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EP2681189A1 - Procédé pour produire des polyisocyanates contenant des groupes biuret - Google Patents

Procédé pour produire des polyisocyanates contenant des groupes biuret

Info

Publication number
EP2681189A1
EP2681189A1 EP12708292.3A EP12708292A EP2681189A1 EP 2681189 A1 EP2681189 A1 EP 2681189A1 EP 12708292 A EP12708292 A EP 12708292A EP 2681189 A1 EP2681189 A1 EP 2681189A1
Authority
EP
European Patent Office
Prior art keywords
diisocyanate
cyclo
aliphatic
reaction
polyisocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12708292.3A
Other languages
German (de)
English (en)
Inventor
Julia Leschinski
Torsten Mattke
Gerrit Waters
Horst Binder
Harald Schäfer
Matthias Kroner
Alexander Bayer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP12708292.3A priority Critical patent/EP2681189A1/fr
Publication of EP2681189A1 publication Critical patent/EP2681189A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/46—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylureas
    • C07C275/58—Y being a hetero atom
    • C07C275/62—Y being a nitrogen atom, e.g. biuret
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups

Definitions

  • the present invention relates to a process for the preparation of biuret-containing polyisocyanates from di- or polyisocyanates with diamines.
  • DE 196 33 404 describes the preparation of biuret-containing polyisocyanates using a high shear mixing element.
  • the application mentions the use of acid catalysts in the simultaneous presence of water or tert-butanol.
  • a disadvantage of the metered addition of water or dehydrating agents is the degradation of isocyanate groups to amine groups, the isocyanates being prepared industrially from the corresponding amines.
  • reaction gases in particular carbon dioxide and isobutene
  • reaction gases in particular carbon dioxide and isobutene
  • the explicit examples without water have been consistently carried out at a high temperature and result in slightly colored products. Isobutene and the exhaust gas flow must also be burned in a technically designed facility.
  • EP-A1 716 080 also describes a process for the preparation of biuret-containing isocyanates from isocyanates and water or steam, wherein the water is introduced to control the reaction in finely dispersed form.
  • biuret-based polyisocyanates by reaction of diisocyanates and diamine was also investigated.
  • the first advantage of these methods compared to the reaction of diisocyanate with biuretizing agents is that neither isobutene (from tert-butanol) nor carbon dioxide are formed as unwanted by-products.
  • the second advantage is that the starting material diisocyanate is theoretically replaced by about one sixth of the diamine input (which is cheaper than the diisocyanate).
  • the diisocyanate is prepared by complex phosgenation or on a phosgene-free path from the diamine.
  • Method using The aim of preparing diisocyanates and diamines in comparison with the reaction with water is therefore that the conversion of the diamine into the isocyanate can be dispensed with for part of the starting material.
  • the disadvantage is, first, that after the mixing of diamine and diisocyanate usually suspended solids are formed, which are not or only with difficulty dissolved in the course of the further reaction or can react further to the biuret polyisocyanate. If the solids are too much and / or too large, material deposits and blockages may occur in the apparatus, or a cloudy product may be formed, or the over-tempering effort for the conversion into soluble biurets may become too long or require too high temperatures.
  • DE 2,609,995 describes a process for the preparation of biuret-containing polyisocyanates by gaseous introduction of diamines in diisocyanates at temperatures of 100 to 250 ° C. Disadvantages are the thermal stress during evaporation of the diamines, or the extra effort when using vacuum. A disadvantage of the participation of gases is the mass transport limitation between gas and liquid phase with a negative influence on the space-time yield. According to this method, for color improvement, a heat treatment at 120-195 ° C, preferably 160-180 ° C, for 6 to 10 hours is required, thereby deteriorating the space-time yield.
  • EP 3 505 describes the preparation of biurets based on diisocyanates and diamine in a plain jet mixing device, in which the educts are mixed under high mixing power.
  • a disadvantage of the process is the use of high reaction temperatures up to 250 ° C.
  • a special apparatus is necessary (smooth jet nozzle).
  • higher oligomers and by-products occur, which leads to an increase in viscosity, undesired lowering of the NCO content, and poorer dilutability with nonpolar solvents (cf EP 277 353, page 2).
  • EP 12 973 describes a process for the preparation of biuret-containing polyisocyanates using strong, mixed with isocyanate Carbamidklarean- hydride-forming acids.
  • a disadvantage is the high residence times of the reaction mixture to achieve a clear biuret-containing liquid, which lead to unacceptable discoloration of the product.
  • EP 277 353 describes a process for the preparation of polyisocyanates containing biuret groups, in which the reactants are reacted at temperatures above 250 ° C. These are still distinguished by a slightly reduced monomer stability and reduced dilution stability (cf., EP 1 158 013, page 2).
