DE102008026341A1 - Catalysts for the synthesis of polyurethanes - Google Patents

Abstract

There are described new catalysts for the synthesis of polyurethanes corresponding to the general formulas I or II: $ F1 in the R1 for a radical from the series: C1-C10-alkyl, C2-C10-alkenyl, C3-C12-cycloalkyl, C6 C100-polyoxyalkylene, C5-C10-aryl or C5-C10-hetaryl, in which R2 represents a residue from the series: C1-C10-alkoxy, C5-C12-cycloalkoxy, C6-C100-polyoxyalkylene, C5-C10- Aryloxy, C 1 -C 10 perfluoroalkyl, C 1 -C 10 perchloroalkyl, partially fluorinated C 1 -C 10 alkyl, partially chlorinated C 1 -C 10 alkyl, perfluorinated C 5 -C 10 aryl, partially fluorinated C 5 -C 10 aryl, perchlorinated C 5 -C 10 aryl, partially chlorinated C5-C10-aryl, preferably a radical: methoxy, ethoxy, iso-propoxy, tert-butyloxy, iso-butyloxy, 2-ethylhexyloxy, phenyloxy, cyclohexyloxy, CF3, CCl3, pentafluorophenyl, tetrafluorophenyl may have, in the A and D independently represent a methylene radical, CHR3, and CR3R3 or A and D taken together for a radical of the series: propylene, 1,2-phenylene or with a C1-C10 alkyl, C 2-C10 alkenyl, C3-C12 cycloalkyl, C6-C100 polyoxyalkylene, C5-C10 aryl or C5-C10-hetaryl substituted 1,2-phenylene, -CH = N-, -CH2-NR3 -, -CH 2 -CHR 3 -, -CHR 3 -CH 2 -, -CHR 3 -CHR 3 -, vinylene, -CH 2 = CHR 3 -, -CHR 3 = CH 2 -, -CHR 3 = CHR 3 - stand, wherein the radicals R3 independently of each other the above R1 given meaning, and in the X for ...

Description

The The invention relates to novel catalyst compounds for the synthesis of Polyurethanes and a process for the preparation of polyurethanes using these catalysts.

Two Component polyurethane systems find as paints, foams, fibers and non-porous molded articles broad application. The polymer is mixed by mixing and then Reaction of an isocyanate group-containing component with an OH group containing component. Often the reaction becomes the isocyanate group with the OH group with the addition of basic compounds, such as tertiary amines or amidine-containing compounds catalyzed. Examples of such compounds are 1,4-diazabicyclo [2.2.2] octane or diazabicycloundecene (DBU). A significantly higher catalytic However, they have organometallic compounds such as dibutyltin dilaurate or different zinc carboxylates. The amount of catalyst used generally depends on what time after the application should elapse until the polymer by the polymerization minimum property level has reached, for example, the prerequisite for a subsequent processing step. Indeed the catalysts mentioned above are characterized in that they, regardless of the degree of catalytic action, their possess catalytic activity at all times. This As a result, after addition of the catalyst in the Mixture of polyisocyanate and polyol accelerates the crosslinking and thus the processing time of such a mixture is limited. There is therefore a need for compounds which can be used as catalyst precursors or latent catalysts. Own such compounds initially no catalytic effect. You can but by exposing certain conditions to a catalytic one active species are transferred. Thus appears it is possible to add the catalyst precursor into the mixture of polyisocyanate and polyol without the processing time adversely affect. After application, the catalyst precursor then, for example, by gentle heating or irradiation be activated with light, so that the polymerization with a for the application acceptable speed expires.

Polyurethane catalysts, who take advantage of this concept, are known in principle.

For example, describes EP 989 146 A1 the use of tertiary amines blocked with dicarboxylic acids as latent catalysts for the production of polyurethane foams. However, only minimal delays in the catalytic activity of 1-2 seconds are described.

EP 1 354 903 A1 discloses latent tin-organic catalysts which are thermally activated in a temperature range of 30-99 ° C with elimination of a substitute on the tin. Organotin compounds, however, are often toxicologically questionable, so that, if possible, the use of tin-based catalysts is dispensed with.

WO 2006/030029 A1 claims, for example, a polythiourethane formulation which is latently curable using photobases. In this process, a tertiary amine-blocking group is split off under irradiation with UV light of suitable wavelength and intensity, and the catalytically active tertiary amine is liberated. The disadvantage, however, is that the catalytic effect of tertiary amines is so low that for catalysts very high amounts must be used to achieve a drying of polyurethanes within a few minutes. Therefore, the use of such tertiary amino groups containing photobases is limited to the Polythiourethanbildung. In addition, in the activation of the catalyst coupling products are released, which may possibly lead to an odor nuisance.

task The present invention was therefore blocked catalysts to develop for polyurethane chemistry, on the one hand do not adversely affect the pot life of 2-part polyurethanes and converted by thermal activation into a catalytically active species which, at a very high level, catalyzes the NCO-OH reaction.

It it was surprisingly found that the NCO-OH reaction catalyzed with N-heterocyclic carbenes (NHC) at a high level can be. The NHCs can be blocked in one Formed and in the mixture of polyisocyanate and polyol formulated, and for example after application by heating released to a characteristic activation temperature.

