DE102005006550A1 - Process for the preparation of polyisocyanates and their use - Google Patents

Abstract

A process for the preparation of polyisocyanates by a partial oligomerization of diisocyanates in the presence of at least one oligomerization catalyst from the group of ionic liquids and the use of the thus obtainable polyisocyanates as a polyisocyanate component in polyurethane paints.

Description

The The present invention relates to a novel process for the preparation of polyisocyanates by a partial oligomerization of diisocyanates in the presence of at least one oligomerization catalyst the group of ionic liquids and the use of the so available Polyisocyanates as a polyisocyanate component in polyurethane coatings.

method for partial or complete Trimerization of organic polyisocyanates for the preparation of Biuret, allophanate or isocyanurate polyisocyanates or cellular or compact isocyanurate polyurethanes are known and are published in numerous literature described.

The use of 2-hydroxyalkylammonium cations with a counterion as catalysts in the preparation of polyisocyanates is widespread and already known, for example from US 4,801,663 , DE-OS 29 16 201 (= US 4,454,317 ) US 3,862,150 DE-OS 26 31 733 or EP 17 998 ,

adversely in the known 2-hydroxyalkylammonium catalysts is that it is These are solids that are poorly dosed as such.

such 2-Hydroxyalkylammonium catalysts are partially commercially available, but mostly only as a solution in alcohols, such as ethylene glycol, diethylene glycol, Propylene glycol, dipropylene glycol, etc. However, alcohols react with isocyanates and thus cause by-products.

JP-A 2002 097244 describes a process in which the isocyanurate formation with a known catalyst having a 2-hydroxyalkylammonium structure carried out is in the presence of ascorbic acid as a co-catalyst. ascorbic acid is thus added as a further component, but does not provide the anion of the catalyst.

US 5905151 and US 5955609 describe lithium salicylate as a catalyst for isocyanurate formation.

adversely Lithium salicylate on this catalyst is that it is a difficult to dose Solid is and in addition not readily thermally deactivated.

WHERE 03/093246 describes ionic liquids, also as catalysts in the oligomerization of isocyanates can be used those of a five-membered one Nitrogen heteroaromatics exist and one with 4 hydrocarbon radicals substituted Ammonium or Phosphoniumkation, wherein the hydrocarbon radicals contain up to 3 heteroatoms and optionally be halogen-substituted can.

WHERE 02/092656 describes a process for the oligomerization of isocyanates with the help of ionic liquids, their anions have a 1,2,3- and / or 1,2,4-triazolate structure. cations can Alkali or alkaline earth metals or ammonium or phosphonium ions be substituted with 4 hydrocarbon radicals.

WHERE 02/092657 describes a process for the oligomerization of isocyanates with the help of ionic liquids, their anions have a 1,2,3- and / or 1,2,4-triazolate structure. cations can Alkali or alkaline earth metals or ammonium or phosphonium ions be saturated with hydrogen or unsaturated aliphatic or cycloaliphatic, optionally substituted aromatic or araliphatic radicals having up to 24 carbon atoms and optionally contain up to 3 heteroatoms and optionally substituted by halogen atoms or hydroxy groups may be substituted are.

such Cations have the disadvantage that they thermally not be deactivated and thus a reaction only via catalyst poisons to stop.

The Object of the present invention was to further catalysts for the preparation of polyisocyanates according to the simplest possible method in very good quality provide highly reactive, easy to dose and thermal should be deactivated.

und einem Schmelzpunkt von nicht mehr als 100 °C
handelt,
worin
R¹, R², R³, R⁴, R⁵, R⁶ und R⁷ unabhängig voneinander jeweils gleich oder verschieden sein können und für eine geradkettige oder verzweigte C₁- bis C₂₀-Alkylgruppe, eine gegebenenfalls substituierte C₅- bis C₁₂-Cycloalkylgruppe, eine gegebenenfalls substituierte C₇- bis C₁₀-Aralkylgruppe, oder eine gegebenenfalls substituierte C₆-C₁₂-Arylgruppe stehen oder
zwei oder mehr der Reste R¹ bis R³ gemeinsam miteinander eine 4-, 5- oder 6-gliedrige Alkylenkette bilden oder zusammen mit einem Stickstoffatom einen 5- oder 6-gliedrigen Ring bilden, der noch ein zusätzliches Stickstoff- oder Sauerstoffatom als Brückenglied enthalten kann oder gemeinsam ein mehrgliedriges, vorzugsweise sechsgliedriges Mehrringsystem, vorzugsweise Zweiringsystem bilden, das noch ein oder mehrere zusätzliche Stickstoffatome, Sauerstoffatome oder Stickstoff- und Sauerstoffatome als Brückenglieder enthalten kann und
R⁴, R⁵, R⁶ und R⁷ zusätzlich Wasserstoff
sein können.This object has been achieved by a process for the preparation of polyisocyanates containing isocyanurate, biuret and / or allophanate groups by at least partial oligomerization of diisocyanates, in which the reaction is carried out in the presence of at least one oligomerization catalyst, which is an ionic liquid the structure

and a melting point of not more than 100 ° C
These,
wherein
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ can each independently be the same or different and for a straight-chain or branched C ₁ - to C ₂₀ -alkyl group, an optionally substituted C ₅ - C ₁₂ -cycloalkyl group, an optionally substituted C ₇ - to C ₁₀ -aralkyl group, or an optionally substituted C ₆ -C ₁₂ -aryl group or
two or more of R ¹ to R ³ together form a 4-, 5- or 6-membered alkylene chain or together with a nitrogen atom form a 5- or 6-membered ring, which still contain an additional nitrogen or oxygen atom as a bridge member may or together form a multi-membered, preferably six-membered multi-ring system, preferably Zweiringsystem, which may contain one or more additional nitrogen atoms, oxygen atoms or nitrogen and oxygen atoms as bridge members, and
R ⁴ , R ⁵ , R ⁶ and R ⁷ additionally hydrogen
could be.

Ionian liquids For the purposes of this document, those are compounds that consist of at least consist of a cation and at least one anion and at atmospheric pressure have a melting point of not more than 100 ° C, preferably not more than 90 ° C, more preferably not more than 80 ° C, most preferably of not more than 70 ° C, in particular not more than 60 ° C and especially not more than 50 ° C.

In a preferred embodiment it may make sense that the Ionic liquids under the conditions of the reaction are liquid, but on cooling to lower temperatures, for example at least 10 ° C below the Reaction temperature, preferably 20 ° C, particularly preferably 25 and most preferably at least 30 ° C below the reaction temperature, become firm, so that the Compounds by a solids separation, for example a Filtration or sedimentation, can be separated.

In a particularly preferred embodiment are the ionic liquids liquid under the conditions of the reaction and remain so in the reaction mixture to a temperature of room temperature, preferably up to 20 ° C, more preferably up to 15 ° C and most preferably up to 15 ° C.

In the above radicals mean
a straight-chain or branched C ₁ - to C ₂₀ -alkyl group, for example methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl or 1,1,3,3-tetramethylbutyl,
an optionally substituted C ₅ to C ₁₂ cycloalkyl group, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl,
an optionally substituted C ₇ to C ₁₀ aralkyl group, for example, benzyl, 1-phenylethyl, 2-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) ethyl, o, m or p-chlorobenzyl, 2,4-dichlorobenzyl, o-, m- or p-methoxybenzyl or o-, m- or p-ethoxybenzyl,
an optionally substituted C ₆ -C ₁₂ -aryl group, for example phenyl, 2-, 3- or 4-methylphenyl, α-naphthyl or β-naphthyl, furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl , Dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl, tert-butylthiophenyl, pyridazinyl, pyrimidinyl, pyrazinyl, imidazolyl or Pyrazolyl.

Examples of R ¹ to R ³ are each independently of one another methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, phenyl, α- or β-naphthyl, benzyl, cyclopentyl or cyclohexyl.

If two or more of the radicals R ¹ to R ^{3 form} at least one ring, these may be, for example, 1,4-butylene, 1,5-pentylene, 3-oxa-1,5-pentylene, 3-aza-1,5-pentylene or 3-methyl-3-aza-1,5-pentylene.

Methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, phenyl and benzyl are particularly preferred for the radicals R ¹ to R ³ , with methyl, ethyl, n-butyl, phenyl and benzyl being particularly preferred preferred are methyl, ethyl and n-butyl and especially methyl.

Examples of R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently hydrogen, methyl, ethyl, n-propyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, phenyl, α - or β-naphthyl, benzyl, cyclopentyl or cyclohexyl. Preference is given to hydrogen, methyl and phenyl, more preferably at least one of the radicals R ⁴ and R ^{5 is} hydrogen and very particularly preferably both radicals R ⁴ and R ^{5 are} hydrogen.