  • EP 1 158 013 describes the preparation of biurets based on diisocyanates and diamines at temperatures above 170 ° C. in the presence of an acid-reacting substance as catalyst.
  • the mixing of the components in a mixing chamber that is not specified in more detail with rapid heating of the starting materials is described. It is generally unspecified static and dynamic units of the prior art are used, but is preferred as a mixing chamber, a simple reaction tube without any internals.
  • a disadvantage of this process, as in EP 277 353, is the higher color number compared to products prepared by the processes using biuretizing agents.
  • a disadvantage is also the still high temperature mentioned in the examples on product stability and color formation, as well as a necessary high energy consumption.
  • the HDI feed temperature is 250 or 230 ° C (Example 2).
  • the temperature of the mixture rises to 280 or 260 ° C. (cf., EP 2 287 151, Comparative Example 2 corresponding to EP 1 158 013).
  • a very rapid cooling of the mixture is necessary because the mixtures are not stable at the temperature.
  • EP 2 287 151 relates to EP 1 158 013. It differs in that a partial flow of hexamethylene diisocyanate is added only in a second stage. This has advantages in better variability of the mixing ratios of hexamethylene diisocyanate and hexamethylene diamine at constant volume flow in the first stage, higher possible catalyst concentration in the mixing of hexamethylene diisocyanate and hexamethylene diamine, and use of the second amount of hexamethylene diisocyanate to cool the reaction mixture.
  • the maximum temperature is 255 ° C, which is detrimental to color formation and stability at this temperature.
  • DE-C1 197 07 576 describes a process for the preparation of biuret-containing aromatic polyisocyanates from isocyanates and diamines in which diamine and isocyanate are reacted in a simple mixing chamber with each other and then reacted in a single-stage stirred tank or optionally also a multi-stage stirred tank cascade.
  • WO 2008/1 10492 describes a process for the preparation of biuret-containing polyisocyanates in which diamine and diisocyanate are mixed together in a mixing device with a minimum mixing work.
  • mixing devices various mixing devices are mentioned, explicitly disclosed is a mixing of the components in a mixing pump. However, it lacks a concrete teaching, which technical apparatuses can be used for such a mixture.
  • the object of the present invention was to provide technical apparatus for the production of biurets from isocyanates and diamines, with the colorless products than under comparable reaction conditions or using apparatuses from the prior art, which comprises the biuretizing-free preparation of biurets , wherein the storage stability according to the prior art should at least be maintained.
  • the object was achieved by a process for the preparation of biuret-containing polyisocyanates
  • the advantage of the present invention is that by means of the method or apparatus according to the invention biuret group-containing polyisocyanates of low color can be obtained with fewer problems with solids formation than with the methods known from the prior art.
  • the packing of a rotating fixed bed reactor is an additional reaction zone that other mixers such as rotor-stator elements, Ultra-Turrax, intensive mixers and shear disk mixers do not have. It comes to multiple mixing on different packing elements.
  • the residence time in the high shear zone is significantly longer in a rotating fixed bed reactor than in the other mixing equipment.
  • the mixture in the rotating fixed bed reactor produces fewer and finer agglomerates than with alternative methods. Good mixing can minimize the formation of solids.
  • Suitable di- and polyisocyanates a) for the process according to the invention are (cyclo) aliphatic isocyanates, ie those compounds which have at least 2, preferably 2 to 6, more preferably 2 to 4, very preferably 2 to 3 and in particular exactly 2 Have isocyanate groups bonded to carbon atoms which are part of an aliphatic and / or cycloaliphatic system.
  • Suitable diisocyanates are preferably diisocyanates having 4 to 20 C atoms.
  • Cycloaliphatic isocyanates are those which contain at least one cycloaliphatic ring system.
  • Aliphatic isocyanates are those which contain exclusively straight or branched chains, ie acyclic compounds.
  • aliphatic and cycloaliphatic are summarized in this document as (cyclo) aliphatic.
  • Particularly preferred aliphatic diisocyanates are tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, deca methylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, tetramethylxylylene diisocyanate, 2,4,4- and / or 2,2,4-trimethylhexane diisocyanate or Tetramethylhexandiisocyanat, and as cycloaliphatic diisocyanates 1, 4, 1, 3 or 1, 2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1
  • the aliphatic or cycloaliphatic isocyanates are preferably hexamethylene diisocyanate or isophorone diisocyanate, more preferably hexamethylene diisocyanate. There may also be mixtures of said diisocyanates.