in der R₁ für einen Rest aus der Reihe: C₁-C₁₀-Alkyl, C₂-C₁₀-Alkenyl, C₃-C₁₂-Cycloalkyl, C₆-C₁₀₀-Polyoxyalkylen, C₅-C₁₀-Aryl oder C₅-C₁₀-Hetaryl steht,
bevorzugt für einen Rest Methyl, Ethyl, n-Propyl, iso-Propyl, tert.-Butyl, neo-Pentyl, iso-Amyl, Cyclohexyl, Phenyl, 2,6-Dimethylphenyl, 2,6-Diisopropylphenyl, Mesityl
und besonders bevorzugt für iso-Propyl, Phenyl 2,6-Dimethylphenyl, 2,6-Diisopropylphenyl oder Mesityl steht,
in der R₂ für einen Rest aus der Reihe: C₁-C₁₀-Alkoxy, C₅-C₁₂-Cycloalkoxy, C₆-C₁₀₀-Polyoxyalkylen, C₅-C₁₀-Aryloxy, C₁-C₁₀-perfluoralkyl, C₁-C₁₀-perchloralkyl, teilfluoriertes C₁-C₁₀-Alkyl, teilchloriertes C₁-C₁₀-Alkyl, perfluoriertes C₅-C₁₀-aryl, teilfluoriertes C₅-C₁₀-aryl, perchloriertes C₅-C₁₀-aryl, teilchloriertes C₅-C₁₀-aryl steht,
bevorzugt für einen Rest Methoxy, Ethoxy, iso-Propoxy, tert.-Butyloxy, iso-Butyloxy, 2-Ethylhexyloxy, Phenyloxy, Cyclohexyloxy, CF₃, CCl₃, Pentafluorphenyl, Tetrafluorphenyl steht,
in der A und D unabhängig voneinander für einen Methylenrest, CHR₃, und CR₃R₃ oder A und D zusammengenommen für einen Rest der Reihe: Propylen, 1,2-Phenylen oder mit einer C₁-C₁₀-Alkyl-, C₂-C₁₀-Alkenyl-, C₃-C₁₂-Cycloalkyl-, C₆-C₁₀₀-Polyoxyalkylen-, C₅-C₁₀-Aryl- oder C₅-C₁₀-Hetarylgruppe substituiertes 1,2-Phenylen, -CH=N-, -CH₂-NR₃-, vinylen, -CH₂=CHR₃-, -CHR₃=CH₂-, -CHR₃=CHR₃- stehen, wobei die Reste R₃ unabhängig von einander die oben für R₁ angegebene Bedeutung haben,
und in der X für Sauerstoff, Schwefel oder -NR₃'-, steht, wobei R₃' die oben für R₁ angegebene Bedeutung hat,
oder Verbindungen der allgemeinen Formel II:

wobei R₄ die oben in Formel I zu R₁, X' die zu X, A' die zu A und B' die zu B angegebene Bedeutung haben,
oder Verbindungen, die durch die Reaktion eines Metallsalzes der Metalle: Magnesium, Calcium, Yttrium, Lanthan, Titan, Zirkonium, Mangan, Eisen, Kobalt, Zink, Aluminium, Zinn, mit einem Anion der Reihe: Fluorid, Chlorid, Bromid, Sulfonat, Trifluormethansulfonat, Methansulfonat, Benzolsulfonat, para-Toluolsulfonat, Carboxy-C₁-C₁₀-alkyl, Carboxy-C₃-C₁₀-cycloalkyl, Carboxy-C₂-C₁₀-alkenyl, C₁-C₁₀-alkoxy, Acetylacetonat, Trifluoracetlyacetonat oder Hexafluoracetylacetonat,
bevorzugt eines Metallsalzes der Reihe: Zirkonium-, Zink-, Aluminium- oder Zinnchlorid, -bromid oder -acetat
mit N-heterocyclischen Verbindungen der allgemeinen Struktur I;
oder mit N-heterocyclischen Verbindungen der allgemeinen Struktur II;
oder mit N-heterocyclischen Verbindungen der allgemeinen Struktur III,

wobei R₅ die oben in Formel I zu R₁, X' die zu X, A' die zu A und B' die zu B angegebene Bedeutung haben, und Y für F, Cl, Br, I, BF₄ oder SbF₆ steht,
erhalten werden.The invention relates to novel catalysts for the synthesis of polyurethanes comprising compounds of general formula I:

in which R _{1 is} a radical from the series: C ₁ -C ₁₀ -alkyl, C ₂ -C ₁₀ -alkenyl, C ₃ -C ₁₂ -cycloalkyl, C ₆ -C ₁₀₀ -polyoxyalkylene, C ₅ -C ₁₀ -aryl or C ₅ -C ₁₀ -Hetaryl,
preferably represents a radical methyl, ethyl, n-propyl, iso-propyl, tert-butyl, neo-pentyl, iso-amyl, cyclohexyl, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, mesityl
and particularly preferably represents iso-propyl, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl or mesityl,
in the R _{2 is} a radical from the series: C ₁ -C ₁₀ alkoxy, C ₅ -C ₁₂ cycloalkoxy, C ₆ -C ₁₀₀ polyoxyalkylene, C ₅ -C ₁₀ aryloxy, C ₁ -C ₁₀ perfluoroalkyl , C ₁ -C ₁₀ -perchloroalkyl, partially fluorinated C ₁ -C ₁₀ -alkyl, partially chlorinated C ₁ -C ₁₀ -alkyl, perfluorinated C ₅ -C ₁₀ -aryl, partially fluorinated C ₅ -C ₁₀ -aryl, perchlorinated C ₅ -C ₁₀ -aryl, partially chlorinated C ₅ -C ₁₀ -aryl,
preferably a radical is methoxy, ethoxy, isopropoxy, tert-butyloxy, isobutoxy, 2-ethylhexyloxy, phenyloxy, cyclohexyloxy, CF ₃ , CCl ₃ , pentafluorophenyl, tetrafluorophenyl,
in the A and D are independently of one another a methylene radical, CHR ₃ , and CR ₃ R ₃ or A and D taken together for a radical of the series: propylene, 1,2-phenylene or with a C ₁ -C ₁₀ alkyl, C C ₂ -C ₁₀ -alkenyl, C ₃ -C ₁₂ -cycloalkyl, C ₆ -C ₁₀₀ -polyoxyalkylene, C ₅ -C ₁₀ -aryl or C ₅ -C ₁₀ -Hetarylgruppe substituted 1,2-phenylene, - CH = N-, -CH ₂ -NR ₃ -, vinylene, -CH ₂ = CHR ₃ -, -CHR ₃ = CH ₂ -, -CHR ₃ = CHR ₃ - stand, where the radicals R _3, independently of each other, the above have the meaning given for R ₁ ,
and in which X is oxygen, sulfur or -NR ₃ '-, where R ₃ ' has the meaning given above for R ₁ ,
or compounds of general formula II:

where R _{4 is} the same as in R ₁ above, X 'is X, A' is A and B 'is B,
or compounds obtained by the reaction of a metal salt of the metals: magnesium, calcium, yttrium, lanthanum, titanium, zirconium, manganese, iron, cobalt, zinc, aluminum, tin, with an anion of the series: fluoride, chloride, bromide, sulfonate, Trifluoromethanesulfonate, methanesulfonate, benzenesulfonate, para-toluenesulfonate, carboxy-C ₁ -C ₁₀ -alkyl, carboxy-C ₃ -C ₁₀ -cycloalkyl, carboxy-C ₂ -C ₁₀ -alkenyl, C ₁ -C ₁₀ -alkoxy, acetylacetonate, Trifluoroacetylacetonate or hexafluoroacetylacetonate,
preferably a metal salt of the series: zirconium, zinc, aluminum or tin chloride, bromide or acetate
with N-heterocyclic compounds of general structure I;
or with N-heterocyclic compounds of general structure II;
or with N-heterocyclic compounds of general structure III,

wherein R _{5 is} the formula I to R ₁ , X 'to X, A' to A and B 'have the meaning given above for B, and Y is F, Cl, Br, I, BF ₄ or SbF ₆ .
to be obtained.

