multi-stage process of the cycloaliphatic diisocyanates of preparation formula (I)
OCN-R-NCO
Wherein, the R representative has 4 to 18, the divalence cycloaliphatic hydrocarbon residue of preferred 5 to 15 carbon atoms, its condition is, two nitrogen-atoms directly are connected with the hydrocarbon ring, have arranged three carbon atoms therebetween at least, are converted into cyclic aliphatic diamino acid ethyl ester by cycloaliphatic diamine and urea and/or urea derivatives and alcohols reaction, and cyclic aliphatic diamino acid ethyl ester thermo-cracking, wherein
A) cycloaliphatic diamine of formula (II)
H
2N-R-NH
2
Wherein, the R representative has 4 to 18, the divalence cycloaliphatic hydrocarbon residue of preferred 5 to 15 carbon atoms, and its condition is that two nitrogen-atoms directly are connected with the hydrocarbon ring, have arranged three carbon atoms therebetween at least, with the alcohols of urea and/or urea derivatives and formula (III)
R
1-OH
Wherein, R
1Represent residue, as by the uncle who contains 3 to 8 carbon atoms or kept after the second month in a season, (ring) aliphatics alcohols removed hydroxyl, it does not exist or exists under dialkyl carbonate, urea acid alkyl ester or the condition by the mixture of dialkyl carbonate and urea acid esters, and reaction generates cyclic aliphatic diamino acid ethyl ester under the condition that does not have or exist catalyzer, can isolate the ammonia of generation simultaneously;
B) isolate dialkyl carbonate and/or urea acid alkyl ester by the reaction mixture of the alcohols that makes, send alcohols and optional dialkyl carbonate and/or urea acid alkyl ester in a) back in step of reaction;
C) waste material of the optional high boiling substance that contains in all or part of reaction mixture that is discarded in acquisition in separation;
D) superincumbent step b) and optional c) in, the reaction mixture that contains the diamino acid ethyl ester of purifying is being 180-280 ℃ in temperature in the presence of the catalyzer and under condition of no solvent, preferred 200-260 ℃, under 0.1-200mbar pressure, Continuous Heat cracking under the preferred 0.2-100mbar pressure, so that with reaction mixture based on the mark of charging at 10%-60wt%, the mark that is preferably based on charging progressively takes out in the part of 15%-45wt%;
E) in thick cycloaliphatic diisocyanates and methyl alcohol, go out split product by rectifying separation;
F) thick cycloaliphatic diisocyanates is by distillation purifying and isolate pure product fractions;
G) will be in recyclable logistics and overflow from d) the bottom extract separate, the overflow of enrichment high boiling component is taken out and is abandoned by this process;
H) from g) recyclable logistics under the condition that has or do not exist catalyzer in 1-150min, in the preferred 3-60min, in temperature is 20-200 ℃, preferred 50-170 ℃, pressure is 0.5-20bar, under the condition of preferred 1-15bar with from e) the alcohols reaction, at this moment, the molar content ratio of NCO-group and OH-group is at most 1: 100, and preferred 1: 20, preferred especially 1: 10;
I) purifying distillation f) scission reaction d is taken out and fed to the part of bottom fraction continuously) or urethane esterification stage h) in;
J) optionally will distill f at purifying) in the thick subsidiary overhead fraction that produces of cycloaliphatic diisocyanates be fed back to urethane esterification stage h) equally;
K) will be from h) urethanum once more flow back to and transport to stage b);
Or
L) will be from h) urethanum once more flow back to and transport to step of reaction a), prerequisite is, stage h) is selected from catalyzer in the presence of the halogenide of Fe (III) and/or Cu (I) and carries out,
Wherein use the urea of unconditional restriction and/or by the urea equivalent of the urea preparation of unconditional restriction.
3. as the multi-stage process of claim 1 or 2, it is characterized in that, use 4,4 '-methylene radical dicyclohexyl diamines, 2,4-methylene radical dicyclohexyl diamines, 2,2 '-methylene radical dicyclohexyl diamines and at least wherein any mixture that constitutes of two kinds of isomer as cycloaliphatic diamine.
4. as the multi-stage process of claim 1 or 2, it is characterized in that use 4,4 '-methylene radical dicyclohexyl diamines and/or isomery cycloaliphatic diamine are as cycloaliphatic diamine.
5. as the multi-stage process of claim 1 or 2, it is characterized in that use 1, the 4-diamino-cyclohexane is as cycloaliphatic diamine.
6. as at least one multi-stage process in the claim of front, it is characterized in that, in a distillation reactor or the level combination oven that refluxes, carry out the stage a) continuously.
7. as at least one multi-stage process in the claim of front, it is characterized in that, the stage a) reaction of transfer be diamines with the mol ratio: urea: alcohols is to carry out in 1: 2.01: 4.0 to 1: 2.2: 10.
8. as at least one multi-stage process in the claim of front, this moment the stage a) in residence time of educt be 2 to 20 hours, preferably 4-9 hour.
9. as at least one multi-stage process in the claim of front, it is characterized in that at 140 to 270 ℃, pressure is to carry out under the 2-80bar to step a) in reactor.