  • 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate generally fall in the ratio of 1: 5: 1 to 1: 1, 5, preferably in the form of an isomer mixture
  • Diisocyanates may be industrially e.g. by phosgenation of diamines according to the processes described in DE-PS 20 05 309 and DE-OS 2 404 773 or by a phosgene-free process (cleavage of urethanes) as described in the
  • EP-B-0 126 299 (US-A-4 596 678), EP-B-0 126 300 (US-A-4 596 679),
  • EP-A-0 355 443 (US-A-5 087 739) and EP-A-0 568 782. According to the invention, it does not matter whether the isocyanate used has been obtained after a phosgene-free or a phosgene-containing preparation route.
  • Isocyanates derived from a phosgenation process often have a total chlorine content of 100-800 mg / kg (according to Wickbold), whereas the phosgene-free isocyanates have a total chlorine content of less than 80 mg / kg, preferably less than 60, more preferably less than 40, most preferably less than 20 and especially less than 10 mg / kg.
  • the total bromine content (according to Wickbold) is generally less than 100 mg / kg, preferably less than 50 mg / kg and especially less than 20 mg / kg.
  • the hydrolyzable chlorine content is determined according to ASTM D4663-98 and is less than 200 ppm, preferably less than 40 ppm, more preferably less than 30 ppm and most preferably less than 20 ppm by weight.
  • the biuret polyisocyanates are reacted by mixing with at least one, preferably exactly one diamine b).
  • Typical organic diamines having exclusively aliphatic and / or cycloaliphatic bonded primary and / or secondary amino groups have a molecular weight below 300.
  • Examples are 1, 2-diaminoethane, 1, 2-diaminopropane, 1, 3-diamino-1, 1-dimethyl-propane , 1, 3-diamino-2,2-dimethyl-propane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, neopentanediamine, 1, 5-diamino-2-methylpentane, 1, 6 Diaminohexane, 1,6-diamino-2,2,4-trimethylhexane and / or 1,6-diamino-2,4,4-trimethylhexane, 1,4- and / or 1,5-diaminohexane, 1, 1-bis (aminomethyl) cyclopentane, 2,4- and
  • any mixtures of such diamines can also be used.
  • 4,4'-diaminodicyclohexylmethane, isophoronediamine and 1,6-diaminohexane are particularly preferred, very particular preference is given to isophoronediamine and 1,6-diaminohexane and in particular 1,9'-diaminohexane.
  • diamines of polyethers preferably polyethylene glycols and polypropyleneglycols, of which 3-oxapentane-1, 5-diamine, 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane 1, 13-diamine, propylene oxide derivatives such as Jeffamine® or polyetheramine D 230, D 400, D 2000, D 4000 from Huntsman or BASF SE, polyethylene / polypropylene derivatives such as Jeffamine® EDR-176, ED-600 , ED-900, ED-2003, HK-51 1, as well as polytetrahydrofuran derivatives such as polytetrahydrofuranine 1700, and polytetrahydrofuran-polypropylene glycol derivatives such as Jeffamine® THF-100, THF-140, XTJ-542, XTJ-559 are preferred , Also conceivable is the use of mixtures
  • triamines for example, polyether triamines such as 3-amino-methyl-1, 6-hexamethylenediamine, 4-aminomethyl-1, 8-octanmethylenediamine, polyetheramine, e.g. BASF SE.
  • An advantage of direct biuretization ie the direct conversion of amines with isocyanates to biurets, is that by using amines instead of water, it is not necessary first to build up amine to isocyanate and then to hydrolyze it back to the amine by means of water.
  • reaction gases in particular carbon dioxide (and isobutene) as a by-product of the reaction and in the exhaust gas.
  • Another advantage of direct biuretization is that the choice of amines is not limited to the amines given by the availability of isocyanate monomers (by their hydrolysis).
  • a further advantage of direct biuretization is that it is not necessary to use the same basic bodies as the isocyanate monomers.
  • said isocyanates a) and diamines b) are reacted in proportions which correspond to an equivalent ratio of isocyanate groups to amino groups of at least 4: 1, preferably from 4: 1 to 50: 1 from 5: 1 to 40: 1 and especially 5: 1 to 30: 1, where the primary amino groups are mono- functional groups are included in the calculation.
  • the conversion of the total mass of isocyanates a) is preferably between 5 and 70%, preferably between 10 and 55%, particularly preferably between 20 and 40%.
  • the diamine b) is completely reacted in the reaction, and the excess isocyanate a) distilled off.
  • the diamine b) can be metered into the reaction in liquid or gaseous form, preferably liquid.
  • the reaction can optionally be carried out in the presence of at least one catalyst c). It is an advantage of the process according to the invention that it is possible to dispense with a catalyst.
  • a catalyst is present.
  • the reaction can be accelerated by metered addition of a catalyst.
  • Suitable catalysts in the process according to the invention are any acids, preferably protic acids, having a pKa ⁇ 10, more preferably ⁇ 9 and most preferably ⁇ 8.