object The invention further relates to a process for the preparation of polyurethanes by the reaction of polyisocyanates A) with compounds B) with isocyanate-reactive hydrogen atoms, in particular with polyhydroxy compounds in the presence of catalysts C) and optionally adjuvants and additives with optionally increased Temperature, characterized in that as catalysts the above said catalysts of the invention used become.

Prefers is a process characterized in that the reaction temperature at least 60 ° C.

The polyisocyanates from A) suitable for the preparation of polyurethanes are the organic aliphatic, cycloaliphatic, aromatic or heterocyclic polyisocyanates known to those skilled in the art having at least two isocyanate groups per molecule and mixtures thereof. Examples of suitable aliphatic or cycloaliphatic polyisocyanates are di- or triisocyanates such as. As butane diisocyanate, pentane diisocyanate, hexane diisocyanate (hexamethylene diisocyanate, HDI), 4-Isocyanatomethyl-1,8-octane diisocyanate (Triisocyanatononan, TIN) or cyclic systems, such as. For example, 4,4'-methylenebis (cyclohexyl isocyanate), 3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), and ω.ω'-diisocyanato-1,3-dimethylcyclohexane (H ₆ XDI ). As aromatic polyisocyanates z. As 1,5-naphthalene diisocyanate, diisocyanatodiphenylmethane (2,4'- and 4,4'-MDI or mixtures thereof), Diisocyanatomethylbenzol (2,4- and 2,6-toluene diisocyanate, TDI), in particular the 2,4- and the 2,6-isomers and technical mixtures of the two isomers and 1,3-bis (isocyanatomethyl) benzene (XDI) can be used.

moreover but can also be the known derivatives of the aforementioned organic aliphatic, cycloaliphatic, aromatic or heterocyclic polyisocyanates with carbodiimide, uretonimine, Uretdione, allophanate, biuret and / or isocyanurate structure, as well Prepolymers obtained by reacting the polyisocyanate with compounds with isocyanate-reactive hydrogens be used.

The Polyisocyanate component A) may be in a suitable solvent available. Suitable solvents are those which have a sufficient Have solubility of the polyisocyanate component and free of isocyanate-reactive groups. Examples for such solvents are acetone, methyl ethyl ketone, Cyclohexanone, methyl isobutyl ketone, methyl isoamyl ketone, diisobutyl ketone, Ethyl acetate, n-butyl acetate, ethylene glycol diacetate, butyrolactone, Diethyl carbonate, propylene carbonate, ethylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, methylal, ethylal, butylal, 1,3-dioxolane, glycerol formal, benzene, toluene, n-hexane, cyclohexane, Solvent naphtha, 2-methoxypropyl acetate (MPA).

When Polyhydroxy compounds in B) can all those skilled in the art known compounds which have a mean OH functionality of at least 1.5. These can be, for example, low molecular weight Diols (eg 1,2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol), Triols (eg, glycerin, trimethylolpropane) and tetraols (eg, pentaerythritol) be, but also higher molecular weight polyhydroxy compounds such as Polyether polyols, polyester polyols, polycarbonate polyols and polybutadiene polyols.

polyether polyols are in a conventional manner by alkoxylation of suitable Starter molecules under base catalysis or use of Double metal cyanide (DMC) compounds accessible. suitable Starter molecules for the production of polyether polyols are, for example, simple, low molecular weight polyols, water, organic polyamines having at least two N-H bonds or any Mixtures of such starter molecules. Preferred starter molecules for the preparation of polyether polyols by alkoxylation, in particular according to the DMC process, especially simple polyols such as ethylene glycol, propylene glycol-1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 2-ethylhexanediol-1,3, Glycerol, trimethylolpropane, pentaerythritol and low molecular weight, Hydroxyl-containing esters of such polyols with dicarboxylic acids the following exemplary mentioned type or low molecular weight Ethoxylation or Propoxylierungsprodukte such simpler Polyols or any mixtures thereof modified or not modified alcohols. Suitable for the alkoxylation Alkylene oxides are in particular ethylene oxide and / or propylene oxide, in any order or even in the mixture during the alkoxylation can be used.

Polyester polyols can in a known manner by polycondensation of low molecular weight polycarboxylic acid such as succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer fatty acid, trimer acid, phthalic acid, phthalic anhydride, isophthalic acid , Tereph thalian acid, citric acid or trimellitic acid, with low molecular weight polyols such as ethylene glycol, diethylene glycol, neopentyl glycol, hexanediol, butanediol, propylene glycol, glycerol, trimethylolpropane, 1,4-hydroxymethylcyclohexane, 2-methyl-1,3-propanediol, butanetriol-1,2,4 , Triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol, or by ring-opening polymerization of cyclic carboxylic acid esters such as ε-caprolactone. In addition, hydroxycarboxylic acid derivatives such as, for example, lactic acid, cinnamic acid or ω-hydroxycaproic acid can also be polycondensed to form polyester polyols. However, it is also possible to use polyester polyols of oleochemical origin. Such polyester polyols can be prepared, for example, by complete ring opening of epoxidized triglycerides of an at least partially olefinically unsaturated fatty acid-containing fat mixture with one or more alcohols having 1 to 12 carbon atoms and subsequent partial transesterification of the triglyceride derivatives to alkyl ester polyols having 1 to 12 C atoms in the alkyl radical getting produced.