Preferred radicals R ⁶ and R ⁷ are hydrogen, methyl and phenyl, more preferably at least one of R ⁶ and R ^{7 is} hydrogen or methyl and most preferably both R ⁶ and R ^{7 are} hydrogen.

ring systems containing ammonium ions are, for example, methylated, ethylated or benzylated piperazines, piperidines, pyrrolidine, morpholines, Quinuclidines (1-azabicyclo [2.2.2] octane) or triethylenediamines.

Preferably, R ¹ , R ² and R ^{3 are the} same and at least one of R ⁴ and R ^{5 is} hydrogen and both R ⁶ and R ^{7 are} hydrogen, more preferably R ¹ , R ² and R ^{3 are the} same and both R ⁴ and R ⁴ R ^{5 is} hydrogen and both R ⁶ and R ^{7 are} hydrogen.

Examples of ammonium cations are
2-hydroxyethyltrimethylammonium, 2-hydroxypropyltrimethylammonium, 2-hydroxyethyltriethylammonium, 2-hydroxypropyltriethylammonium, 2-hydroxyethyltri-n-butylammonium, 2-hydroxypropyltri-n-butylammonium, 2-hydroxyethyltrimethylammonium n -octylammonium, 2-hydroxypropyltri-n-octylammonium, 2-hydroxyethyldimethylbenzylammonium, 2-hydroxypropyldimethylbenzylammonium, 2-hydroxyethyldiethylbenzylammonium, 2-hydroxypropyldiethylbenzylammonium, 2-hydroxyethyl-di-n-butylbenzylammonium, 2 Hydroxypropyl-di-n-butylbenzylammonium, 2-hydroxyethylmethyldiethylammonium, 2-hydroxypropylmethyldiethylammonium, 2-hydroxyethyl-ethyldimethylammonium, 2-hydroxypropyl-ethyldimethylammonium, 2-hydroxyethyl-di-n-butylmethyl-ammonium, 2-hydroxypropyl-di-n butylmethylammonium, 2-hydroxyethyl-di-n-butylethylammonium, 2-hydroxypropyl-di-n-butylethylammonium, 2-hydroxyethyl-di-iso-propylethylammonium, 2-hydroxypropyl-di-iso-propylethylammonium, N- (2-hydroxyethyl) - N, N-dimethylpiperidinium, N- (2-hydroxypropyl) -N, N-dimeth ylpiperidinium, N- (2-hydroxyethyl) -N, N-diethylpiperidinium, N- (2-hydroxypropyl) -N, N-diethylpiperidinium, N- (2-hydroxyethyl) -N, N-dimethylmorpholinium, N- (2-hydroxypropyl ) -N, N-dimethylmorpholinium, N- (2-hydroxyethyl) -N, N-diethylmorpholinium, N- (2-hydroxypropyl) -N, N-diethylmorpholinium, N- (2-hydroxyethyl) -N, N-dimethylpiperazinium, N- (2-hydroxypropyl) -N, N-dimethylpiperazinium, N- (2-hydroxyethyl) -N-methyl-diazabicyclo [2,2,2] octane, N- (2-hydroxypropyl) -N-methyl-diazabicyclo [ 2,2,2] octane, N- (2-hydroxyethyl) -N-ethyl-diazabicyclo [2,2,2] octane, N- (2-hydroxypropyl) -N-ethyl-diazabicyclo [2,2,2] octane, N- (2-hydroxyethyl) -N-benzyl-diazabicyclo [2,2,2] octane or N- (2-hydroxypropyl) -N-benzyl-diazabicyclo [2,2,2] octane.

Prefers are 2-hydroxyethyltrimethylammonium, 2-hydroxypropyltrimethylammonium, 2-hydroxyethyl-triethylammonium, 2-hydroxypropyltriethylammonium, 2-hydroxyethyl-tri-n-butylammonium, 2-hydroxypropyl tri-n-butylammonium, 2-hydroxyethyltri-n-octylammonium, 2-hydroxypropyltri-n-octylammonium, 2-hydroxyethyldimethylbenzylammonium, 2-hydroxypropyl dimethylbenzylammonium, 2-hydroxyethyl-diethylbenzylammonium and 2-hydroxypropyl-diethylbenzylammonium.

Especially preferred are 2-hydroxyethyltrimethylammonium, 2-hydroxypropyltrimethylammonium, 2-hydroxyethyltriethylammonium, 2-hydroxypropyl-triethylammonium, 2-hydroxyethyl tri-n-butyl ammonium, 2-hydroxypropyl tri-n-butyl ammonium, 2-hydroxyethyl tri-n-octyl ammonium and 2-hydroxypropyl tri-n-octylammonium.

Very particular preference is given to 2-hydroxyethyltrimethylammonium, 2-hydroxypropyltrimethylam monium, 2-hydroxyethyl-triethylammonium, 2-hydroxypropyltriethylammonium, 2-hydroxyethyl-tri-n-butylammonium and 2-hydroxypropyl-tri-n-butylammonium.

Especially preferred are 2-hydroxyethyltrimethylammonium and 2-hydroxypropyltrimethylammonium and especially 2-hydroxyethyl-trimethylammonium.

The corresponding anions according to the invention are arbitrary, as long as you use the cation an ionic liquid with the above Form melting point. They are preferably selected from the group of the carboxylates, Sulfates, sulfites, sulfonates, sulfinates, phosphates, phosphonates, Phosphinates and / or metal halides.

Carboxylates are those compounds which have at least one COO ^- group, sulfates those compounds which have at least one SO ₄ ^2- or R ^a -O- (SO ₂ ) -O ^- group, the same applies to sulfites (SO ^2- ₃ ^- or R ^a -O- (SO) -O ^-), sulfonates (R ^a -SO ₃ ^-), sulfinates (R ^a - (SO) -O ^-), phosphate (PO ₄ ^3-, R ^a -O-PO ₃ ^2- or (R ^a -O) ₂ -PO ₂ ^- ), phosphonates (secondary phosphites, HPO ₃ ^2- , R ^a PO ₃ ^2- , (R ^b -O) -R ^a PO ₂ ^- ,) and phosphinates (hypophosphites, H ₂ PO ₂ ^- , R ^a R ^b PO ₂ ^- ,).

In this formula, R ^a and R ^b independently of one another denote straight-chain or branched C ₁ - to C ₂₀ -alkyl group, an optionally substituted C ₅ - to C ₁₂ -cycloalkyl group, an optionally substituted C ₇ - to C ₁₀ -aralkyl group, or an optionally substituted C ₆ -C ₁₂ -aryl group in the meanings as indicated above.

Metal halides are such compounds M _x Hal _y ^z- ,
wherein
M is a metal of the 1st to 5th main group or the 1st to 8 subgroup or a lanthanide or actinide and also phosphorus, silicon or boron
Hal is a halide or pseudohalide
x and y are independently a positive integer and
z is the sum of the charge of the metal and the charges of the halides.

Examples for metals M are Li, Na, K, Cs, Mg, Ca, Ba, Al, Ga, Sn, Sb, Bi, Ti, Zr, V, Nb, Cr, Mo, W, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, Hg, Ce or Sm and also P, Si and B.

Examples of Hal are F, Cl, Br, I, SCN, OCN and CN.
x can be from 1 to 5.
y is dependent on the oxidation state of the particular metal M used, and is at least 1 greater than the sum of the charges of x metals M.

Examples of carboxylates are those of the formula R ⁸ -COO ^- , in which R ^{8 is} a straight-chain or branched C ₁ - to C ₂₀ -alkyl group, an optionally substituted C ₅ - to C ₁₂ -cycloalkyl group, an optionally substituted C ₇ - to C ₁₀ -Aralkylgruppe, an optionally substituted C ₆ -C ₁₂ aryl group or optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino or by functional groups, aryl, alkyl, aryloxy, alkyloxy , Halogen, heteroatoms and / or heterocycles substituted C ₁ -C ₂₀ alkyl or C ₆ to C ₁₂ aryl.

In addition to the meanings given above
optionally C ₁ -C ₂₀ -alkyl interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups or substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles For example, 2-carboxyethyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl) -ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl , Diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl , 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl , 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 1-hydroxy-1,1-dimethylmethyl, 2-hydr oxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2- Ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl and
optionally by one or more oxygen and / or sulfur atoms and / or one or more sub substituted or unsubstituted imino groups interrupted or substituted by functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or heterocycles substituted C ₆ to C ₁₂ aryl for example phenyl, 2-, 3- or 4-methylphenyl, 2-, 3 or 4-hydroxyphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-aminophenyl, α-naphthyl or β-naphthyl, xylyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, Dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso -propylphenyl, tert-butylphenyl, dodecylphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6 -Dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, furyl, thiophenyl, pyrryl, pyridyl , Indolyl, benzoxazolyl, benzimidazolyl, benzthiazole yl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl, tert-butylthiophenyl, pyridazinyl, pyrimidinyl, pyrazinyl, imidazolyl or pyrazolyl.