  • Suitable protonic acids are, for example, hydrogen sulfates, in particular tetralkylammonium hydrogen sulfates, their aliphatic, branched
  • sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, 2- or 4-toluenesulfonic acid, benzenesulfonic acid, cyclododecanesulfonic acid, camphorsulfonic acid or naphthalene-1 - or -2-sulfonic acid, or mono- and dicarboxylic acids such as formic acid, Acetic acid, propionic acid, butyric acid, pivalic acid, stearic acid, cyclohexanecarboxylic acid, oxalic acid, malonic acid, succinic acid, adipic acid, benzoic acid or phthalic acid.
  • the dicarboxylic acids mentioned are less preferred, as far as they are significant under the reaction conditions, for example more than 10 mol% with respect to the amount used, preferably more than 8 mol%, more preferably more than 5 mol% and very particularly preferably More than 3 mol%, release water, as can be released from these by anhydride water as a biuretizing agent.
  • the (ar) aliphatic carboxylic acids described, for example, in EP-A-259,233 are found to be less effective.
  • phosphoric acids and / or their (mono- and / or) dialkyl esters or aryl esters and / or hydrogen sulfates Use is preferably made of mono- and / or dialkyl esters or aryl esters of phosphoric acid whose aliphatic, branched aliphatic, araliphatic or aromatic radicals have 1 to 30, preferably 4 to 20, carbon atoms.
  • Di-iso-propyl phosphate, di (2-ethylhexyl) phosphate, di (n-butyl) phosphate and di-hexadecyl phosphate are particularly preferably used.
  • low-valency acidic derivatives of phosphoric acid for example phosphorous acid
  • phosphoric acid for example phosphorous acid
  • the packing contains catalytically active solid components such as acidic ion exchangers. These can completely or partially replace a catalyst added to the raw material stream.
  • acids are used in the process according to the invention in amounts of from 0.01 to 1.0% by weight, preferably from 0.02 to 0.5% by weight and very particularly preferably from 0.05 to 0.5% by weight. , based on the total amount of diisocyanates used.
  • the acids may be added dissolved or dispersed in a suitable solvent. Preferably, the acids are added in substance.
  • catalyst for example, strong inorganic Lewis or
  • Branstedt acids such as boron trifluoride, aluminum trichloride, sulfuric acid, phosphorous acid, hydrochloric acid and / or salts of nitrogenous bases and inorganic and / or organic acids, as described in DE-A-19 31 055, Page 3, last paragraph to page 6, first full paragraph, which hereby by reference is the subject of the present disclosure, are used.
  • a stabilizer f selected from the group urea, ammonia, biuret, urea derivatives or carboxamides as described in WO 96/25444, preferably urea, N-methylurea, N-ethylurea, ⁇ , ⁇ -dimethylurea, ⁇ , ⁇ '-dimethylurea, N, N-diethylurea, ⁇ , ⁇ '-diethylurea, ethyleneurea or phenylurea; urea is particularly preferred.
  • stabilizers e.g. Urea
  • water or solvent When the process is to be carried out in the absence of CO2, water is less preferred as a solvent.
  • stabilizers are used in amounts of 0.01-2.0, preferably 0.05-1 mol%, based on the isocyanate groups in (a).
  • these stabilizers are dissolved or dispersed in at least one solvent d), as listed below.
  • solvents d) may optionally additionally be used as solubilizers.
  • solubilizers for example, ethers such as dioxane or tetrahydrofuran; Alkoxyalkyl carboxylates, such as e.g.
  • Ketones such as 2-butanone, 4-methyl-2-pentanone, cyclohexanone, aromatic solvents, for example toluene, xylene, flavoring mixtures having 8-20 carbon atoms, chlorobenzene, o-dichlorobenzene, hexane, hydrocarbon mixtures and / or trialkyl phosphates.
  • N-methylpyrrolidone and other N- (cyclo) alkylpyrrolidones for example N-methylpyrrolidone, N-ethylpyrrolidone, N-n-butylpyrrolidone and N-cyclohexylpyrrolidone.
  • Methoxypropyl acetate, methoxyethyl acetate, trimethyl phosphate, tri-n-butyl phosphate and triethyl phosphate are preferably used according to the invention. It is also possible to use any desired mixtures of the solvents.
  • the diamine is preferably dissolved in this and this diamine solution is fed into the reaction.
  • the concentration of the diamine in the solvent is from 2 to 100% by weight (solvent-free), preferably from 5 to 30% by weight, more preferably from 10 to 25% by weight, and most preferably from 15 to 20% by weight.
  • solvent-free preferably from 5 to 30% by weight, more preferably from 10 to 25% by weight, and most preferably from 15 to 20% by weight.
  • the compound e) may be liquid or vaporous water or at least one dehydrating compound.
