Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
  • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
  • C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
  • C07C273/1863—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety from urea
• • 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

Definitions

• the invention relates to a multistage process for the continuous preparation of organic polyisocyanates, preferably of diisocyanates, more preferably of aromatic, aliphatic or cycloaliphatic diisocyanates, by reacting the corresponding organic polyamines with urea and secondary amines in low molecular weight monomeric polyureas and their division.
• Another object of the invention is an associated production process, in which in certain reaction stages, the polyisocyanates prepared and recyclable residues separated and reusable by-products and intermediates are recycled in precursors.
• organic polyisocyanates e.g. of aromatic, aliphatic or cycloaliphatic polyisocyanates
• the technical processes for the preparation of organic polyisocyanates are based on the phosgenation of the corresponding organic polyamines to form polycarbamoyl chlorides and their cleavage to the polyisocyanates and hydrogen chloride.
• these processes suffer from other significant disadvantages.
• the preparation of aliphatic or cycloaliphatic polyisocyanates succeeds only with fairly moderate space-time yields due to the greater basicity of the starting polyamines.
• HDI hexamethylene diisocyanate 1, 6
• phosgene-free process can be prepared only undecomposed distillable isocyanates with these methods.
• WO 98/54129 describes a process for the decomposition of diureas, each formed from secondary amines. These secondary amines are very specific amines in which the amino groups are substituted with a tertiary carbon atom, for example, tertiary butyl groups or 2,2-disubstituted piperidine groups. The decomposition takes place purely thermally optionally in the presence of a carrier gas or an inert solvent.
• the disadvantage here is that in this type of reaction, the decomposition products secondary amine and isocyanate react quickly with each other, which is particularly due to the high reactivity of the secondary amines.
• the object of the present invention was to inexpensively produce organic polyisocyanates with high selectivity in improved yields in a simple manner without the use of costly and / or safety-threatening starting materials or auxiliaries.
• This object has been achieved by a process for the preparation of polyisocyanates by reacting at least one polyamine with urea and at least one secondary amine to give the corresponding polyurea and subsequent acidic cleavage of the polyureas thus obtained into the corresponding polyisocyanates.
• the invention further relates to a multi-stage process for the continuous production of organic isocyanates by reacting the corresponding organic polyamines with urea and at least one secondary amine to the corresponding polyureas in at least one mixing device with downstream reactor and their cleavage, comprising the following steps and in which a) at least one organic polyamine with urea in the presence or preferably in the absence of at least one catalyst and at least one secondary amine optionally mixed together in the presence of at least one solvent, b) the mixture obtained from a) is reacted in at least one subsequent residence time reactor or more residence time reactors c) separating off the resulting ammonia simultaneously with the course of the reaction in step b) or subsequently, d) removing excess secondary amine and further secondary components boiling more readily than the polyureas from the effluent from b), f) the polyureas in a continuous splitter into the corresponding isocyanate and secondary amine acidic, wherein at least one isocyanate-containing stream and at least
• n are suitable polyamines of the formula R (NH2) n, an n-valent R, preferably three or divalent and more preferably divalent organic Rest, such as an optionally substituted, for example, substituted with an alkyl group substituted aromatic, a linear or branched chain aliphatic or optionally substituted cycloaliphatic radical.
• suitable aromatic polyamines which may be mentioned are 2,4- and 2,6-toluylenediamine, 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethanes and the corresponding isomer mixtures.
• aromatic amines can also be reacted with the process according to the invention to give the corresponding isocyanates, which are polyamine mixtures of the diphenylmethane series, as obtained in a conventional manner by polycondensation of formaldehyde with aniline can.
• Suitable secondary amines are, in principle, those secondary amines which are stable under the reaction conditions, i. Under the reaction conditions per hour to less than 5 mol%, preferably less than 3, more preferably less than 2 and most preferably less than 1 mol% based on the material decompose, especially those secondary amines having a molecular weight below 500 g / mol, which have no further functional groups and carry apart from the secondary amino function exclusively hydrocarbon radicals and ether groups, preferably exclusively hydrocarbon radicals.