Examples of carboxylates are aromatic carboxylates, ie those in which R ^{8 is} an optionally substituted C ₆ to C ₁₂ -aryl, especially an aryl containing at least one oxygen or nitrogen atom and / or substituted with at least one oxygen or nitrogen-containing substituent is particularly preferably an aryl containing at least one oxygen or nitrogen atom and / or substituted with at least one hydroxy and / or amino group, most particularly preferred are salicylic acid and nicotinic acid.

Examples for sulfates are sulfate, hydrogen sulfate, methyl sulfate and ethyl sulfate,

Examples for sulfites are sulfite, hydrogen sulfite, methyl sulfite and ethyl sulfite,

Examples for sulfonates are methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, p-toluenesulfonate, p-bromobenzenesulfonate, Camphorsulfonate and dodecane sulfonate

Examples for sulfinates are hydroxymethanesulfinate (formaldehyde sulfoxylate)

Examples for phosphates are phosphate, hydrogen phosphate, dihydrogen phosphate, methyl phosphate, dimethyl phosphate, Ethyl phosphate, diethyl phosphate, glycerophosphate, di-n-butyl phosphate, Di-2-ethylhexyl phosphate, diphenyl phosphate,

Examples for phosphonates are phenylphosphonate and methylphosphonate

Examples for phosphinates are phosphinate.

Examples of metal halides are AlCl ₄ ^-, FeCl ₄ ^-, AlBr ₄ ^-, ZnCl ₃ ^-, BeCl ₃ ^-, ZnBr ₃ ^-, Znl ₃ ^-, CuCl ₃ ^-, CuCl ₂ ^-, CoCl ₃ ^-, Col ₃ ^-, Fel ₃ ^- , FeCl ₃ ^- , TiCl ₅ ^- , TiCl ₆ ^2- , TiCl ₄ ^- , SnCl ₃ ^- , SnCl ₄ ^- , SnCl ₄ ^2- , MnCl ₃ ^- , MnCl ₄ ^2- , MnBr ₃ ^- , ScCl ₄ ^- , BCl ₄ ^-, BBr ₄ ^-, GaCl ₄ ^-, ReCl ₆ ^-, ZrCl ₅ ^-, NbCl ₆ ^-, VCl ₄ ^-, CrCl ₃ ^-, MoCl ₆ ^-, YCl ₄ ^-, CdCl ₃ ^-, CdBr ₃ ^-, SbCl ₄ ^- , SbCl ₆ ^-, BiCl ₄ ^-, ZrCl ₅ ^-, UCl ₅ ^-, UCl ₆ ^2-, LaCl ₄ ^-, CeCl ₄ ^-, SmCl ₄ ^-, Sml ₃ ^-, TaCl ₆ ^-, BF ₄ ^-, PCl ₄ ^-, PCl ₆ ^- or PF ₆ ^- .

Further examples of metal halides are mixtures of halides or pseudohalides of the abovementioned cations with Lewis acids, for example AlCl ₃ , FeCl ₃ , AlBr ₃ and ZnCl ₂ , BeCl ₂ , ZnBr ₂ , Znl ₂ , ZnSO ₄ , CuCl ₂ , CuCl, Cu (O ₃ SCF ₃ ) ₂ , CoCl ₂ , Col ₂ , Fel ₂ , FeCl ₂ , FeCl ₂ (THF) ₂ , TiCl ₄ (THF) ₂ , TiCl ₄ , TiCl ₃ , ClTi (OiPr) ₃ , SnCl ₂ , SnCl _4, Sn (SO _4), Sn (SO _{4) 2,} MnCl _2, MnBr _2, ScCl _3, BPh _3, BCl _3, BBr _3, BF ₃ · OEt _2, BF ₃ OMe _2, BF ₃ · MeOH , BF ₃ .CH ₃ COOH, BF ₃ .CH ₃ CN, B (CF ₃ COO) ₃ , B (OEt) ₃ , B (OMe) ₃ , B (OiPr) ₃ , PhB (OH) ₂ , 3-MeO -PhB (OH) ₂ , 4-MeO-PhB (OH) ₂ , 3-F-PhB (OH) ₂ , 4-F-PhB (OH) ₂ , (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) AlCl ₂ , (C ₈ H ₁₇ ) AlCl ₂ , (C ₈ H ₁₇ ) ₂ AlCl, (iso-C ₄ H ₉ ) ₂ AlCl, Ph ₂ AlCl, PhAlCl ₂ , Al (acac) ₃ , Al (OiPr) ₃ , Al (OnBu) ₃ , Al (OsekBu) ₃ , Al (OEt) ₃ , GaCl ₃ , ReCl ₅ , ZrCl ₄ , NbCl ₅ , VCl ₃ , CrCl ₂ , MoCl ₅ , YCl ₃ , CdCl ₂ , CdBr ₂ , SbCl ₃ , SbCl ₅ , BiCl ₃ , ZrCl ₄ , UCl ₄ , LaCl ₃ , CeCl ₃ , Er (O ₃ SCF ₃ ), Yb (O ₂ CCF ₃ ) ₃ , SmCl ₃ , Sml ₂ , B (C ₆ H ₅ ) ₃ , TaCl ₅ .

there For example, the mixtures of halides or pseudohalides are those of the above listed Cations with Lewis acids in a molar ratio 1: 0.5 to 1: 5, preferably 1: 0.75 to 1: 3, more preferably 1 0.85 to 1: 2.5, most preferably in the ratio of 1 : 0.9 to 1: 2, and more preferably 1: 1.0 to 1: 1.5.

According to the invention only those of the compounds mentioned as ionic liquids used, which have a melting point below that defined above Have temperature.

The oligomerization catalysts according to the invention are usually over a temperature range of about 30 to 100 ° C catalytically effective and can be thermally deactivated at temperatures above 100 ° C, which can advantageously dispense with catalyst poisons.

The preferred reaction temperature is generally 10 to 150 ° C, especially preferably 30-100 ° C. In the case of 1,6-hexamethylene diisocyanate is the reaction temperature most preferably 80 to 90 ° C and in the case of isophorone diisocyanate is most preferably 60 to 70 ° C.

The reaction rate of the oligomerization reaction, by using the ionic liquids of the invention in comparison to commercially available oligomerization catalysts, such as, preferably N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate (DABCO TMR ^® from Air Products) at least maintained or even increased. In addition, polyisocyanates having extremely low Hazen color numbers (DIN ISO 6271), for example preferably less than 40 (in the case of HDI), or less than 200, preferably less than 100 (in the case of IPDI), are obtained.

The usable according to the invention Oligomerization catalysts can be prepared by known methods. For the production of Ionic liquids can the corresponding tertiary amines with an alkylating agent, for example alkyl halides, dialkyl carbonates or dialkyl sulfates, in the absence or presence of solvents, e.g. Chlorobenzene, toluene or xylene, at temperatures of appropriate 100 to 180 ° C be reacted. Optionally, the reaction can take place under Pressure performed when the amine used is under the reaction conditions gaseous is.

preferred Alkylating agents are methyl chloride, ethyl chloride, methyl iodide, Dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, dimethyl sulfate and diethyl sulfate and also benzyl chloride.

When suitable tertiary Amines for the alkylation may be mentioned: dimethylethanolamine, di-n-butylethanolamine, Dioctylethanolamine, hydroxyethylpiperidine and hydroxyethylmorpholine.

Farther can the ionic according to the invention liquids be prepared by quaternization with alkylene oxides. To the corporal teriary amines are substituted with substituted ones or unsubstituted alkylene oxides having 2 to 24 carbon atoms, in particular with alkylene oxides with halogen, hydroxy, noncyclic Ether or ammonium substituents. In particular: aliphatic 1,2-alkylene oxides with 2 to 4 carbon atoms, for example ethylene oxide, propylene oxide, Vinyloxirane, 1,2-butylene oxide, 2,3-butylene oxide or isobutylene oxide, aliphatic 1,2-alkylene oxides with 5 to 24 carbon atoms, cycloaliphatic alkylene oxides, for example Cyclopentene oxide, cyclohexene oxide or cyclododecatriene (1,5,9) -monoxide, Araliphatic alkylene oxides, for example styrene oxide.

preferred substituted alkylene oxides are, for example, epichlorohydrin, epibromohydrin, 2,3-epoxy-1-propanol, 1-allyloxy-2,3-epoxypropane, 2,3-epoxy-phenyl ether, 2,3-epoxypropyl isopropyl ether, 2,3-epoxypropyl-octyl ether or 2,3-epoxypropyltrimethyl-ammonium chloride.

Especially Preference is given to using 1,2-alkylene oxides having 2 to 4 C atoms, in particular ethylene oxide and / or propylene oxide and especially ethylene oxide.

To become the tertiary Amine and the alkylene oxide usually in a molar ratio of 1 to 0.4 to 1 to 10 used. Particularly advantageous is a molar ratio of 1 to 1 to 1 to 1.5, especially from 1 to 1.03 to 1 to 1.2.