The Preparation of suitable polyacrylate polyols is known to those skilled in the art known. They are obtained by radical polymerization of hydroxyl groups having, olefinically unsaturated monomers or by free-radical copolymerization of hydroxyl groups, olefinically unsaturated monomers with optionally other olefinically unsaturated monomers, such as. Ethyl acrylate, Butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, methyl methacrylate, Ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, Styrene, acrylic acid, acrylonitrile and / or methacrylonitrile receive. Suitable hydroxyl-containing, olefinically unsaturated In particular, monomers are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, the obtainable by addition of propylene oxide to acrylic acid Hydroxypropyl-acrylate isomer mixture and by addition from propylene oxide to methacrylic acid available Hydroxypropyl methacrylate isomer mixture. Suitable radical initiators are from the group of azo compounds, such as azoisobutyronitrile (AIBN), or from the group of peroxides, such as di-tert-butyl peroxide.

The Polyhydroxy component B) may be in a suitable solvent available. Suitable solvents are those which have a sufficient Have solubility of the polyhydroxy component. Examples for such solvents are acetone, methyl ethyl ketone, Cyclohexanone, methyl isobutyl ketone, methyl isoamyl ketone, diisobutyl ketone, Ethyl acetate, n-butyl acetate, ethylene glycol diacetate, butyrolactone, Diethyl carbonate, propylene carbonate, ethylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, methylal, Ethylal, butylal, 1,3-dioxolane, glycerol formal, benzene, toluene, n-hexane, cyclohexane, solvent naphtha, 2-methoxypropyl acetate (MPA). In addition, the solvents can also carry isocyanate-reactive groups. Examples for such reactive solvents are those which an average functionality towards isocyanates have reactive groups of at least 1.8. This can For example, low molecular weight diols (eg 1,2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol), triols (for example glycerol, trimethylolpropane) but also low molecular weight diamines, such as polyaspartic acid ester.

Non-limiting examples of catalysts usable in C) are the compounds 1a-1q:

The Compounds of the formulas 1a to 1q are particularly preferred catalysts, which is also preferred in the process according to the invention be used.

The Compounds of formula 1g, 1j, 1k, 1l, 1m, 1o, and 1p are made not known in the prior art. Subject of the invention are Therefore, the compounds of formula 1g, 1j, 1k, 1l, 1m, 1o, and 1p as such.

Another The invention relates to the use of the invention Catalysts for the production of polyisocyanate polyaddition products.

The invention further provides a curable polyisocyanate composition comprising at least
10 to 90 parts by weight, preferably 20 to 80 parts by weight of polyisocyanates and
90 to 10 parts by weight, preferably 80 to 20 parts by weight of compounds with isocyanate-reactive hydrogen atoms, in particular polyhydroxy compounds and
0.001 to 5 parts by weight, preferably 0.01 to 2.5 parts by weight of the catalysts according to the invention,
where the sum of all parts by weight must be 100.

The obtainable with the catalysts according to the invention Polyisocyanate compositions can be used to prepare Coatings, adhesives, sealants or porous (Foams) or non-porous moldings be used.

Examples

Preparation of the catalysts

Example 1a

100 mg of 2,3,4,5,6-pentafluorobenzaldehyde are concentrated in 0.5 ml. Acetic acid dissolved and with 150 mg N, N'-bis (2,4,6-trimethylphenylamino) ethane was added. It is stirred for 30 min at room temperature and then filtered through silica. The solvent is removed on a rotary evaporator. 180 mg of compound 1a are obtained.

Example 1b

100 mg N, N'-bis (2,4,6-trimethylphenylamino) ethane, 50 mg trifluoroacetaldehyde ethylhemiacetal and 5 mg of p-toluenesulfonic acid are dissolved in 5 ml of toluene and stirred at 40 ° C for 24 h. It is about filtered basic alumina and the solvent on Rotary evaporator removed. 83 mg of the compound are obtained 1b.

Example 1c

61 mg 2,3,5,6-tetrafluorobenzaldehyde are concentrated in 1 ml. acetic acid dissolved and with 100 mg of N, N'-bis (2,4,6-trimethylphenylamino) ethane added. It is stirred for 30 min at room temperature and then filtered over silica. The solvent is removed on a rotary evaporator to give 114 mg of compound 1c.

Example 1d

In a typical experiment is 381 mg of 1,3-bis (2,4,6-trimethylphenyl) imidazolinium chloride suspended in 20 ml of THF. 150 mg of potassium hydride are added at room temperature added and it is stirred for 3 h. The mixture is over Celite filtered, the solvent on a rotary evaporator removed and the residue is recrystallized from hexane. This gives 220 mg of 1,3-bis (2,4,6-trimethylphenyl) imidazolin-2-ylidene.

800 mg of 1,3-bis (2,4,6-trimethylphenyl) imidazolin-2-ylidene are in 20 ml of THF (absolute) and 0.5 ml of methanol. It will be 30 Stirred at room temperature and the solvent removed on a rotary evaporator. The backlog will be out Recrystallized pentane to give 620 mg of the compound 1d.

Example 1e

In a typical experiment is 381 mg of 1,3-bis (2,4,6-trimethylphenyl) imidazolinium chloride suspended in 20 ml of THF. 150 mg of potassium hydride are added at room temperature added and it is stirred for 3 h. The mixture is over Celite filtered, the solvent on a rotary evaporator removed and the residue is recrystallized from hexane. This gives 220 mg of 1,3-bis (2,4,6-trimethylphenyl) imidazolin-2-ylidene.

800 mg of 1,3-bis (2,4,6-trimethylphenyl) imidazolin-2-ylidene and 2 ml of chloroform are dissolved in 20 ml of THF. It is 2 h at room temperature touched. The solvent is on a rotary evaporator removed and the residue washed with pentane. You get 830 mg of compound 1e.

Example 1f

2.5 g 1,3-bis (2,4,6-trimethylphenyl) imidazolinium chloride and 350 mg Potassium hydride are suspended in 50 ml of THF. It is 4 h at room temperature stirred and then on Celite filtered. Carbon dioxide is passed through the filtrate for 30 min directed. It is filtered and washed with diethyl ether. you receives 1.2 g of compound 1f.