  • the latter can be, for example, tert-butanol or dicarboxylic acids, which can release water by anhydride formation, or compounds containing water of crystallization. The addition of such compounds is less preferred.
  • the reaction mixture may also contain additional inert gas streams, e.g. contain a liquid or gaseous inert stream.
  • the inert stream is preferably added in gaseous form.
  • Suitable inert medium are all gases which are not essential, i. at the reaction conditions less than 5 mol%, preferably less than 2 mol%, more preferably less than 1 mol%, react with the isocyanate stream, the amine-containing stream and / or the catalyst.
  • a rotating fixed bed reactor (Engl.: Rotating Packed Bed or Hi-Gee reactor) is understood according to the invention a reactor in which a liquid phase with a difference in relative velocity on a rotating solid element meets, resulting in a division and mixing of liquid phase leads.
  • Preferred rotating fixed-bed reactors have structured or unstructured packages as rotating solid element, with which the mixing of the liquid phase takes place.
  • the reactor contains a continuous gas phase. It comes on the pack to a strong film and droplet flow.
  • Film flow means a three-phase system of packing, liquid and gas phase.
  • Droplet flow means a two-phase system liquid-gaseous (or liquid-liquid) when, after the first mixture of polyisocyanate and diamine component, their mixtures fly farther outward from the trapping edges of the packing.
  • the presence of a gas phase allows for film and three-phase formation.
  • the gas phase must be present at least to such an extent that there is a continuous gas phase within the packing.
  • FIG. 1 shows an exemplary schematic embodiment of a rotating fixed bed reactor as can be used for the present invention.
  • the reference signs are as follows:
  • gas inlet for example for inert gas
  • R2 Outer radius between axis of rotation and packing, thickness of the mixing zone
  • R 3 Inner radius between axis of rotation and packing
  • Structured internals such as packages (inter alia also of wire nets and fabrics), static mixers, separating plates, metal plates (thin, corrugated and / or perforated) as well as unstructured porous systems such as fillings of packing or open-pore foam structures may be mentioned here as elements 2.
  • the packs can optionally be stabilized by webs. In a preferred form such webs are not present to avoid potential solid deposits.
  • the rotating fixed bed reactor has the advantage that its height H2 can be variably adjusted by installing fixed elements in relation to parts of the packing. This allows for a variable volume flow in the mixing reactor same velocity profile.
  • the liquid stream moves after metering of (cyclo) aliphatic di- and / or polyisocyanate and (cyclo) aliphatic diamine from the center of the package to the outside, and then in mixed and at least partially reacted form via the liquid outlet from the mixing device ,
  • the acceleration acting on the liquid phase in the mixing device is at least 100 g, preferably 100-2000 g, particularly preferably 500-1000 g. Due to the high acceleration, congestion effects of the liquid are reduced in countercurrent. Thus, throughput and space-time yield can be increased.
  • the speed of the liquid phase in the mixing device is generally 0.001-1 m / s, preferably 0.003-0.05 m / s.
  • inert gases is preferred to ensure the presence of a gas phase in the rotating fixed bed reactor so far that the pack is not flooded and thus to ensure a good mix.
  • the gas flow is applied via the housing, the packing passes countercurrently to the liquid flow and exits via the hollow shaft.
  • the liquid application takes place at temperatures of at least 30 ° C. above the melting point of the amines, in the case of hexamethylenediamine preferably above 60 ° C., in particular above 80 ° C.
  • the mixing takes place above 120, especially above 140 ° C outlet temperature from the rotating fixed bed reactor i).
  • the upper limit of the temperature is preferably chosen so that it is not higher at the liquid outlet of i) than in the subsequent reaction reactor ii).
  • the exotherm must be taken into account in the reaction of (cyclo) aliphatic di- and / or polyisocyanate (a) and (cyclo) aliphatic diamine (b) in the rotating fixed bed reactor.
  • the upper limit of the temperature of the reaction mixture during mixing i) is less than 270 ° C, preferably not more than 250 ° C.
  • the temperature is not more than 200 ° C.
  • the absolute pressure at the outlet of the mixing device is in the range of 0.3 bar to 10 bar, preferably from 0.6 bar to 7 bar, more preferably from 0.8 bar to 5 bar.
  • the educts a) and b) and the catalyst c) are mixed with or without solvent and with or without inert gas and with or without compound e).
  • reaction apparatus for stage ii it is possible to use all customary residence time reactors, such as stirred tanks, jet loop reactors, tube reactors, vessels, columns. Combinations or multiple uses of the types of apparatus are also possible.
  • a stirred tank can be combined with a tubular reactor.
  • a cascade of stirred tanks can be used as a reaction apparatus.
  • the flow state is preferably set so that the Newton number characterizing the power input does not depend inversely proportionally on the Reynolds number formed with the stirrer diameter with variation of the speed.