The Implementation of the tertiary Amine with the alkylene oxide can be carried out at 20 to 200 ° C. Preferred is a Temperature range from 30 to 150 ° C, in particular from 40 to 100 ° C.

The Reaction can take place both at atmospheric pressure or under reduced pressure, as well as at elevated pressure, for example, at a pressure of 0.8 to 50 bar, in particular be carried out at a pressure of 1 to 10 bar.

When suitable tertiary Amines for the alkoxylation may be mentioned by way of example: trimethylamine, triethylamine, Tri-n-butylamine, ethyl-diisopropylamine, N, N'-dimethyl-piperazine, N-methoxyphenyl-piperazine, N-methylpiperidine, N-ethyl-piperidine, quinuclidine and trialkylamines, such as. Trimethyl, triethyl and tripropylamine, and preferably 1,4-dimethyl-piperazine, N, N-dimethylbenzylamine and triethylenediamine.

at Reaction of an amine with an unsymmetrically substituted epoxide, The amine usually reacts with the least substituted one Carbon atom. Depending on the steric claim of the amine can be Mixtures of the two possible ones Regioisomeren form.

The available after quaternization tetrasubstituted ammonium ions with the alkylating agent as Counterion such as chloride, iodide, methyl carbonate or Methyl sulfate, if they are not already the ionic according to the invention liquids are then in a preferred embodiment by treating with an anion exchanger into which tetrasubstituted Converted ammonium hydroxide, the then afterwards with the corrosive acid of the desired Gegenions can be implemented. The resulting equivalents Quantities of water can either left in the catalyst or can preferably be treated by with desiccant, such as molecular sieve or zeolite, or Azeotropic distillation with an entrainer, such as Cyclohexane, benzene or toluene, removed or depleted. As a rule, a water content in the catalyst is less than 0.5% by weight. for use in the reaction according to the invention sufficient and is desired.

The Presence of water in the reaction usually results from hydrolysis the isocyanates and decarboxylation of the resulting carbamic acids too Amines, in turn, with isocyanates to sparingly soluble, undesirable Urea reacts.

One can also perform a direct exchange on an ion exchange column. (Such as Amberlyst ^® -, Dowex ^® or Sephadex ^® type) by a basic ion exchange resin is activated with potassium hydroxide solution or sodium hydroxide solution and loaded with the korrspondierenden acid of the desired counterion. Thereafter, the chromatography column with the quart. Ammonium salt is charged and eluted. The eluate contains the desired quart. Ammonium salt. The solvent can be removed by applying a vacuum.

in the Trap of the quart. Ammonium halides can be the catalysts also obtained by cation exchange in solution in very pure form, if as reactants the silver salts underlying the anions be used.

The preparation of the catalysts of the invention can be carried out, for example, analogously to the working instructions, as in US 5,691,440 , Sp. 11, Z. 24-Sp. 12, Z. 41.

The alkylation of tertiary amines can be carried out, for example, as follows: the tertiary amine is optionally dissolved in a suitable solvent, for example a C ₁ -C ₄ -alcohol, preferably methanol or ethanol, with the alkylating agent in over or under stoichiometric or preferably equimolar amounts, for example, 0.75-1.25 mol / mol, preferably 0.9-1.1 mol / mol, based on the tertiary amine optionally at elevated pressure for 30 minutes to 24 h at a temperature between room temperature and 120 ° C, optionally at implemented in the course of the reaction increasing temperature. After completion of the reaction, the volatiles are separated by distillation and optionally washed or recrystallized.

The tetrasubstituted ammonium ion thus obtained with the counterion of the alkylating agent may then be added, for example, to one with hydroxide ions exchanged anion exchanger exchanged for a Hydroxidgegenion Be as, for example, in DE-OS 25 27 242, p. 6, below or Id. in Preparation Examples 1 and 2 on pages 13 and 14 is.

The tetrasubstituted ammonium hydroxide thus obtained or a commercially available one can then be reacted with the desired corresponding counterion to the catalyst of the present invention. For this purpose, for example, the tetrasubstituted ammonium hydroxide is initially charged, for example in a solvent, preferably a solvent which forms an azeotrope with water, for example a C ₁ -C ₄ alcohol, preferably methanol or ethanol, and to the desired corresponding counterion, optionally also in the same or a different solvent, added slowly. The addition may be carried out at 0 to 100 ° C., preferably 0 to 80, particularly preferably 0 to 60, very particularly preferably 10 to 40 ° C. and in particular at room temperature. After removal of the optionally present solvent with water of reaction formed, for example by distillation, if appropriate under reduced pressure, the catalyst according to the invention can be used and optionally can be taken up in a solvent. Such a solvent may also contain isocyanate-reactive groups.

Of the catalyst according to the invention can be in substance or as a solution, preferably be used in substance as a melt.

It may be useful to use the catalyst in solution, although he as an ionic liquid already liquid is, for example, a stronger one diluted solution to dose better.

Becomes the catalyst as a solution used, so will, depending on the solubility in the solvent used in usually a 10-80%, preferably 10-50, more preferably 15-45 and most preferably 30-40 % By weight solution set.

When Oligomerization catalysts can also mixtures with other known oligomerization catalysts be used, which in wide proportions, e.g. in proportions from 90:10 to 10:90, preferably 80:20 to 20:80 and especially preferably 60:40 to 40:60 can be mixed.

to Preparation of polyisocyanates are the oligomerization catalysts according to the invention in dependence of their catalytic activity expediently as possible small effective amounts, which are determined experimentally in a simple manner can be used.

in the In general, in the process according to the invention, the ionic species are obtained liquids in an amount of 0.002 to 0.05% by weight, preferably 0.005 to 0.02 wt .-% based on the weight of the diisocyanates, used.

With the method according to the invention can be over Ionic liquids Biuret, allophanate and / or isocyanurate group-containing polyisocyanates produce. Therefore must of course the preparation of allophanate groups at least one hydroxy group-containing Compound or in the production of biuret groups at least a biuretizing agent such as amine, water or dehydrating compounds, for example tert-butanol, and / or a urea will be present.

The inventive method is expediently at a temperature in the range of 10 to 100 ° C and reaction times of 10 min - 6 Hours, preferably from 20 minutes to 3 hours, more preferably from 20 minutes to 2 hours.

at Use of the ionic compounds according to the invention liquids are preferably reaction temperatures above 50 ° C, more preferably of 60 up to 120 ° C and essentially colorless oligomerization products receive.

The Oligomerization can be continuous, semi-continuous or batchwise carried out be, preferably discontinuously.

In As a rule, it is of minor importance which components submitted or added. In most cases, this is to be oligomerized Isocyanate at least partially, preferably completely, submitted and the at least a catalyst added slowly and / or in portions, then to the desired Reaction temperature brought and the rest of the catalyst, optionally in portions, added.

A Alternative production variant proceeds as follows: In the discontinuous Method is in a stirred reactor worked. In this case, the mixture of diisocyanate and catalyst is customary at not more than 40 ° C submitted, since at this temperature usually no reaction takes place. Following is the temperature of the reaction mixture for the initiation of the oligomerization at 50 to 120 ° C, preferably on 55 to 90 ° C, elevated. Alternatively, the catalyst may also be metered in after the Diisocyanate has reached the temperature necessary for the reaction. The oligomerization is usually exothermic, the catalyst can preferably be used in pure form. It is also possible the Dissolve catalyst in a suitable solvent and in this form to use.

A continuous oligomerization is conveniently carried out in a reaction coil with continuous, simultaneous addition of diisocyanate and the catalyst at 50 to 140 ° C and within 30 seconds to 4 hours. A reaction coil with a small diameter leads to the achievement of high flow velocities and consequently good mixing. Furthermore, it is advantageous to heat the diisocyanate / catalyst mixture before entering the reaction coil to about 50 to 60 ° C. For more accurate metering and optimal mixing of the catalyst, it is also advantageous to dissolve the catalyst in a suitable solvent. Suitable in principle are those solvents in which the catalyst has good solubility. The continuous oligomerization can also be carried out in a kettle cascade become. Also conceivable is a combination of boiler cascade and tubular reactor.

The reaction is usually carried out in a gas or gas mixture which is inert under the reaction conditions, for example those having an oxygen content of less than 2, preferably less than 1, particularly preferably less than 0.5,% by volume, nitrogen, argon, helium, nitrogen-noble gas mixtures are preferred. particularly preferred is nitrogen. In addition or alone, carbon dioxide (CO ₂ ) can also be used as the gas. This is preferred, for example, when 1,6-hexamethylene diisocyanate is used, but less preferably when isophorone diisocyanate is used.

To Achieve the desired Oligomerisierungsgrads or NCO content or degree of conversion (relative the NCO content before the reaction) of the oligomer / diisocyanate reaction mixture and what usually Reaction times from 0.05 to 4 hours, preferably 10 min to 3 hours, may require the oligomerization reaction for example, thermally or by deactivating the oligomerization catalyst to be ended.

in the in general, a conversion of 10 to 60% (based on the NCO content before the reaction). For 1,6-hexamethylene diisocyanate the conversion preferably controlled to 20 to 50%, with isophorone diisocyanate preferably at 10 to 40%.