10. as at least one multi-stage process in the claim of front, it is characterized in that, is 160 to 250 ℃ in temperature of reaction in step a), and pressure is to transform for 7 to 15bar times.
11., it is characterized in that step a) is carried out in the pressure distillation reactor as at least one multi-stage process in the claim of front.
12. as at least one multi-stage process in the claim of front, this moment the stage a) in educt submit to the bottom continuously topmost, the ammonia that discharges is discharged from by means of the alcohols waste gas by the feeding of distillation reactor bottom.
13. as at least one multi-stage process in the claim of front, it is characterized in that, use the alcohols that contains 1-6 carbon atom in a) in the stage.
14. as at least one multi-stage process in the claim of front, it is characterized in that, use butanols in a) in the stage.
15., it is characterized in that stage being reflected under the condition that catalyzer exists in a) carried out as at least one multi-stage process in the claim of front.
16., it is characterized in that stage b) carries out in two steps as at least one multi-stage process in the claim of front.
17. the multi-stage process as claim 16 is characterized in that, is 1 to 500mbar at the reaction mixture of fs in step of reaction stress level decompression a), preferred 2 to 150mbar.
18. multi-stage process as claim 16 or 17, it is characterized in that, discharge by thin film evaporation at 180 to 250 ℃ at the second step fluid, preferred 200 to 230 ℃, pressure is 0.1 to 20mbar, preferred 1 to 10mbar, by discharging in the optional remaining alcohols that exists and mid-boiling point material such as dialkyl carbonate and/or the urea acid alkyl ester.
19. the multi-stage process as claim 16 or 17 is characterized in that, the waste gas of stage b) is further entering step of reaction a) behind the distillation purifying.
20., it is characterized in that as at least one multi-stage process in the claim of front, in stage c), separate, if use, be 180 to 260 ℃ in temperature, preferred 200 to 240 ℃, under 0.01 to 10mbar pressure, carry out under preferred 0.02 to the 5mbar pressure.
21., it is characterized in that stage c) if use, is undertaken by thin layer or short-path evaporator as at least one multi-stage process in the claim of front.
22. as at least one multi-stage process in the claim of front, it is characterized in that,,, be removed and abandon if use from the by product of stage c).
23., it is characterized in that in stage c), if use, substance flow is processed as at least one multi-stage process in the claim of front, make before its distillation purifying, to be divided into two strands of part streams, wherein the direct feeding scission reaction (stage d) of one part stream.
24., it is characterized in that stage d) carries out in joint cracking and rectifying tower as at least one multi-stage process in the claim of front.
25., it is characterized in that as at least one multi-stage process in the claim of front, in stage d), be 180 to 280 ℃ in temperature, preferred 200 to 260 ℃, under 0.1 to 200mbar pressure, Continuous Heat cracking under preferred 0.2 to the 100mbar pressure.
26., it is characterized in that cracking in liquid phase under condition of no solvent in stage d) as at least one multi-stage process in the claim of front.
27., it is characterized in that stage d) carries out in the presence of catalyzer as at least one multi-stage process in the claim of front.
28. as at least one multi-stage process in the claim of front, it is characterized in that, the thermoinducible diamino acid ethyl ester cracking of stage d) is carried out in tube furnace or preferred vaporizer, vaporizer is as hanging sheet vaporizer, thin layer evaporator or vaporizer in bulk, is selected from Robert evaporator, Herbert vaporizer, drives younger brother's type vaporizer, Oscar vaporizer and hot candle vaporizer.
29. as at least one multi-stage process in the claim of front, it is characterized in that, in stage d), freely select then the diamino acid ethyl ester is converted into vulcabond, depend on employed diamino acid ethyl ester, preferred its scope in the diamino acid ethyl ester amount (charging) that feeds is that preferred 35% to 85wt% in 10% to the 95wt% scope.
30. as at least one multi-stage process in the claim of front, it is characterized in that, in stage d), contain unconverted diamino acid ethyl ester, high boiling point by-products produced and other are valuable and the part of the reaction mixture of unworthy by product is taken out continuously.
31. the multi-stage process as claim 30 is characterized in that, the amount of extract account for charging 10% to 60wt%, preferred 15% to 45wt%.
32., it is characterized in that stage e) carries out in joint cracking and rectifying tower as at least one multi-stage process in the claim of front.
33., it is characterized in that as at least one multi-stage process in the claim of front, be 95 to 260 ℃ in temperature, preferred 110 to 245 ℃, pressure is 0.5 to 250mbar, carries out under preferred 1 to 200mbar.
34. as at least one multi-stage process in the claim of front, it is characterized in that, in stage f), the thick cut that is made of cycloaliphatic diisocyanates, part cracking cyclic aliphatic diamino acid ethyl ester and optional a small amount of cyclic aliphatic diamino acid ethyl ester that is obtained by stage e) is by being 95 to 260 ℃ in temperature, preferred 110 to 245 ℃, under 0.5 to 150mbar pressure, pass through distillation purifying under preferred 1 to the 75mbar pressure.
35. the multi-stage process as claim 34 is characterized in that, separates as pure products or is fed back in the stage h) at the subsidiary cut that produces of stage f).