  • the flow state is adjusted so that the Newton number does not depend on the Reynolds number with variation of the speed.
  • the Reynolds number is preferably at least 2300, more preferably at least 2700, most preferably at least 3000, in particular at least 4000, at least 7000 or especially at least 10000.
  • At least one longitudinally flow-through stirred tank vessel with a diameter to length ratio of 1 to 1.2 to 1 to 10, preferably from 1 to 1.5 to 1 to 6, is used.
  • the volume-specific power input in this stirred tank should be at least 0.1 watt / l, preferably at least 0.3, more preferably at least 0.5 watt / l. As a rule, up to 20 watt / l, preferably up to 6 watt / I and more preferably to 2 watts / I sufficient.
  • the performance can be entered via all types of stirrers, such as angled blades, anchors, discs, turbines, bar stirrers.
  • Disc and turbine stirrers are preferably used.
  • stirrers installed on the shaft.
  • a stirrer is used on the shaft per segment of the cascade.
  • the diameter of the stirring elements is 0.1 to 0.9 times the Rhakkessel bemessers, preferably 0.2 to 0.6 times the Rhakkessel bemessers.
  • the stirred tank or cascaded stirred tank can be operated with or without baffles.
  • the operation is carried out with baffles.
  • the operation is usually carried out with 1 to 10 baffles, preferably with 2 to 4 baffles per segment.
  • the reaction mixture is fed after leaving the mixing stage i) the reactor.
  • the reactor is a predominantly vertically arranged apparatus (for example, a vertical tubular reactor, column or slender stirred tank).
  • the supply of the reaction mixture from below (direct current of the liquid phase with the inert gas) or from above (countercurrent to the inert gas), preferably from below.
  • the removal of the optionally added inert gas can take place at any point in the system. Preferably, the removal takes place only after complete reaction of the reaction mixture.
  • the residence time in the reaction apparatus ii) is preferably in the range from 1 minute to 8 hours, preferably 1 minute to 8 hours, more preferably from 30 minutes to 6 hours and most preferably 1 to 4 hours.
  • the reaction time is favorably chosen so that at the end of the theoretical NCO value is reached.
  • the theoretical NCO value is the NCO value which the reaction mixture has when the total amount of amine used has formed the theoretically expected amount of biuret groups.
  • the temperature is in the range of the reaction distance ii) in the range of 30-300 ° C, preferably 80 to less than 300 ° C, particularly preferably from 120 to 250 ° C.
  • the absolute pressure in the reaction apparatus is in the range from 0.3 to 100 bar, preferably from 0.5 to 10 bar, more preferably from 0.6 to 4 bar, more preferably from 0.8 to 2 bar.
  • the catalyst c) is added to the reaction mixture in the mixing device i).
  • the mixing of the catalyst stream may also instead or additionally separately in the reaction apparatus ii) or at several points.
  • the catalyst is mixed into one of the streams, which are fed to the rotating fixed bed reactor.
  • the catalyst stream is fed to the isocyanate group-containing stream which passes into the mixing device.
  • the invention consists of the combination mixing device i) and reaction apparatus ii).
  • the isocyanate stream a) and catalyst c) are then premixed and mixed with the amine-containing stream b) and then introduced into the reaction apparatus ii) after passing through the mixing device.
  • the mixing device i) and the reaction apparatus ii) must not be separated in terms of apparatus, but the reaction apparatus ii) can also be connected directly to the mixing device.
  • the reaction may already start immediately after mixing of the components, so that the reaction is not necessarily limited to the reaction apparatus ii).
  • an isocyanate partial stream can be introduced only after the mixing device, for example between mixing device and reaction apparatus, or directly into the reaction apparatus. The mixing effort for this is lower than that for the isocyanate and amine stream. As a result, in the event that the mixing temperature in the mixing device is higher than in the after-reaction, rapid cooling of the product takes place before and / or in the reaction apparatus.
  • the apparatuses used for this are flash, falling-film, thin-layer or short-path evaporators, to which optionally a distillation column can be placed.
  • the distillation is generally carried out at a pressure between 0.1 and 300 hPa, preferably below 200 hPa and more preferably below 100 hPa.
  • Another object of the present invention is a process for the preparation of biuret polyisocyanates by reacting a diisocyanate with a diamine in the presence of at least one acid and optionally a solvent ses, in which the (cyclo) aliphatic di- and / or polyisocyanate stream 1 and the Diaminstrom 2 and a stream 9 of recycled optionally present solvent and recycled excess diisocyanate 13 in the presence of at least one catalyst in a mixing device (I) mixed together, then the resulting mixture of diamine and diisocyanate in at least one reaction apparatus (II) and biuret weakness restroomn Polyisocyanate reacts, then optionally existing solvent, excess diisocyanate and biuret-containing polyisocyanate by distillation separated from each other and the optionally present solvent and the excess diisocyanate in the mixing device (I) leads back (see Figure 2).