Example 1g

5.0 g of 3-ethyl-1-methylimidazolium bromide and 3.5 g of potassium tert-butoxide are suspended in 100 ml of THF. It will be at room temperature for 16 h stirred and filtered through Celite. carbon dioxide gas is passed through the filtrate for 30 minutes. After filtration and wash diethyl ether gives 3.75 g of compound 1g.

Example 1h

2.5 g 1,3-bis (2,4,6-trimethylphenyl) imidazolium chloride and 0.986 g potassium t-butoxide are suspended in 50 ml of THF. It will be at room temperature for 16 h stirred and then filtered Celite. Carbon dioxide will passed through the filtrate for 4 h. After filtration and Washing with diethyl ether gives 2.3 g of the compound 1h.

Example 1j

1,3-dimesityl-3,4,5,6-tetrahydropyrimidine-1-iumbromide becomes analogous Mayr, M .; Wurst, K .; Ongania, K.-H .; Buchmeiser, MR Chem. Eur. J. 2084, 10, 1256-1266 produced.

5 g 1,3-dimesityl-3,4,5,6-tetrahydropyrimidine-1-iumbromide and 1.68 g Potassium tert-butoxides are suspended in 100 ml of THF. It will Carbon dioxide was introduced with stirring for 4 h. After filtration and washing with diethyl ether gives 3.39 g of the compound 1j.

Example 1k

1,3-Diisopropyl-3,4,5,6-tetrahydropyrimidine-1-ium tetrafluoroborate is analogous Alder, RW; Blake, ME; Bortolotti, C .; Bufali, S .; Butts, CP; Linehan, E .; Oliva, JM; Orpen, G .; Quayle, MJ Chem. Commun. 1999, 241-242 produced

1.0 g 1,3-Diisopropyl-3,4,5,6-tetrahydropyrimidine-1-ium tetrafluoroborate and 526 mg of potassium tert-butoxide are suspended in 20 ml of THF. It is stirred for 16 h at room temperature and then over Celite filtered. Carbon dioxide is passed through the filtrate for 30 minutes. The solvent is removed on a rotary evaporator and the residue was washed with diethyl ether. You get 0.7 g of compound 1k.

Example 1l

300 mg 1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-1-ium-2-carboxylate are suspended in 15 ml of benzene. 113 mg of zinc chloride are added and the suspension is stirred at 85 ° C for 2 h. The solvent is removed in vacuo. The residue is taken up in dichloromethane, filtered and the solvent withdrawn on a rotary evaporator. This gives 338 mg of Compound 1l.

Example 1m

789 mg of compound 1h are suspended in 15 ml of benzene. 315 mg zinc chloride are added and the suspension is stirred at 85 ° C for 2 h. The solvent is removed in vacuo. The residue is taken up in dichloromethane, filtered and the solvent withdrawn on a rotary evaporator. This gives 1020 mg of Connection 1m.

Example 1n

649 mg of compound 1h are suspended in 15 ml of benzene. 349 mg zinc acetate are added and the suspension is stirred at 85 ° C for 2 h. The solvent is removed in vacuo. The residue is taken up in dichloromethane, filtered and the solvent withdrawn on a rotary evaporator. This gives 929 mg of Connection 1n.

Example 1o

1,3-dimesityl-3,4,5,6-tetrahydropyrimidine-1-iumbromide becomes analogous Mayr, M .; Wurst, K .; Ongania, K.-H .; Buchmeiser, MR Chem. Eur. J. 2004, 10, 1256-1266 produced.

1.5 g of 1,3-dimesityl-3,4,5,6-tetrahydropyrimidine-1-iumbromid are dissolved in 50 ml of diethyl ether. At -30 ° C., 360 mg of n-butyllithium are added. After 15 minutes, 710 mg of SnCl _{2 are} added and the mixture is stirred for 6 hours at room temperature. The mixture is filtered, the solvent removed in vacuo and the residue recrystallized from dichloromethane / diethyl ether. 1.8 g of compound 1o are obtained.

Example 1p

1,3-bis (2,4,6-trimethylphenyl) imidazolin-2-ylidene becomes analogous Arduengo, AJ; Krafczyk, R .; Schmutzler, R. Tetrahedron 55 (1999) 14523-14534 produced.

100 mg of 1,3-bis (2,4,6-trimethylphenyl) imidazolin-2-ylidene are dissolved in 20 ml of THF. 62 mg SnCl ₂ are added and the mixture is stirred for 3 h at room temperature. The solvent is removed in vacuo and the residue is taken up in dichloromethane and filtered. The solvent is removed in vacuo and the residue is recrystallized from dichloromethane / diethyl ether. 145 mg of compound are obtained 1p.

Example 1q

1,3-bis (2,4,6-trimethylphenyl) imidazolin-2-ylidene becomes analogous Arduengo, AJ; Krafczyk, R .; Schmutzler, R. Tetrahedron 55 (1999) 14523-14534 produced.

250 mg of 1,3-bis (2,4,6-trimethylphenyl) imidazolin-2-ylidene are dissolved in 20 ml of benzene. 214 mg of AlBr ₃ are added and the mixture is stirred for 30 minutes at room temperature. The solvent is removed in vacuo and the residue is recrystallized from dichloromethane / diethyl ether. 345 mg of compound 1q are obtained.

Testing the catalysts

Comparative example without catalyst

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. The course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C.

Comparative example with dibutyltin dilaurate (DBTL) as a catalyst

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. 12.5 μl of dibutyltin dilaurate (50% by weight in butyl acetate) are added. The course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C.

Investigation of the catalytic activity

Example 2 with catalyst 1a

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. 5.3 μl of compound 1a (50% by weight in butyl acetate) are added. The course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C (see 1 ). It can be seen in comparison to the comparative example without catalyst accelerated curing of the faster decrease in the isocyanate.

Example 3 with catalyst 1d

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. 2.6 μl of Compound 1d (50% by weight in butyl acetate) are added. The course of the reaction is monitored by the degradation of the isocyanate band in the IR spectrum at 60 ° C (see 2 ). It can be seen in comparison to the comparative example without catalyst accelerated curing of the faster decrease in the isocyanate.

Example 4 with catalyst 1e

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. 2.3 μl of Compound 1e (50% by weight in butyl acetate) are added. The course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C (see 3 ). It can be seen in comparison to the comparative example without catalyst accelerated curing of the faster decrease in the isocyanate.