The In addition to monomeric isocyanate, the product may contain other compounds contain one or more oligomer structures, for example, isocyanurate, uretdione, biuret, urethane, oxadiazinetrione, Iminooxadiazinetrione, urea, amide and / or allophanate groups. links of this type are described in the literature.

When Deactivating agents are, for example, inorganic acids, such as e.g. Hydrogen chloride, phosphorous acid or phosphoric acid, carboxylic acid halides, such as. Acetyl chloride or benzoyl chloride, sulfonic acids or ester, e.g. methane, p-toluenesulfonic acid, p-toluenesulfonic acid methyl or -ethylester, m-chloroperbenzoic acid and preferably dialkyl phosphates, e.g. Di-2-ethylhexyl phosphate and in particular Dibutyl phosphate.

The Deactivating agents can, based on the oligomerization catalysts, in equivalent or excess amounts be used, with the smallest effective amount, the experimental can be determined, already preferred for economic reasons becomes. For example, the deactivating agent is proportionate to the Oligomerization catalyst of 1-2.5: 1 mol / mol, preferably 1-2: 1, more preferably 1-1.5 : 1 and most preferably 1-1.2: 1 mol / mol used.

The Addition is dependent on the nature of the deactivator. So is hydrogen chloride preferably gaseous over or preferably passed through the reaction mixture, become liquid deactivating agents mostly in substance or as a solution in a reaction inert solvent and solid deactivating agent in bulk or as a solution or Suspension in a solvent inert under the reaction conditions added.

The Addition of the deactivating agent is usually carried out at the reaction temperature, but can also be done at a lower temperature.

Prefers However, the thermal deactivation of the catalyst is the most is preferably connected to the separation of excess monomer (see below). It may also be by brief heating of the reaction mixture in the reactor or in a downstream tubular reactor at temperatures above of 130 ° C, for example, 140-180 ° C with few Second residence time.

The inventive method is preferably solvent-free carried out. However, when the diisocyanates are in the presence of solution or diluents partially oligomerized, both inert and nonpolar are suitable for this purpose also inert polar solution or diluents, such as. Toluene, xylene, cyclic ethers, carboxylic esters and ketones or their Mixtures.

The biuret, allophanate and / or isocyanurate groups prepared by the novel polyisocyanates can in known manner, for example by thin film distillation at a temperature of 100 to 180 ° C, optionally in vacuo, optionally additionally with passing inert stripping gas, or Extraction of solvent or diluent optionally present and / or preferably freed of excess, unreacted diisocyanates, so that the polyisocyanates containing monomeric diisocyanates of, for example, below 1.0 wt .-%, preferably below 0.5 wt .-%, more preferably below 0.3, most preferably below 0.2 and in particular not more than 0.1% by weight are available.

Without Separation of the excess monomers Diisocyanates are the biuret, allophanate and / or isocyanurate groups having polyisocyanates, for example for the production of PU foams, cellular or compact elastomers, potting compounds and adhesives. The monomer-free and monomer-containing biuret, allophanate and / or Isocyanurate group-containing polyisocyanates may further in a manner known per se by introduction of e.g. Urethane, allophanate, Urea, biuret and / or carbodiimide modified and / or the isocyanate groups with suitable blocking agents, e.g. ε-caprolactam, dimethyl malonate, Acetessigester or aromatic hydroxyl groups are blocked.

To the method according to the invention can any organic diisocyanates with aromatic, araliphatic, aliphatic and / or cycloaliphatic bound isocyanate groups or their mixtures are oligomerized.

aromatic Isocyanates are those containing at least one aromatic ring system contain.

cycloaliphatic Isocyanates are those which contain at least one cycloaliphatic ring system contain.

aliphatic Isocyanates are those that are exclusively straight or branched Contain chains, ie acyclic compounds.

suitable (cyclo) aliphatic diisocyanates advantageously have 3 to 16 C-atoms, preferably 4 to 12 C atoms in the linear or branched-chain alkylene radical and suitable cycloaliphatic diisocyanates advantageously 4 to 18 C atoms, preferably 6 to 15 C atoms in the cycloalkylene radical. Examples include: 1,4-diisocyanato-butane, 2-ethyl-1,4-diisocyanato-butane, 1,5-diisocyanato-pentane, 2-methyl-1,5-diisocyanato-pentane, 2,2-dimethyl-1,5-diisocyanato-pentane, 2-propyl-2-ethyl-1,5-diisocyanato-pentane, 2-butyl-2-ethyl-1,5-diisocyanato-pentane, 2-alkoxymethylene-1,5-diisocyanato-pentane, 3-methyl, 3-ethyl-1,5-diisocyanatopentane, 1,6-hexamethylene diisocyanate, 2,4,4- and / or 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,7-diisocyanatoheptane, 1,8-diisocyanato-octane, 1,10-diisocyanato-decane, 1,12-diiso-cyanato-dodecane, 4,4'-diisocyanato-dicyclohexylmethane, 2,4'-diisocyanatodicyclohexylmethane and mixtures of the diisocyanato-dicyclohexylmethane isomers, 1,3-diisocyanato-cyclohexane and isomer mixtures of diisocyanato-cyclohexanes and 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane. As (cyclo) aliphatic diisocyanates are preferably used 1,6-hexamethylene diisocyanate, isomeric aliphatic diisocyanates with 6 carbon atoms in the alkylene radical and mixtures thereof, 2-butyl-2-ethyl-1,5-diisocyanato-pentane and 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane, particularly preferred are 1,6-hexamethylene diisocyanate and 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane and mixtures thereof, for example in the ratio 10: 90-90: 10, preferably 20: 80-80 : 20 and more preferably 33: 67-67: 33.

suitable aromatic and araliphatic diisocyanates are 2,4- or 2,6-toluene diisocyanate and their isomer mixtures, o-, m- or p-xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate (m-TMXDI), 2,4'- or 4,4'-diisocyanatodiphenylmethane and their isomer mixtures, 1,3- or 1,4-phenylenediisocyanate, 1-chloro-2,4-phenylenediisocyanate, 1,5-naphthylene diisocyanate, diphenyl-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene or diphenyl ether-4,4'-diisocyanate.

The catalysts of the invention are for the oligomerization of (cyclo) aliphatic isocyanates is preferred, especially preferred for the oligomerization of hexamethylene diisocyanate (1,6-diisocyanatohexane) or 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (Isophorone diisocyanate)

The new invention Oligomerization catalysts can for the oligomerization of by any method, for example according to one phosgene-free or one that uses phosgene Procedure, prepared diisocyanates are used.

The diisocyanates which can be used according to the invention can be prepared by any desired process, for example by phosgenation of the corresponding diamines and thermal cleavage of the intermediately formed dicar Baminsäurechloride be prepared. Diisocyanates prepared by phosgene-free processes contain no chlorine compounds as by-products and therefore have a fundamentally different by-product spectrum due to their production.

Of course you can too Mixtures of isocyanates obtained by the phosgene method and according to phosgene-free process are used.

It showed that the usable according to the invention Oligomerization in the oligomerization of obtained by the phosgene method diisocyanates a good have catalytic activity and lower polyisocyanates Color number result.

The in the inventive method usable according to a phosgene-free method and in particular obtainable by thermal cleavage of dicarbamic acid esters Diisocyanates are not limited being obtainable by thermal cleavage of dicarbamic esters Diisocyanates from the group 1,6-hexamethylene diisocyanate, 2-butyl-2-ethyl-pentamethylene-diisocyanate-1,5 and 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane particularly preferably used.

In a preferred embodiment The invention uses isocyanates which have a total chlorine content of 100 ppm by weight or less, preferably 80 ppm by weight or less whereas isocyanates derived from a phosgenation process often a total chlorine content of 100-400 mg / kg exhibit.

To Biuret, allophanate and / or biuret produced by these process variants Isocyanurate group-containing polyisocyanates are particularly suitable for Production of Polyurethane Coatings, e.g. of textile and Leather coatings, for Dispersions and adhesives and find particular use as a polyisocyanate component in one- and two-component polyurethane systems for high quality and weatherproof Polyurethane coatings.

In the following, another embodiment of the present invention will be described:
In addition to the above-mentioned ionic liquids used as a catalyst for the oligomerization reaction, at least one other ionic liquid other than the ionic liquid used as the catalyst may be used in the process.

Also these are compounds that consist of at least one Cation and at least one anion and the above Have melting points. However, these ionic liquids are in contrast usually not thermally deactivatable to the catalysts mentioned above.