• the secondary amines are preferably those of the formula HNR 1 R 2 in which R 1 and R 2 independently of one another have 1 to 20, preferably 1 to 10 and particularly preferably 1 to 6 carbon atoms, alkyl, 3 to 12, preferably 5 to 12, particularly preferably cycloalkyl having from 5 to 6 carbon atoms, from 6 to 14, preferably from 6 to 10, particularly preferably 6 to 8 carbon atoms, or an aralkyl radical having from 6 to 14, preferably from 6 to 8, carbon atoms in the aryl and 1 to 6, preferably having 1 to 3 carbon atoms in the alkyl radical, or the radicals R 1 and R 2 together may form a five- to twelve-membered, preferably five- to six-membered ring, including the nitrogen atom, wherein the radicals may less preferably additionally have ether groups.
• aralkyl groups are benzyl, phenethyl and 2- or 3-phenylpropyl, preferred are benzyl and phenethyl, particularly preferred is benzyl.
• Preferred secondary amines are dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, dihexylamine, dioctylamine, ethylmethylamine, iso-propyl-methylamine, n-butylmethylamine, tert-butylmethylamine, iso- Propyl ethylamine, n-butyl ethylamine, tert-butyl ethylamine, morpholine, piperidine and pyrrolidine, preferred are dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, di-n-butylamine, piperidine and pyrrolidine, particularly preferred are dimethylamine, diethylamine, di-iso-propylamine, di-n-butylamine, very particularly preferred are dimethylamine and di-n-butylamine and especially di-n-but
• the polyamines are reacted with urea and at least one, preferably exactly one secondary amine in a molar ratio of polyamine, urea and secondary amine of 1: 2 to 20: 5 to 40, preferably 1: 2 , 0 to 5: 6 to 10 at temperatures of 50 - 300 ° C and in particular at 130 - 220 ° C under a pressure of 0.1 to 30 bar, preferably 1 - 10 bar mixed together.
• step a all three starting components polyamine, urea and secondary amine are mixed together in step a).
• urea can be metered either as a melt, as a solid or as a solution in a solvent, preferably as a melt or as a solution.
• the mixing in step (a) can be carried out in the presence of substituted ureas, expediently in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, based on the polyamine, preferably diamine.
• substituted ureas expediently in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, based on the polyamine, preferably diamine.
• mixtures of substituted ureas in the proportions mentioned are used.
• Substituted ureas used are preferably those whose substitution patterns correspond to those of the secondary amine used, ie the formal reaction products of urea with one or two equivalents of secondary amine.
• the mixing in step (a) may optionally take place in the presence of at least one solvent.
• Suitable solvents are preferably hydrocarbons which are optionally substituted by halogen atoms, such as hexane, benzene, nitrobenzene, anisole, chlorobenzene, chlorotoluene, o-dichlorobenzene, trichlorobenzene, diethyl isophthalate (DEIP), tetrahydrofuran (THF), dimethylformamide (DMF), Xylene, chloronaphthalene, decahydronaphthalene and toluene.
• the solvent used is particularly preferably dichlorobenzene.
• the mixing in stage (a) or else the reaction in stage b) can also be carried out in the presence of catalysts.
• Suitable catalysts are inorganic or organic compounds containing one or more cations, preferably a cation of metals of group IA, IB, IIA, IIB, HIB, IVA, IVB, VA, VB, VIB, VI IB, VIIIB of the Periodic Table of the Elements as defined in Handbook of Chemistry and Physics 14th Edition, published by Chemical Rubber Publishing Co., 23 Superior Ave. N.E., Cleveland, Ohio.
• the catalyst may further comprise at least one anion, for example halides, such as chlorides and bromides, sulfates, phosphates, nitrates, borates, alcoholates, phenates, sulfonates, oxides, oxide hydrates, hydroxides, carboxylates, chelates, carbonates and thio- or dithiocarbamates.
• halides such as chlorides and bromides, sulfates, phosphates, nitrates, borates, alcoholates, phenates, sulfonates, oxides, oxide hydrates, hydroxides, carboxylates, chelates, carbonates and thio- or dithiocarbamates.
• the catalysts can also be used in the form of their hydrates or ammoniaates without noticeable significant disadvantages.