36., it is characterized in that as at least one multi-stage process in the claim of front, in stage g), be 180 to 270 ℃ in temperature, preferred 200 to 250 ℃, under 0.01 to 100mbar pressure, carry out under preferred 0.02 to the 5mbar pressure.
37., it is characterized in that distillation is carried out by means of thin layer or short-path evaporator in the step g) as at least one multi-stage process in the claim of front.
38., it is characterized in that stage g) can be realized by extraction as at least one multi-stage process in the claim of front.
39., it is characterized in that the bottom extract in step g) before the distillation purifying is divided into two strands of part streams as at least one multi-stage process in the claim of front, wherein one directly feeds in the urethane esterification stage h) again.
40. the multi-stage process as claim 39 is characterized in that, the ratio of two strands of part streams that separate is 99: 1 to 1: 99, preferred 95: 5 to 5: 95.
41., it is characterized in that stage h) is carrying out in cascade boiler or the tubular reactor continuously as at least one multi-stage process in the claim of front.
42. as at least one multi-stage process in the claim of front, it is characterized in that, being reflected in the stage h) be selected from Sn-and/or Zn-carboxylate salt or-catalyzer of halogenide and/or tertiary amine carries out under existing.
43., it is characterized in that i in the stage as at least one multi-stage process in the claim of front) be back to urethane esterification stage g).
44. as at least one multi-stage process in the claim of front, it is characterized in that, in stage i) the amount of extract account for purify the thick polymeric polyisocyanate in ingress in the distillation stage 0.1% to 50wt%, preferred 0.2% to 25wt%.
45. as at least one multi-stage process in the claim of front, it is characterized in that, in stage j) the amount of the overhead fraction of time per unit output account in the purifying distillation thick vulcabond in ingress 0.1% to 3wt%, preferred 0.3% to 1wt%.
46., it is characterized in that, in the stage 1 as at least one multi-stage process in the claim of front) in use Fe (III)-muriate, Fe (III)-bromide, Cu (I)-muriate and Cu (I)-bromide.
47. as at least one multi-stage process in the claim of front, 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 4 '-methylene radical dicyclohexyl vulcabond or at least two kinds of isomery methylene radical dicyclohexyl vulcabond.
48., it is characterized in that the diamines of use is selected from 1,3-and 1,4-diamino methylcyclohexane, hexamethylene diamine as at least one multi-stage process in the claim of front, 6,2,2,4-or 2,4,4-trimethylammonium hexylamine-1,6 and 3-amino methyl-3,5,5-trimethylcyclohexyl amine.
49. as at least one multi-stage process in the claim of front, it is characterized in that, the maximum concentration of formaldehyde of used urea or used urea equivalent (and Paraformaldehyde 96) is 0.01% to 0.10wt%, and preferred 0.001% to 0.01wt%, especially preferably is lower than 0.001wt%.
50., it is characterized in that urea inorganic substance of no use and/or formaldehyde carry out surface treatment as at least one multi-stage process in the claim of front.
51., it is characterized in that urea does not contain talcum powder, wilkinite, diatomite, Diatomacae, kaolin or other silicates material as at least one multi-stage process in the claim of front.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006061474.7 | 2006-12-23 | ||
| DE102006061474A DE102006061474A1 (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 |
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| Publication Number | Publication Date |
|---|---|
| CN101205198A true CN101205198A (en) | 2008-06-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200710152720XA Pending CN101205198A (en) | 2006-12-23 | 2007-08-07 | Multilevel method for continuously producing cycloaliphatic diisocyanates |
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| CN (1) | CN101205198A (en) |
| DE (1) | DE102006061474A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108290822A (en) * | 2015-12-04 | 2018-07-17 | 巴斯夫欧洲公司 | The isomerization of MDACH |
| 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 |
| CN114644576A (en) * | 2022-04-21 | 2022-06-21 | 中国科学院过程工程研究所 | 1, 3-cyclohexanedimethylene dicarbamate and preparation method and application thereof |
| CN115572245A (en) * | 2022-09-29 | 2023-01-06 | 四川元理材料科技有限公司 | Industrial method for producing IPDI (isophorone diisocyanate) by thermal cracking of n-butyl isophorone dicarbamate |
-
2006
- 2006-12-23 DE DE102006061474A patent/DE102006061474A1/en not_active Withdrawn
-
2007
- 2007-08-07 CN CNA200710152720XA patent/CN101205198A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108290822A (en) * | 2015-12-04 | 2018-07-17 | 巴斯夫欧洲公司 | The isomerization of MDACH |
| 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 |
| CN114644576A (en) * | 2022-04-21 | 2022-06-21 | 中国科学院过程工程研究所 | 1, 3-cyclohexanedimethylene dicarbamate and preparation method and application thereof |
| CN115572245A (en) * | 2022-09-29 | 2023-01-06 | 四川元理材料科技有限公司 | Industrial method for producing IPDI (isophorone diisocyanate) by thermal cracking of n-butyl isophorone dicarbamate |
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| Publication number | Publication date |
|---|---|
| DE102006061474A1 (en) | 2008-06-26 |
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