Prefers as cation are ammonium or phosphonium ions, or such cations, the at least one to six-membered heterocycle containing at least one phosphorus or nitrogen atom and optionally an oxygen or sulfur atom particularly preferably those compounds which are at least a five- to contain six-membered heterocycle, the one, two or three Has nitrogen atoms and a sulfur or an oxygen atom, very particularly preferably those with one or two nitrogen atoms.

Especially preferred ionic liquids are those which have a molecular weight below 1000 g / mol, completely more preferably below 350 g / mol.

sowie Oligo- bzw. Polymere, die diese Strukturen enthalten,
worin
R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶ und R¹⁷ unabhängig voneinander jeweils Waserstoff, C₁-C₁₈-Alkyl, gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C₂-₁₈-Alkyl, C₆-C₁₂-Aryl, C₅-C₁₂-Cycloalkyl oder einen fünf- bis sechsgliedrigen, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisenden Heterocyclus bedeuten oder zwei von ihnen gemeinsam einen ungesättigten, gesättigten oder aromatischen und gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenen Ring bilden, wobei die genannten Reste jeweils durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiert sein können.Furthermore, preference is given to those cations which are selected from the compounds of the formulas (Ia) to (Iw)

and oligo- or polymers containing these structures,
wherein
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently hydrogen, C ₁ -C ₁₈ alkyl, optionally by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C ₂ - ₁₈ alkyl, C ₆ -C ₁₂ aryl, C ₅ -C ₁₂ cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle or two of them together form an unsaturated, saturated or aromatic ring which is optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, where the radicals mentioned are in each case denoted by functional groups, aryl, alkyl, aryloxy, alkyloxy, Halogen, heteroatoms and / or heterocycles can be substituted.

R ¹⁷ may furthermore be C ₁ -C ₁₈ -alkyloyl (alkylcarbonyl), C ₁ -C ₁₈ -alkyloxycarbonyl, C ₅ -C ₁₂ -cycloalkylcarbonyl or C ₆ -C ₁₂ -aryloyl (arylcarbonyl), where the radicals mentioned are each represented by functional groups Groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles may be substituted.

In the radicals R ¹¹ to R ¹⁷ mean
optionally C ₁ -C ₁₈ -alkyl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, Pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3- Tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) -ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m- Ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl) -ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2- Isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl , 1,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4 Hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl , 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl , 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl and,
optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C ₂ -C ₁₈ alkyl interrupted, for example, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6-dioxa- octyl, 11-hydroxy-3,6,9-trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, 11-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa pentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy-5,10-oxa-tetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxo-octyl, 11-methoxy 3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy 5-oxa-nonyl, 14-methoxy-5,10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy-3,6,9- trioxa undecyl, 7-ethoxy-4-oxa-heptyl, 11-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8,12-trioxa-pentadecyl, 9-ethoxy-5-oxa-no nyl or 14-ethoxy-5,10-oxa-tetradecyl.

If two radicals form a ring, these radicals may together be 1,3-propylene, 1,4-butylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propylene, 2-oxa-1, 3-propylene, 1-oxa-1,3-propenylene, 1-aza-1,3-propenylene, 1-C ₁ -C ₄ -alkyl-1-aza-1,3-propenylene, 1,4-butadiene 1,3-dienylene, 1-aza-1,4-buta-1,3-dienylene or 2-aza-1,4-buta-1,3-dienylene.

The Number of oxygen and / or sulfur atoms and / or imino groups is not limited. Usually amounts to Do not spend more than 5 in the rest, preferably not more than 4 and most preferably not more than 3.

Farther are usually between two heteroatoms at least a carbon atom, preferably at least two.

substituted and unsubstituted imino groups may be, for example, imino, Methylimino, iso-propylimino, n-butylimino or tert-butylimino be.

Furthermore mean
carboxy, carboxamide, hydroxy, di (C ₁ -C ₄ alkyl) amino, C ₁ -C ₄ alkyloxycarbonyl, cyano or C ₁ -C ₄ alkyloxy functional groups,
optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C ₆ -C ₁₂ aryl for example phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl , Trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2, 4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl,
optionally substituted by functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or heterocycles substituted C ₅ -C ₁₂ -cycloalkyl, for example cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl , Dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl,
a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxy, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, Methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl and
C ₁ to C ₄ alkyl, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

C ₁ -C ₁₈ -alkyloyl (alkylcarbonyl) may be, for example, acetyl, propionyl, n-butyloyl, sec-butyloyl, tert-butyloyl, 2-ethylhexylcarbonyl, decanoyl, dodecanoyl, chloroacetyl, trichloroacetyl or trifluoroacetyl.

C ₁ -C ₁₈ -Alkyloxycarbonyl may be, for example, methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl or benzyloxycarbonyl.

C ₅ -C ₁₂ -cycloalkylcarbonyl may be, for example, cyclopentylcarbonyl, cyclohexylcarbonyl or cyclododecylcarbonyl.

C ₆ -C ₁₂ -Aryloyl (arylcarbonyl) may be, for example, benzoyl, toluyl, xyloyl, α-naphthoyl, β-naphthoyl, chlorobenzoyl, dichlorobenzoyl, trichlorobenzoyl or trimethylbenzoyl.

Preferably R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 are} independently hydrogen, methyl, ethyl, n-butyl, 2-hydroxyethyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- ( Ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, dimethylamino, diethylamino and chloro.

R ¹⁷ is preferably hydrogen, methyl, ethyl, n-butyl, 2-hydroxyethyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, acetyl, Propionyl, t-butyryl, methoxycarbonyl, ethoxycarbonyl or n-butoxycarbonyl.

Particularly preferred pyridinium ions (Ia) are those in which one of the radicals R ¹¹ to R ^{15 is} methyl, ethyl or chlorine, R ^{17 is} hydrogen, acetyl, methyl, ethyl or n-butyl and all others are hydrogen, or R ^{13 is} dimethylamino, R ^{17 is} hydrogen, acetyl, methyl, ethyl or n-butyl and all others are hydrogen or R ^{17 is} hydrogen, acetyl, methyl, ethyl or n-butyl and all others are hydrogen or R ^{12 is} carboxy or carboxamide, R ^{17 is} hydrogen, acetyl, Methyl, ethyl or n-butyl and all others are hydrogen or R ¹¹ and R ¹² or R ¹² and R ^{13 is} 1,4-buta-1,3-dienylene, R ^{17 is} hydrogen, acetyl, methyl, ethyl or n-butyl and all other hydrogen are.

Particularly preferred pyridazinium ions (Ib) are those in which one of the radicals R ¹¹ to R ^{14 is} methyl or ethyl, R ^{17 is} hydrogen, acetyl, methyl, ethyl or n-butyl and all other hydrogen or R ^{17 is} hydrogen, acetyl, methyl, ethyl or n-butyl, and all others are hydrogen.

Particularly preferred pyrimidinium ions (Ic) are those in which R ¹² to R ^{14 is} hydrogen or methyl, R ^{17 is} hydrogen, acetyl, methyl, ethyl or n-butyl and R ^{11 is} hydrogen, methyl or ethyl, or R ¹² and R ^{14 is} methyl , R ^{13 is} hydrogen and R ^{11 is} hydrogen, methyl or ethyl and R ^{17 is} hydrogen, acetyl, methyl, ethyl or n-butyl.

Particularly preferred pyrazinium ions (Id) are those in which
R ¹¹ to R ¹⁴ all methyl and
R ^{17 is} hydrogen, acetyl, methyl, ethyl or n-butyl or R ^{17 is} hydrogen, acetyl, methyl, ethyl or n-butyl and all others are hydrogen.

Particularly preferred imidazolium ions (Ie) are those in which independently of one another
R ^{11 is} selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, 2-hydroxyethyl or 2-cyanoethyl,
R ^{17 is} hydrogen, acetyl, methyl, ethyl or n-butyl and
R ¹² to R ¹⁴ independently of one another denote hydrogen, methyl or ethyl.

Particularly preferred 1H-pyrazolium ions (If) are those in which independently of one another
R ¹¹ is hydrogen, methyl or ethyl,
R ¹² , R ¹³ and R ¹⁴ are hydrogen or methyl and
R ^{17 are selected} from hydrogen, acetyl, methyl, ethyl or n-butyl.

Particularly preferred 3H-pyrazolium ions (Ig) are those in which independently of one another
R ¹¹ is hydrogen, methyl or ethyl,
R ¹² , R ¹³ and R ¹⁴ are hydrogen or methyl and
R ^{17 are selected} from hydrogen, acetyl, methyl, ethyl or n-butyl.

Particularly preferred 4H-pyrazolium ions (Ih) are those in which independently of one another
R ¹¹ to R ¹⁴ are hydrogen or methyl and
R ^{17 are selected} from hydrogen, acetyl, methyl, ethyl or n-butyl.

Particularly preferred 1-pyrazolinium ions (Ii) are those in which independently of one another
R ¹¹ to R ¹⁶ are hydrogen or methyl and
R ^{17 are selected} from hydrogen, acetyl, methyl, ethyl or n-butyl.