• Examples of typical catalysts are lithium methanoate, lithium ethanolate, lithium propoxide, lithium butanolate, sodium methoxide, potassium tert-butoxide, magnesium methoxide, calcium methoxide, tin (II) chloride, tin (IV) chloride, lead acetate , Lead phosphate, antimony (III) chloride, antimony (V) chloride, aluminum acetylacetonate, aluminum isobutylate, aluminum trichloride, bismuth (III) chloride, copper (II) acetate, copper ( II) sulfate, copper (II) nitrate, bis (triphenylphosphine oxide) copper (II) chloride, copper molybdate, silver acetate, gold acetate, zinc oxide, zinc chloride, zinc acetate, zinc acetonyl acetate, zinc octoate, zinc oxalate, zinc hexylate , Zinc benzoate, zinc undecy
• Examples of preferred catalysts are the following compounds: lithium butanolate, aluminum acetylacetonate, zinc acetylacetonate, titanium tetrabutoxide and zirconium tetrabutoxide.
• the mixing of the educt streams can optionally take place in a suitable special mixing device, which is characterized by short mixing times, in order then to achieve the substantial conversion in stage b) in at least one reactor.
• the mixing time in this mixing device is usually from 0.0001 s to 60 s, preferably from 0.0005 to 30 s, particularly preferably from 0.001 to 20 s, very particularly preferably from 0.005 to 10 s and in particular from 0.007 to 5 s.
• the mixing time is understood to be the time which elapses from the start of the mixing operation until 97.5% of the fluid elements of the resulting mixture have a mixing fraction less, based on the value of the theoretical final value of the mixture fracture of the resulting mixture upon reaching the state of perfect mixing 2.5% deviate from this final value of the mixture break (for the concept of mixture fracture, see, for example, J. Warnatz, U.Maas, RW Dibble: Verbrennungs, Springer Verlag, Berlin Heidelberg New York, 1997, 2nd edition, p. 134.) ,
• the mixing device used is preferably a mixing circuit, a stirring vessel, a mixing pump or a nozzle mixing device, for example coaxial mixing nozzles, Y or T mixers, or a vortex impinging jet mixing configuration, preferably a mixing circuit, a stirring vessel, a mixing pump or a nozzle mixing device.
• the temperature of the discharge from the mixing device is generally from 25 to 240 ° C, preferably 30 to 190 and particularly preferably 40 to 180 ° C.
• the discharge from the mixing device can be brought to the desired temperature there before being introduced into the step b) with the aid of a heat exchanger.
• the mixture leaving the mixing device is now fed to at least one, preferably exactly one or more, two-phase (gaseous / liquid) operated residence time reactors, in which the gas phase is conducted in cocurrent with the liquid phase.
• the residence time reactor in step b) is sufficiently back-mixed, for example, it is a stirred tank, it may be advantageous to combine steps a) and b) with one another, ie. H. to carry out the mixing within step b), for example in a stirred tank.
• urea and / or secondary amine or preferably polyamine can be replenished.
• the mean residence time in the reactor is generally 10 minutes to 8 hours, preferably 20 minutes to 5 hours, more preferably 30 minutes to 3 hours.
• the discharge from the reactor can be fed to a phase separator in a preferred embodiment and the liquid phase withdrawn from the phase separator can then be fed to the subsequent stage.
• phase separator is a container in which the phase separation between gas and liquid phase is achieved by the calming of the two-phase, emerging from the DC reactor flow.
• the phase separator can be carried out isothermally or preferably heated to prevent the precipitation of poorly soluble by-products.
• the heating can be done for example via the jacket or via a circuit with an external heat exchanger. When using an external heat exchanger, normal insulation of the heat exchanger is sufficient.
• the temperature in the reactor or the reactor combination and in any phase separator is generally between 50 ° C and 300 ° C, preferably between 180 ° C and 220 ° C.
• the pressure in stage b) is generally between 0.1 bar abs and 30 bar abs and preferably between 3 and 20 bar abs.
• the residence time in stage b) is selected such that the conversion, based on amino groups in the polyamine used to polyurea, after leaving the reactor is at least 95%, preferably at least 98, more preferably at least 99 and most preferably at least 99.5%.
• the total residence time in stage a) and b) together is less than
• the ammonia formed during the reaction is fed directly to an ammonia separation after each reactor section or, if mixed reactors are used, separated in series in each reaction unit in parallel to the reaction progress.