  • the streams of (cyclo) aliphatic diisocyanate and / or polyisocyanate 1 and 13 are preferably mixed and fed together to the rotating fixed bed reactor.
  • the process according to the invention can in one embodiment be carried out in the presence of a solvent as shown in FIG. 2:
  • the process comprises a mixing device (I), at least one reaction apparatus (II), two distillation apparatuses (III) and (IV) and optionally a further mixing device (V) and optionally a further distillation unit (VI).
  • the distillation units (III) to (VI) can also be replaced by any other circuits of distillation units of a different number and design as long as a product having a sufficient purity is obtained.
  • the fresh stream 8 of solvent can be significantly reduced or optionally set to zero.
  • the diamine is preferably mixed as stream 17 instead of stream 2 in an upstream mixing unit (V) with recycled solvent 7 and this mixture is passed as stream 9 into the mixing unit (I). In this case, the current 2 is zero.
  • the mixture of diamine and di- and / or polyisocyanate obtained in the mixing unit (I) is then passed into at least one reaction apparatus (II) and converted into the biuret-group-containing polyisocyanate.
  • the fastest possible cooling takes place between mixing apparatus (I) and reaction apparatus (II) or, less preferably, in the reaction apparatus. This is particularly necessary if a temperature greater than 190, in particular greater than 200 ° C to 270 ° C is selected in mixing apparatus (I) for the reduction of precipitates, which should be kept as short as possible to avoid color formation and for safety reasons (autothermal decomposition ).
  • partial metering of the isocyanate component takes place between mixing apparatus (I) and reaction apparatus (II) or preferably in the reaction apparatus (II).
  • This has the advantage that the isocyanate component at a higher temperature in the mixing chamber does not have to be completely brought to a high temperature, or can be cooled with the second partial flow.
  • this has the advantage of a higher catalyst concentration during the mixing of isocyanate and amine component in the mixing apparatus (at the same concentration of the residual amount of catalyst in the final product) when using a catalyst.
  • reaction mixture 4 thus obtained is then passed into the first distillation unit (III), in which the excess diisocyanate and solvent in the mixture are separated off as stream 5 as low boilers.
  • the distillation unit (III) can have one or more theoretical separation stages, preferably a multistage, preferably at least two-stage, more preferably at least three-stage, very preferably at least four-stage cascade of flash evaporator, falling film evaporator, thin film evaporator and / or short path evaporator.
  • the course 6 from the distillation unit (III) is the biuret group-containing polyisocyanate as desired product, which can generally be further processed without further purification.
  • the vapors of the distillation unit (III), consisting of excess diisocyanate and solvent, are then passed into a further distillation unit (IV), in which the solvent, which preferably boils more easily as the diisocyanate, is separated off from the excess diisocyanate as bottoms effluent 7 as vapors becomes.
  • the distillation unit (IV) is, for example, a distillation unit having 5 to 40, preferably 10 to 30 theoretical plates.
  • this stream may optionally be subjected to a preferably one-stage evaporation (VI), for example in a falling-film evaporator.
  • V evaporation
  • the purified overhead withdrawn diisocyanate 13 is then optionally mixed with catalyst 15 and fed into the mixing unit (I), the bottom outlet 14 is discarded.
  • the distillation unit (VI) when the distillation unit (VI) is present, the freshly used diisocyanate and / or polyisocyanate is not passed through the stream 1 directly into the mixing unit, but added as stream 1 1 the stream 10 and then this mixture 12 is distilled , As a rule, the quality, in particular the color quality of the product, is further improved by this distillation of the freshly added diisocyanate.
  • FIG. 3 A further preferred embodiment is shown in FIG. 3 and differs from that shown in FIG. 2 by the interconnection of the distillation units (III) and (IV):
  • the solvent 7 is separated off as low boilers and excess diisocyanate and biuret group-containing polyisocyanate-containing stream 15 withdrawn in the bottom and preferably in the distillation unit (III), which is a multi-stage, preferably at least two stages, more preferably at least three stages, most preferably at least four stages cascade of flash evaporator, falling film evaporator, thin film evaporator and / or short path evaporator.
  • the excess diisocyanate is withdrawn as vapors 10 and recycled as described above and the biuret polyisocyanate 6 removed as a bottom outlet.
  • the reflux of isocyanate and the fresh feed of (cyclo) aliphatic diisocyanate are combined.
  • the distillation apparatus IV in FIG. 2 can be dispensed with and the distillate stream 5 fed without separation of (cyclo) aliphatic diisocyanate and solvent to the rotating fixed bed reactor or the stream of (cyclo) aliphatic diisocyanate and / or polyisocyanate 1 become.