Particularly preferred 2-pyrazolinium ions (Ij) are those in which independently of one another
R ¹¹ is hydrogen, methyl, ethyl or phenyl,
R ¹⁷ is hydrogen, acetyl, methyl, ethyl or n-butyl and
R ¹² to R ¹⁶ are selected from hydrogen or methyl.

Particularly preferred 3-pyrazolinium ions (Ik) are those in which independently of one another
R ¹¹ or R ¹² is hydrogen, methyl, ethyl or phenyl,
R ¹⁷ is hydrogen, acetyl, methyl, ethyl or n-butyl and
R ¹³ to R ¹⁶ are selected from hydrogen or methyl.

Particularly preferred imidazolinium ions (II) are those in which independently of one another
R ¹¹ or R ¹² is hydrogen, methyl, ethyl, n-butyl or phenyl,
R ¹⁷ is hydrogen, acetyl, methyl, ethyl or n-butyl and
R ¹³ or R ¹⁴ is hydrogen, methyl or ethyl and
R ¹⁵ or R ¹⁶ are selected from hydrogen or methyl.

Particularly preferred imidazolinium ions (Im) are those in which independently of one another
R ¹¹ or R ¹² is hydrogen, methyl or ethyl,
R ¹⁷ is hydrogen, acetyl, methyl, ethyl or n-butyl and
R ¹³ to R ¹⁶ are selected from hydrogen or methyl.

Particularly preferred imidazolinium ions (In) are those in which independently of one another
R ¹¹ , R ¹² or R ¹³ is hydrogen, methyl or ethyl,
R ^{17 is} hydrogen, acetyl, methyl, ethyl or n-butyl and
R ¹⁴ to R ¹⁶ are selected from hydrogen or methyl.

Particularly preferred thiazolium ions (Io) or oxazolium ions (Ip) are those in which independently of one another
R ¹¹ is hydrogen, methyl, ethyl or phenyl,
R ¹⁷ is hydrogen, acetyl, methyl, ethyl or n-butyl and
R ¹² or R ¹³ are selected from hydrogen or methyl.

Particularly preferred 1,2,4-triazolium ions (Iq) and (Ir) are those in which independently of one another
R ¹¹ or R ¹² is hydrogen, methyl, ethyl or phenyl,
R ¹⁷ is selected from hydrogen, acetyl, methyl, ethyl or n-butyl and
R ^{13 are selected} from hydrogen, methyl or phenyl.

Particularly preferred 1,2,3-triazolium ions (Is) and (It) are those in which independently of one another
R ¹¹ is hydrogen, methyl or ethyl,
R ¹⁷ is hydrogen, acetyl, methyl, ethyl or n-butyl and
R ¹² or R ¹³ are selected from hydrogen or methyl or
R ¹² and R ^{13 are} 1,4-buta-1,3-dienylene and all others are hydrogen.

Particularly preferred pyrrolidinium ions (Iu) are those in which independently of one another
R ¹¹ and R ^{17 are selected} from hydrogen, acetyl, methyl, ethyl or n-butyl, and
R ¹² , R ¹³ , R ¹⁴ and R ^{15 are} hydrogen.

Particularly preferred ammonium ions (Iv) are those in which independently of one another
R ¹⁷ is hydrogen, acetyl, methyl, ethyl or n-butyl and
R ¹¹ , R ¹² , and R ^{13 are selected} from methyl, ethyl, n-butyl, 2-hydroxyethyl, benzyl or phenyl.

Particularly preferred phosphonium ions (Iw) are those in which independently of one another
R ¹⁷ is hydrogen, acetyl, methyl, ethyl or n-butyl and
R ¹¹ , R ¹² , and R ^{13 are selected} from phenyl, phenoxy, ethoxy and n-butoxy.

Under these are the ammonium, phosphonium, pyridinium and imidazolium ions prefers.

All 1,2-dimethylpyridinium, 1-methyl-2-ethylpyridinium, 1-methyl-2-ethyl-6-methylpyridinium are particularly preferred as cations, N-methylpyridinium, 1-butyl-2-methylpyridinium, 1-butyl-2-ethylpyridinium, 1-butyl-2-ethyl-6-methylpyridinium, N-butylpyridinium, 1-butyl-4-methylpyridinium, 1-methylimidazolium, 1-butylimidazolium, 1,3-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-n-butyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,3,4-trimethylimidazolium, 2,3-dimethylimidazolium, 1-butyl-2,3-dimethylimidazolium, 3,4-dimethylimidazolium, 2-ethyl-3,4-dimethylimidazolium, 3-methyl-2-ethylimidazole, 3-butyl-1-methylimidazolium, 3-ethyl-1-methylimidazolium, 3-butyl-1-ethylimidazolium, 3-butyl-1,2-dimethylimidazolium, 1,3-di-n-butylimidazolium, 3-butyl-1,4,5-trimethylimidazolium, 3-butyl-1,4-dimethylimidazolium, 3-butyl-2-methylimidazolium, 1,3-dibutyl-2-methylimidazolium, 3-butyl-4-methylimidazolium, 3-butyl-2-ethyl-4-methylimidazolium and 3-butyl-2-ethylimidazolium, 1-methyl-3-octylimidazolium, 1-decyl-3-methylimidazolium.

Especially preferred are 1-methylimidazolium, 1-butylimidazolium, 1-butyl-4-methylpyridinium, 1-n-butyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium and 1-n-butyl-3-ethylimidazolium.

When Anions are in principle all anions conceivable.

Preferred anions are halides, F ^- , Cl ^- , Br ^- , I ^- , acetate CH ₃ COO ^- , trifluoroacetate CF ₃ COO ^- , triflate CF ₃ SO ₃ ^- , sulfate SO ₄ ^2- , hydrogen sulfate HSO ₄ ^- , methylsulfate CH ₃ OSO ₃ ^- , ethylsulfate C ₂ H ₅ OSO ₃ ^- , methanesulfonate H ₃ C-SO ₃ ^- , trifluoromethanesulfonate F ₃ C-SO ₃ ^- , sulfite SO ₃ ^2- , hydrogensulfite HSO ₃ ^- , thiocyanate SCN ^- , aluminum chlorides AlCl ₄ ^- , Al ₂ Cl ₇ ^- , Al ₃ Cl ₁₀ ^- , aluminum tribromide AlBr ₄ ^- , nitrite NO ₂ ^- , nitrate NO ₃ ^- , copper chloride CuCl ₂ ^- , phosphate PO ₄ ^3- , hydrogen phosphate HPO ₄ ^2- , dihydrogen phosphate H ₂ PO ₄ ^- , diethyl phosphate, carbonate CO ₃ ^2- , bicarbonate HCO ₃ ^- .

Particularly preferred are acetates, sulfonates, tosylate p-CH ₃ C ₆ H ₄ SO ₃ ^- , sulfates, phosphates, bis (trifluoromethylsulfonyl) imide (CF ₃ SO ₂ ) ₂ N ^- .

These other ionic liquids can in one embodiment the invention as a solvent for the Catalyst can be used to make the catalyst better in the reaction mixture to distribute. For this purpose, the catalyst is preferred as a 10 to 90% solution 20 to 80, more preferably 30 to 70, and most preferably 40 to 60% solution in the further ionic liquid solved and this solution as a catalyst solution used.

In a further embodiment In the present invention, the further ionic liquid for Extraction of the catalyst or its residues or by-products the reaction can be used. For example, the reaction mixture, optionally after thermal or chemical deactivation of the Catalyst or cooling of the reaction mixture to a temperature at which the reaction no longer significant, with for example 5 to 30% by weight, preferably 10 to 25 and particularly preferably 10 to 20% by weight of the further ionic liquid is mixed and then the Phases separated.

If the further ionic liquid Not catalytically active, it can also stop the reaction be used by extraction of the catalyst.

A Extraction may preferably be carried out when the solubility of the diisocyanate or its oligomer in the ionic liquid less than 10% by weight, preferably less than 5, more preferably less than 3, most preferably less than 2 and in particular is less than 1% by weight and reversed the solubility the ionic liquid in the diisocyanate and / or its oligomer less than 10% by weight, preferably less than 5, more preferably less than 3, most especially preferably less than 2 and in particular less than 1% by weight.

process engineering can for one Such extraction all known extraction and washing methods and apparatuses, e.g. those included in Ullmann's Encyclopedia of Industrial Chemistry, 6th ed, 1999 Electronic Release, Chapter: Liquid - Liquid Extraction - Apparatus, are described. For example, this can be one-level or multi-level, preferably single-stage extractions, as well as those in cocurrent or countercurrent mode, preferably be countercurrent mode. Preferably, sieve tray or packed or packed columns, Stirred tank or Mixer-settler apparatuses, as well as columns with rotating internals used.

With the catalyst can in such an extraction also impurities are separated, the for example, from the decomposition or deactivation of the catalyst arise and are partially degrading the color.