• the conversion based on amino groups in the polyamine used to form urea groups, is not complete after leaving the reactor or the reactor combination and is, for example, less than 95%, then the discharge can be further reacted.
• stages a) and b) in a stirred kettle or a stirred tank cascade, preferably in one to four stirred kettles, more preferably one to three stirred kettles, more preferably two to three stirred kettles, and most preferably to carry out two stirred kettles.
• the first stirred tank at least partially functions as stage a) and the rest as stage b).
• This distillation unit for the separation of ammonia, optionally with a content of secondary amine, from the reaction mixture is of a known type and has the usual internals.
• all standard installations are suitable as column internals, for example trays, packings and / or fillings.
• trays bell bottoms, sieve trays, valve trays, Thormann trays and / or dual-flow trays are preferred, of the trays are those with rings, spirals, calipers, Raschig, Intos or Pall rings, Barrel or Intalox Saddling, top Pak etc. or braids preferred.
• Floors are preferably used, more preferably bubble trays. d) separation of the excess secondary amine
• the remaining secondary amine and optionally the solvent, if used, were separated off and preferably recycled to the reaction stage (a) and / or (b).
• This apparatus may be a container or a combination of container and column, preferably a column, wherein in the head the secondary amine or its mixture and in the bottom of the polyurea can be deducted.
• other substances which boil more easily than the polyurea and which can be recycled, for example, to stage b) may be present in the top of the column in addition to the secondary amine.
• the separation takes place in a pressure range of 0.001 to 1 bar, preferably 0.02 to 0.8 bar.
• the reaction mixture containing polyureas obtained in the reaction step (b) is in a suitable device, preferably in a solvent or solvent mixture in the liquid phase in the presence of acids at temperatures of 20 to 250 ° C, preferably 100 to 200 ° C and under a pressure of 0.1 - 5 bar, preferably in the range of 0.3 - 2 bar continuously acid split.
• the acids are used anhydrous.
• Preferred examples of such acids are sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid and hydrobromic acid.
• Particularly preferred are sulfuric acid and hydrochloric acid, most preferably hydrochloric acid.
• gaseous hydrogen chloride is used.
• the molar ratio of acid to urea should be at least 2: 1, preferably at least 3: 1.
• Suitable acids for the chemical cleavage of the polyureas are the aforementioned inorganic and organic compounds catalyzing urea formation.
• Suitable solvents are preferably hydrocarbons which are optionally substituted by halogen atoms, such as, for example, hexane, benzene, nitrobenzene, anisole, chlorobenzene, Chlorotoluene, o-dichlorobenzene, trichlorobenzene, diethyl isophthalate (DEIP), tetrahydrofuran (THF), dimethylformamide (DMF), xylene, chloronaphthalene, decahydronaphthalene and toluene.
• the solvent used is particularly preferably dichlorobenzene. In a preferred embodiment, the same solvent as in steps a) and b) is used.
• the cleavage can be carried out in a stirred tank or a stirred tank cascade or a tube reactor with a Bodensteiniere up to 5, preferably in a single stirred tank.
• the average residence time is up to one hour, preferably up to 40 minutes, more preferably up to 15 and most preferably up to 10 minutes.
• the reactor constructions known to those skilled in the art for gas-liquid reactions, such as bubble columns or reaction columns, can be used.
• gaseous acid in particular hydrogen chloride
• cleavage in a mixing pump or a nozzle mixing device for example coaxial mixing nozzles, Y or T mixers, or a vortex impinging jet Mixed configuration can be performed, which cause a rapid phase transition from the gas to the liquid phase.
• the temperature in the cleavage in this case is generally from 100 to 200.degree. C., preferably from 120 to 190 and particularly preferably from 140 to 180.degree.
• the temperature in the cleavage in this case is generally from 100 to 200.degree. C., preferably from 120 to 190 and particularly preferably from 140 to 180.degree.
• the temperature in the cleavage in this case is generally from 100 to 200.degree. C., preferably from 120 to 190 and particularly preferably from 140 to 180.degree.
• the temperature in the cleavage in this case is generally from 100 to 200.degree. C., preferably from 120 to 190 and particularly preferably from 140 to 180.degree.