Example 5 with catalyst 1g

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) are mixed and coated on a ATR crystal. 3.2 μl of Compound 1g (50% by weight in butyl acetate) are added. The course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C (see 4 ). It can be seen in comparison to the comparative example without catalyst accelerated curing of the faster decrease in the isocyanate.

Example 6 with catalyst 1k

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. 4.3 μl of Compound 1k (50% by weight in butyl acetate) are added. The course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C (see 5 ). It can be seen in comparison to the comparative example without catalyst accelerated curing of the faster decrease in the isocyanate.

Example 7 with catalyst 1l

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. 5.0 μl of Compound 1l (50% by weight in butyl acetate) are added. The course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C (see 6 ). It can be seen in comparison to the comparative example without catalyst accelerated curing of the faster decrease in the isocyanate.

Example 8 with catalyst 1m

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. 4.7 μl of Compound 1m (50% by weight in butyl acetate) are added. The course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C (see 7 ). It can be seen in comparison to the comparative example without catalyst accelerated curing of the faster decrease in the isocyanate.

Example 9 with catalyst 1n

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. 5.7 μl of Compound 1n (50% by weight in butyl acetate) are added. The course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C (see 8th ). It can be seen in comparison to the comparative example without catalyst accelerated curing of the faster decrease in the isocyanate.

Example 10 with catalyst 1o

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. 6.1 μl of Compound 1o (50% by weight in butyl acetate) are added. The course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C (see 9 ). It can be seen in comparison to the comparative example without catalyst accelerated curing of the faster decrease in the isocyanate.

Example 11 with catalyst 1q

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. 4.7 μl of compound 1q (50% by weight in butyl acetate) are added. The course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C (see 10 ). It can be seen in comparison to the comparative example without catalyst accelerated curing of the faster decrease in the isocyanate.

temperature-dependent Studies of catalytic activity

Example 12 with catalyst 1a

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. 5.3 μl of compound 1a (50% by weight in butyl acetate) are added. The reaction mixture is first examined for 60 min at 45 ° C. Subsequently, the course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C (see 11 ). One first recognizes a rapid increase of the isocyanate band by the evaporation of the solvent. Subsequently, the isocyanate band remains at a constant level. As the temperature is raised to 60 ° C, the isocyanate band decreases rapidly. The catalyst has been converted to its catalytically active form.

Example 13 with catalyst 1g

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. 3.2 μl of Compound 1g (50% by weight in butyl acetate) are added. The reaction mixture is first examined for 20 min at 45 ° C. Subsequently, the course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C (see 12 ). One first recognizes a rapid increase of the isocyanate band by the evaporation of the solvent. Subsequently, the isocyanate band remains at a constant level. As the temperature is raised to 60 ° C, the isocyanate band decreases rapidly. The catalyst has been converted to its catalytically active form.

Example 14 with catalyst 1h

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. 7.6 μl of compound 1h (50% by weight in butyl acetate) are added. The reaction mixture is first examined for 40 min at 45 ° C. Subsequently, the course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C (see 13 ). One first recognizes a rapid increase of the isocyanate band by the evaporation of the solvent. Subsequently, the isocyanate band remains at a constant level. As the temperature is raised to 60 ° C, the isocyanate band decreases rapidly. The catalyst has been converted to its catalytically active form.

Example 15 with catalyst 1j

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. 5.3 μl of Compound 1j (50% by weight in butyl acetate) are added. The reaction mixture is first examined for 40 min at 45 ° C. Subsequently, the course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C (see 14 ). One first recognizes a rapid increase of the isocyanate band by the evaporation of the solvent. Subsequently, the isocyanate band remains at a constant level. As the temperature is raised to 60 ° C, the isocyanate band decreases rapidly. The catalyst has been converted to its catalytically active form.

Example 16 with catalyst 1k

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. 4.3 μl of Compound 1k (50% by weight in butyl acetate) are added. The reaction mixture is first examined for 40 min at 45 ° C. Subsequently, the course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C (see 15 ). One first recognizes a rapid increase of the isocyanate band by the evaporation of the solvent. Subsequently, the isocyanate band remains at a constant level. As the temperature is raised to 60 ° C, the isocyanate band decreases rapidly. The catalyst has been converted to its catalytically active form.

Example 17 with catalyst 1o

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) are mixed and coated on a ATR crystal. 6.1 μl of Compound 1o (50% by weight in butyl acetate) are added. The reaction mixture is first examined for 40 min at 45 ° C. Subsequently, the course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C (see 16 ). One first recognizes a rapid increase of the isocyanate band by the evaporation of the solvent. Subsequently, the isocyanate band remains at a constant level. As the temperature is raised to 60 ° C, the isocyanate band decreases rapidly. The catalyst has been converted to its catalytically active form.

Example 18 with catalyst 1p

100 mg Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 253 mg Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH) and an ATR Crystal applied. 5.8 μl of compound 1p (50% by weight in butyl acetate) are added. The reaction mixture is first examined for 40 min at 45 ° C. Subsequently, the course of the reaction is monitored by changing the isocyanate band in the IR spectrum at 60 ° C (see 17 ). One first recognizes a rapid increase of the isocyanate band by the evaporation of the solvent. Subsequently, the isocyanate band remains at a constant level. As the temperature is raised to 60 ° C, the isocyanate band decreases rapidly. The catalyst has been converted to its catalytically active form.

Investigations of the polymer film

Comparative example without catalyst

38.1 g of Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 100 g of Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% -OH). Immediately after the mixture, after 60 min, 120 min and 180 min, the viscosity is calculated as the flow time ( DIN 53 211 , 4 mm DIN outlet cup at 23 ° C). The drying times T1, T2, T3 and T4 according to DIN 53 150 as well as the pendulum hardness [pendulum damping according to König ( DIN EN ISO 1522 )] when stored at room temperature and stored at 60 ° C.