In a preferred embodiment, such further ionic liquids are used to extract or dissolve the catalyst, which are formed by protonation of the corresponding bases, ie those in which R ^{17 is} hydrogen. These have the advantage that they can be purified by treatment of a base, for example sodium or potassium hydroxide solution or milk of lime and converted into the corresponding bases, can be purified, for example by distillation, and then converted back into the ionic liquids by protonation. So it is possible to regenerate spent extractant without great losses.

The regeneration can also take place, for example, by back-extraction of the ionic liquid to be regenerated with another solvent in which the catalyst is more soluble than in the ionic liquid or by precipitation or crystallization. Thus, also those ionic liquids can be regenerated, in which R ^{17 is} not hydrogen.

In ppm and percentages used in this specification refer to Unless indicated otherwise, by weight and ppm.

The The following examples are intended to illustrate the invention, but not to this Restrict examples.

Examples

In a stirring device, consisting of a 250 ml four-necked flask with stirrer, internal thermometer, reflux condenser, nitrogen inlet tube and oil bath were submitted to 100 g of hexamethylene diisocyanate (HDI) and at 80 ° C bath temperature at 75 ° C Heated inside temperature.

Then were 60 μl a 16.7% solution of the catalyst 2-hydroxyethyl-trimethylammonium Salicylate (melting point below room temperature, 100 ppm on HDI) solved in 2-propanol / propylene carbonate 1: 4 added. The rising Internal temperature to approx. 85 ° C at. The heater was removed until the internal temperature again at 80 ° C had fallen. At this temperature stirring was continued until the NCO value of originally 49% fell to 40%.

Then was cooled to room temperature using a water bath and the reaction by adding 15 μl Bis (2-ethylhexyl) phosphate (= 150 ppm on HDI) stopped.

The Resulting reaction mixture had a Hazen color number of 16th

Claims (11)

Process for the preparation of polyisocyanates containing isocyanurate, biuret and / or allophanate groups by at least partial oligomerization of diisocyanates, characterized in that the reaction is carried out in the presence of at least one oligomerization catalyst which is an ionic liquid having the structure

and a melting point of not more than 100 ° C, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 may} each independently be the same or different and represent a straight-chain or branched C ₁ - to C ₂₀ -alkyl group, an optionally substituted C ₅ - to C ₁₂ -cycloalkyl group, an optionally substituted C ₇ - to C ₁₀ -aralkyl group, or an optionally substituted C ₆ -C ₁₂ -aryl group or two or more of the radicals R ¹ to R ³ together form a 4-, 5- or 6-membered alkylene chain or together with a nitrogen atom form a 5- or 6-membered ring which may contain an additional nitrogen or oxygen atom as a bridging member or together a multi-membered, preferably form a six-membered multi-ring system, preferably a two-ring system, which may contain one or more additional nitrogen atoms, oxygen atoms or nitrogen and oxygen atoms as bridge members, and R ⁴ , R ⁵ , R ⁶ and R ^{7 may} additionally be hydrogen. Process according to claim 1, characterized in that An ^{- is} selected from the group of the carboxylates, sulfates, sulfites, sulfonates, sulfinates, phosphates, phosphonates, phosphinates and metal halides Method according to one of the preceding claims, characterized in that R ¹ , R ² and R ^{3 are the} same and at least one of R ⁴ and R ^{5 is} hydrogen. Method according to one of the preceding claims, characterized characterized in that Cation selected is selected from the group consisting of 2-hydroxyethyltrimethylammonium, 2-hydroxypropyltrimethylammonium, 2-hydroxyethyl-triethylammonium, 2-hydroxypropyl-triethylammonium, 2-hydroxyethyl-tri-n-butylammonium and 2-hydroxypropyl tri-n-butylammonium. A process according to any one of claims 2 to 4, characterized in that the metal halide is a compound M _x Hal _y ^z- , where M is a metal of the 1st to 5th main group or the 1st to 8 subgroup or a lanthanide or actinide and also Phosphorus, silicon or boron Hal is a halide or pseudohalide x and y are independently a positive integer and z is the sum of the charge of the metal and the charges of the halides and M is selected from the group consisting of Li, Na, K, Cs, Mg, Ca, Ba, Al, Ga, Sn, Sb, Bi, Ti, Zr, V, Nb, Cr, Mo, W, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, Hg, Ce, Sm, P, Si and B. Method according to one of claims 2 to 4, characterized in that the metal halide is selected from the group consisting of AlCl ₄ ^- , FeCl ₄ ^- , AlBr ₄ ^- , ZnCl ₃ ^- , BeCl ₃ ^- , ZnBr ₃ ^- , Znl ₃ ^- , CuCl ₃ ^-, CuCl ₂ ^-, CoCl ₃ ^-, Col ₃ ^-, Fel ₃ ^-, FeCl ₃ ^-, TiCl ₅ ^-, TiCl ₆ ^2-, TiCl ₄ ^-, SnCl ₃ ^-, SnCl ₄ ^-, SnCl ₄ ^2-, MnCl ₃ ^-, ₄ MnCl ^2, MnBr ₃ ^-, ScCl ₄ ^-, BCl ₄ ^-, BBr ₄ ^-, GaCl ₄ ^-, ReCl ₆ ^-, ZrCl ₅ ^-, NbCl ₆ ^-, VCl ₄ ^-, CrCl ₃ ^-, MoCl ₆ ^-, YCl ₄ ^-, CdCl ₃ ^-, CdBr ₃ ^-, SbCl ₄ ^-, SbCl ₆ ^-, BiCl ₄ ^-, ZrCl ₅ ^-, UCl ₅ ^-, UCl ₆ ^2-, LaCl ₄ ^-, CeCl ₄ ^-, SmCl ₄ ^- , Sml ₃ ^- , TaCl ₆ ^- , BF ₄ ^- , PCl ₄ ^- , PCl ₆ ^- and PF ₆ ^- . Process according to one of claims 2 to 4, characterized in that the metal halide is a mixture of halides or pseudohalides of a cation according to any one of claims 1 to 4 with Lewis acids selected from the group AlCl ₃ , FeCl ₃ , AlBr ₃ and ZnCl ₂ , BeCl ₂ , ZnBr ₂ , Znl ₂ , ZnSO ₄ , CuCl ₂ , CuCl, Cu (O ₃ SCF ₃ ) ₂ , CoCl ₂ , Col ₂ , Fel ₂ , FeCl ₂ , FeCl ₂ (THF) ₂ , TiCl ₄ (THF) ₂ , TiCl ₄ , TiCl ₃ , ClTi (OiPr) ₃ , SnCl ₂ , SnCl ₄ , Sn (SO ₄ ), Sn (SO ₄ ) ₂ , MnCl ₂ , MnBr ₂ , ScCl ₃ , BPh ₃ , BCl _3, BBr _3, BF ₃ · OEt _2, BF ₃ OMe _2, BF ₃ · MeOH, BF ₃ · CH ₃ COOH, BF ₃ · CH ₃ CN, B (CF ₃ COO) _3, B (OEt) _3, B (OMe) ₃ , B (OiPr) ₃ , PhB (OH) ₂ , 3-MeO-PhB (OH) ₂ , 4-MeO-PhB (OH) ₂ , 3-F-PhB (OH) ₂ , 4- F-PhB (OH) ₂ , (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) AlCl ₂ , (C ₈ H ₁₇ ) AlCl ₂ , (C ₈ H ₁₇ ) ₂ AlCl, (iso-C ₄ H ₉ ) ₂ AlCl, Ph ₂ AlCl, PhAlCl ₂ , Al (acac) ₃ , Al (OiPr) ₃ , Al (OnBu) ₃ , Al (OsekBu) ₃ , Al (OEt) ₃ , GaCl ₃ , ReCl ₅ , ZrCl ₄ , Nb Cl ₅ , VCl ₃ , CrCl ₂ , MoCl ₅ , YCl ₃ , CdCl ₂ , CdBr ₂ , SbCl ₃ , SbCl ₅ , BiCl ₃ , ZrCl ₄ , UCl ₄ , LaCl ₃ , CeCl ₃ , Er (O ₃ SCF ₃ ) Yb (O ₂ CCF ₃ ) ₃ , SmCl ₃ , Sml ₂ , B (C ₆ H ₅ ) ₃ and TaCl ₅ . Method according to one of claims 2 to 7, characterized that it the carboxylate is salicylate or nicotinate. Mixture containing At least one diisocyanate, - at least an ionic liquid as defined in any of the claims 1 to 8, - possibly at least one urethane, alcohol, amine or water as well - possibly at least one more ionic liquid. Use of ionic liquids as defined in one of the claims 1 to 8 in the preparation of polyisocyanates. Use of biuret, allophanate and / or isocyanurate groups containing polyisocyanates available according to one of the claims 1 to 8 in the manufacture of polyurethane coatings, dispersions and Adhesives and as a polyisocyanate component in one- and two-component polyurethane systems for polyurethane paints.