  • the solvent streams are fed to the stream 1 of (cyclo) aliphatic di- and / or polyisocyanate and / or stream 2 of (cyclo) aliphatic diamine and / or stream 15 (catalyst).
  • diisocyanate is separated from the biuret in a distillation apparatus (III), mixed with fresh di- and / or polyisocyanate, optionally added catalyst and fed separately from the Diaminstrom the rotating fixed bed reactor.
  • the optional catalyst is preferably added to the di- and / or polyisocyanate stream and not separately.
  • the catalyst is added after the rotating fixed bed reactor before the reaction apparatus.
  • clear products are generally obtained which have a color number of less than 100, preferably less than 50, in particular It prefers less than 20 APHA according to DIN ISO 6271 and / or a viscosity of 1000 to 15000 mPas, preferably 1000 to 10000 mPas at 23 ° C according to
  • biuret polyisocyanates having a viscosity of 2,000 to 15,000, preferably from 2,500 to 10,000 mPas (based on a solids content of 100% measured at a temperature of 23 ° C and a shear rate of 100 s 1 ), desired.
  • Such polyisocyanates may be diluted with solvents if necessary, for example the ones mentioned above, preferably ethyl acetate, butyl acetate, methoxypropyl acetate, xylene and aromatic mixtures having 8-20 carbon atoms and mixtures thereof.
  • uretdione- and / or carbodiimide-containing polyisocyanates and / or isocyanurate may also be present to a lesser extent, and allophanate-containing polyisocyanates in the presence of alcohols.
  • the proportion of oxadiazinetrione group-containing polyisocyanates in the reaction mixture according to the invention is less than 1% by weight, preferably 0.75% by weight, more preferably less than 0.5% by weight, very preferably less than 0.3% by weight and especially less as 0.1% by weight.
  • the biuret-containing polyisocyanates obtained by the process according to the invention can also be subsequently reversibly blocked with blocking groups.
  • the biuret-containing polyisocyanates obtained by the process according to the invention are generally used in the coatings industry and can be used, for example, in coating compositions for 1K or 2K polyurethane coatings, for example for primers, fillers, basecoats, unpigmented topcoats, pigmented topcoats and clearcoats Industrial, in particular aircraft, marine or large vehicle painting, wind turbine paint, wood, plastics, automotive, especially OEM or car refinish, or decorative paint can be used. Particularly suitable are the coating compositions for applications in which a particularly high application safety, outdoor weathering resistance, appearance, solvent and / or chemical resistance are required. The curing of these coating compositions is not essential according to the invention.
  • gas inlet for example for inert gas
  • R2 Outer radius between axis of rotation and packing, thickness of the mixing zone
  • R 3 Inner radius between axis of rotation and packing

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé pour produire des polyisocyanates contenant des groupes biuret à partir de di ou polyisocyanates présentant des diamines.
EP12708292.3A 2011-03-03 2012-03-02 Procédé pour produire des polyisocyanates contenant des groupes biuret Withdrawn EP2681189A1 (fr)

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EP11156783 2011-03-03
PCT/EP2012/053660 WO2012117099A1 (fr) 2011-03-03 2012-03-02 Procédé pour produire des polyisocyanates contenant des groupes biuret
EP12708292.3A EP2681189A1 (fr) 2011-03-03 2012-03-02 Procédé pour produire des polyisocyanates contenant des groupes biuret

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US8933262B2 (en) 2011-05-24 2015-01-13 Basf Se Process for preparing polyisocyanates from biomass
CN103724234B (zh) * 2014-01-03 2015-07-15 万华化学集团股份有限公司 一种制备含有缩二脲的聚异氰酸酯的方法
CN105601565B (zh) * 2014-11-20 2018-05-15 万华化学集团股份有限公司 一种存储稳定的含缩二脲结构的多异氰酸酯的制备方法
EP3305863A1 (fr) * 2016-10-07 2018-04-11 Basf Se Procédé de production de polyisocyanates de diisocyanates (cyclo)aliphatiques résistants à la floculation dans les solvants
CN108559048B (zh) * 2018-04-19 2021-01-08 山东师范大学 一种pH值敏感性可生物降解聚氨酯脲材料及其制备方法
CN108586293B (zh) * 2018-04-19 2020-07-14 济南羽时信息科技有限公司 一种可生物降解高强度聚醚酯型聚氨酯脲泡沫及其制备方法
CN110483337B (zh) * 2018-05-14 2020-08-28 中国科学院过程工程研究所 一种苯二亚甲基二异氰酸酯产品的分离精制系统及方法
CN111171893A (zh) * 2018-11-13 2020-05-19 中国石油天然气股份有限公司 聚脲润滑脂的制备方法

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