Comparative example with dibutyltin dilaurate

38.1 g of Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 100 g of Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% OH) and 3, 2 g of dibutyltin dilaurate (1 wt% in butyl acetate). Immediately after the mixture, after 60 minutes, after 120 minutes and after 180 minutes, the viscosity is determined as the flow time ( DIN 53 211 , 4 mm DIN outlet cup at 23 ° C). The drying times T1, T2, T3 and T4 according to DIN 53 150 as well as the pendulum hardness [pendulum damping according to König ( DIN EN ISO 1522 )] when stored at room temperature and stored at 60 ° C.

Example 19 with compound 1j

38.1 g of Desmodur ^® N3390BA (HDI polyisocyanate of Fa. Bayer MaterialScience AG, NCO 19.6%) are mixed with 100 g of Desmophen ^® A870BA (Polyol Fa. Bayer Material Science AG, 2.95% OH) and 1, 9 g of compound 1j (10% by weight in dichloromethane) mixed. Immediately after the mixture, after 60 min, 120 min and 180 min, the viscosity is calculated as the flow time ( DIN 53 211 , 4 mm DIN outlet cup at 23 ° C). The drying times T1, T2, T3 and T4 according to DIN 53 150 as well as the pendulum hardness [pendulum damping according to König ( DIN EN ISO 1522 )] when stored at room temperature and stored at 60 ° C. Table 1: Flow time [s] Without DBTL 1j 0 h 21 21 20 1 h 22 27 21 2 h 24 nm 25 3 h 26 nm 29

The flow time from a standard cup determined in Table 1 is representative of the measurement of the increase in viscosity which occurs in the reaction between isocyanate and hydroxyl groups. While Without the addition of catalyst, the reaction is very slow, the addition of DBTL within 2 h, the crosslinking to an extent that the processing makes impossible due to the viscosity increase. When compound 1j is added, no reaction is initially observed at room temperature because the catalyst is in its blocked form at room temperature. Table 2: Drying times for room temperature storage [h] Without DBTL 1j T1 3 2 3 T2 > 6 > 6 > 6 T3 > 6 > 6 > 6 T4 > 6 > 6 > 6

The drying time determined in Table 2 reflects the progress of crosslinking after application to a substrate. It can be clearly seen that both without and with catalyst, the paint film does not dry sufficiently at room temperature. Table 3: Drying times at 60 ° C storage [h] Without DBTL 1j T1 0.5 0.5 0.5 T2 1.5 0.5 0.5 T3 3.5 0.5 0.5 T4 4.5 1.5 1.5

The drying time determined in Table 3 reflects the progress of crosslinking after application to a substrate. The paint film is stored at 60 ° C for 30 min and the progress of the drying is followed at room temperature. It can be seen clearly that with the addition of a catalyst, the paint film cures much faster. In this connection, compound 1j reaches the level of comparison DBTL. Table 4: Pendulum hardness after 60 ° C storage [s] Without DBTL 1j 1d 115 100 158 3d 182 162 184 7d 190 178 192

The The pendulum hardness determined in Table 4 is used for determination the progress of crosslinking (after application to a substrate and storage for 30 min at 60 ° C) a longer period. One recognizes clearly that through Addition of compound 1j the final properties of the paint film clearly are reached sooner, so by an improved service life of the Catalyst can be assumed.

Example 20 with compound 1l

18.07 g Desmodur ^® XP2410 (HDI polyisocyanate of Messrs. Bayer MaterialScience AG, 23.5% NCO) are mixed with 50.56 g Desmophen ^® XP A2594 (Polyol Fa. Bayer MaterialScience AG, 3.40% OH) and 0.12 g of Compound 1l (10% by weight in dichloromethane). Immediately after the mixture, after 30 min, 60 min, 120 min and 240 min, the viscosity is calculated as the flow time ( DIN 53 211 , 4 mm DIN outlet cup at 23 ° C). The drying times T1, T3 and T4 according to DIN 53 150 when stored at room temperature and stored at 60 ° C. Table 5: Flow time [s] DBTL 1l 0 h 19 19 1 h 25 20 2 h 34 21

The flow time from a standard cup determined in Table 5 is representative of the measurement of the increase in viscosity which occurs in the reaction between isocyanate and hydroxyl groups. While the crosslinking leads to an increase in the viscosity when DBTL is added, no reaction is initially observed on addition of compound 1 l at room temperature, since the catalyst is in its blocked form at room temperature. Table 6: Drying times at room temperature storage [h] DBTL 1l T1 2.5 2.5 T3 > 6 > 6 T4 > 6 > 6

The drying time determined in Table 6 reflects the progress of crosslinking after application to a substrate. It can be clearly seen that with catalyst the paint film does not dry sufficiently at room temperature. Table 7: Drying times at 60 ° C storage [h] DBTL 1l T1 Immediately Immediately T3 5 6 T4 10 8.25

The in Table 7 certain drying time reflects the progress of Crosslinking after application to a substrate again. It is the Paint film stored for 30 min at 60 ° C and the progress of Drying at room temperature followed. One recognizes clearly that with the addition of compound 1l compared to DBTL a comparable Curing can be observed.

Investigation of catalytic activity in an MDI-based, non-foamed, elastic Polyurethane Systems

Recipe A

Comparative example without catalyst

200 g Desmodur ^® MS 192 (. MDI prepolymer from Bayer Material Science AG, 19.2% -NCO) are (with 170 g Baytec ^® VP.PU 20GE12 polyol from Bayer Material Science AG, OH number. 64 mg KOH / g) and 30 g of 1,4-butanediol at 50 ° C in a 500 ml tinplate can (diameter: 85 mm, height: 110 mm) mixed. The tinplate box is located in an oil bath tempered at 50 ° C. The temperature profile is followed by a thermocouple immersed in the reaction mixture.

Comparative example with 1,4-diazabicyclo [2.2.2] octane (Dabco) as catalyst (I)

200 g Desmodur ^® MS 192 (. MDI prepolymer from Bayer Material Science AG, 19.2% -NCO) are (with 170 g Baytec ^® VP.PU 20GE12 polyol from Bayer Material Science AG, OH number. 64 mg KOH / g), 30 g of 1,4-butanediol and 0.42 g (0.1%) of Dabco at 50 ° C in a 500 ml tin can (diameter: 85 mm, height: 110 mm). The tinplate box is located in an oil bath tempered at 50 ° C. The temperature profile is followed by a thermocouple immersed in the reaction mixture.