• the temperature in the cleavage in this case is generally from 100 to 200.degree. C., preferably from 120 to 190 and particularly preferably from 140 to 180.degree.
• the temperature in the cleavage in this case is generally from 100 to 200.degree. C., preferably from 120 to 190 and particularly preferably from 140 to 180.
• Reaction time is significantly less than 10 minutes, preferably up to 5 minutes, more preferably up to 3 minutes and most preferably up to 1 minute.
• the separation may be a solid-liquid separation, for example centrifugation or filtration, preferably a filtration of the solid salt phase.
• the reaction mixture is cooled again to reduce the solubility prior to the solid-liquid separation.
• any type of crystallization and phase separation can also be used in suitable apparatus known to the person skilled in the art, such as, for example, crystallizers.
• the reaction can be separated by extraction of an extractive extractive agent.
• a solvent was used in one of the previous reaction steps, this can be separated by distillation in a first purification step gl).
• the solution thus separated agent can then preferably in stage a) and / or b) and / or f), if required there, out.
• the crude isocyanate mixture is freed in a subsequent distillation of recombination products, by-products and any remaining traces of solvent.
• the by-products are preferably recycled to the reaction steps a) and b). A part can also be removed.
• the subscript "L” is used to denote low-boiling streams of the individual stages, with the index "H” high-boiling and "M” medium-boiling.
• the crude polyisocyanate mixture (givi), preferably obtained by rectification, can be further purified in a further distillation at a temperature of 100 to 180 ° C. and under a pressure of 1 to 50 mbar, the resulting pure polyisocyanate stream having a purity of at least 98% by weight. , in particular more than 99 wt.% Has.
• the bottoms fraction (gH) can also be recycled to the distillation column (d) for the separation of crude polyisocyanate and secondary amine or into the reaction stage (a) and / or (b), the polyurea formation. It is also possible to divide the sump fraction into 2 or 3 product streams, these preferably being recycled in the polyurea formation (a) and the cleavage apparatus (f) and optionally in the distillation column (g).
• the isocyanate prepared is a non-distillable isocyanate, it can optionally be purified in a step g2b) by a non-distillative route, for example by extraction or washing with a solvent. i) recovery of the secondary amine
• the product obtained from stage f) in the form of a salt of secondary amine and the acid used for the cleavage in a solvent can, in a preferred embodiment, be form for working up with a base are released, for example with hydroxides, oxides, carbonates or bicarbonates of alkali or alkaline earth metals, preferably sodium hydroxide, sodium bicarbonate, sodium carbonate or milk of lime.
• a base for example with hydroxides, oxides, carbonates or bicarbonates of alkali or alkaline earth metals, preferably sodium hydroxide, sodium bicarbonate, sodium carbonate or milk of lime.
• ammonia more preferably at least partially with the ammonia separated in step c).
• an excess of ammonia over the secondary amine must be used, for example from 1: 1 to 20: 1 and preferably from 1.5: 1 to 15: 1.
• the release is carried out at a temperature of 0 to 60 ° C, preferably 0 to 40 ° C at a residence time of 10 minutes to 3 hours, preferably 20 to 120 minutes and more preferably 30 to 90 minutes.
• the released secondary amine is then preferably recycled to the reaction.
• polystyrene diisocyanate and also polymeric diphenylmethane diisocyanate (pMDl).
• the polyisocyanates prepared are particularly suitable for the production of urethane, isocyanurate, amide and / or urea group-containing plastics by the polyisocyanate polyaddition process. They are also used for the preparation of urethane, biuret and / or isocyanurate-modified polyisocyanate mixtures.
• Such polyisocyanate mixtures of aliphatic or cycloaliphatic diisocyanates are used in particular for the production of light-resistant polyurethane coatings and coatings.
• the concentration of the urea (1,1-dibutyl-3- [6- (3,3-dibutylureido) hexyl] urea) analyzed by GPC was about 12.6% by weight. This corresponded to a yield of 99.7 mol%.
• the mixture of A) was freed from a large portion of the dibutylamine in vacuo at about 25 mbar. In the distillate, about 50% by weight of amine could be determined by GC analysis. The rest was solvent.

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