Comparative example with Dabco as catalyst (II)

200 g Desmodur ^® MS 192 (. MDI prepolymer from Bayer Material Science AG, 19.2% -NCO) are (with 170 g Baytec ^® VP.PU 20GE12 polyol from Bayer Material Science AG, OH number. 64 mg KOH / g), 30 g 1,4-butanediol and 0.05 g (0.013%) Dabco at 50 ° C in a 500 ml tinplate can (diameter: 85 mm, height: 110 mm) mixed. The tinplate box is located in an oil bath tempered at 50 ° C. The temperature profile is followed by a thermocouple immersed in the reaction mixture.

Comparative Example with Thorcat 535 (80% Phenyl-Hg-neodecanoate, 20% neodecanoic acid; Fa. Thor Especialidades, S.A.) as a catalyst

200 g Desmodur ^® MS 192 (. MDI prepolymer from Bayer Material Science AG, 19.2% -NCO) are (with 170 g Baytec ^® VP.PU 20GE12 polyol from Bayer Material Science AG, OH number. 64 mg KOH / g), 30 g of 1,4-butanediol and 0.42 g (0.1%) Thorcat 535 at 50 ° C in a 500 ml tinplate can (diameter: 85 mm, height: 110 mm) mixed. The tinplate box is located in an oil bath tempered at 50 ° C. The temperature profile is followed by a thermocouple immersed in the reaction mixture.

Example 21 with compound 1k

200 g Desmodur ^® MS 192 (. MDI prepolymer from Bayer Material Science AG, 19.2% -NCO) are (with 170 g Baytec ^® VP.PU 20GE12 polyol from Bayer Material Science AG, OH number. 64 mg KOH / g), 30 g 1,4-butanediol and 0.2 g (0.05%) compound 1k at 50 ° C in a 500 ml tinplate can (diameter: 85 mm, height: 110 mm) mixed. The tinplate box is located in an oil bath tempered at 50 ° C. The temperature profile is followed by a thermocouple immersed in the reaction mixture.

Example 22 with compound 1k

200 g Desmodur ^® MS 192 (. MDI prepolymer from Bayer Material Science AG, 19.2% -NCO) are (with 170 g Baytec ^® VP.PU 20GE12 polyol from Bayer Material Science AG, OH number. 64 mg KOH / g), 30 g of 1,4-butanediol and 0.12 g (0.03%) of compound 1k at 50 ° C in a 500 ml tinplate can (diameter: 85 mm, height: 110 mm) mixed. The tinplate box is located in an oil bath tempered at 50 ° C. The temperature profile is followed by a thermocouple immersed in the reaction mixture.

From the in 18 shown temperature curves show that the catalytic activity of compound 1k in Formulation A significantly delayed compared to Dabco, ie only begins at higher temperature.

From the in 19 shown temperature curves show that the latent character of compound 1k in Formulation A is at least as pronounced as that of the established, Hg-containing latent catalyst Thorcat 535th

Recipe B

Comparative example without catalyst

140 g Desmodur ^® MS 192 (. MDI prepolymer from Bayer Material Science AG, 19.2% -NCO) are (with 235 g Baytec ^® VP.PU 20GE12 polyol from Bayer Material Science AG, OH number. 64 mg KOH / g) and 15 g of 1,4-butanediol at 50 ° C in a 500 ml tinplate can (diameter: 85 mm, height: 110 mm) mixed. The tinplate box is located in an oil bath tempered at 50 ° C. The temperature profile is followed by a thermocouple immersed in the reaction mixture.

Comparative example with Dabco as catalyst (I)

140 g Desmodur ^® MS 192 (. MDI prepolymer from Bayer Material Science AG, 19.2% -NCO) are (with 235 g Baytec ^® VP.PU 20GE12 polyol from Bayer Material Science AG, OH number. 64 mg KOH / g), 15 g of 1,4-butanediol and 0.6 g (0.15%) of Dabco at 50 ° C in a 500 ml tinplate can (diameter: 85 mm, height: 110 mm) mixed. The tinplate box is located in an oil bath tempered at 50 ° C. The temperature course is followed with a submerged in the reaction mixture thermocouple.

Comparative example with Dabco as catalyst (II)

140 g Desmodur ^® MS 192 (. MDI prepolymer from Bayer Material Science AG, 19.2% -NCO) are (with 235 g Baytec ^® VP.PU 20GE12 polyol from Bayer Material Science AG, OH number. 64 mg KOH / g), 15 g 1,4-butanediol and 0.075 g (0.019%) Dabco at 50 ° C in a 500 ml tinplate can (diameter: 85 mm, height: 110 mm) mixed. The tinplate box is located in an oil bath tempered at 50 ° C. The temperature profile is followed by a thermocouple immersed in the reaction mixture.

Comparative Example with Thorcat 535 as catalyst

140 g Desmodur ^® MS 192 (. MDI prepolymer from Bayer Material Science AG, 19.2% -NCO) are (with 235 g Baytec ^® VP.PU 20GE12 polyol from Bayer Material Science AG, OH number. 64 mg KOH / g), 15 g of 1,4-butanediol and 0.21 g (0.054%) Thorcat 535 at 50 ° C in a 500 ml tinplate can (diameter: 85 mm, height: 110 mm) mixed. The tinplate box is located in an oil bath tempered at 50 ° C. The temperature profile is followed by a thermocouple immersed in the reaction mixture.

Example 23 with compound 1k

140 g Desmodur ^® MS 192 (. MDI prepolymer from Bayer Material Science AG, 19.2% -NCO) are (with 235 g Baytec ^® VP.PU 20GE12 polyol from Bayer Material Science AG, OH number. 64 mg KOH / g), 15 g 1,4-butanediol and 0.075 g (0.019%) compound 1k at 50 ° C in a 500 ml tinplate can (diameter: 85 mm, height: 110 mm) mixed. The tinplate box is located in an oil bath tempered at 50 ° C. The temperature profile is followed by a thermocouple immersed in the reaction mixture.

Example 24 with compound 1k

140 g Desmodur ^® MS 192 (. MDI prepolymer from Bayer Material Science AG, 19.2% -NCO) are (with 235 g Baytec ^® VP.PU 20GE12 polyol from Bayer Material Science AG, OH number. 64 mg KOH / g), 15 g 1,4-butanediol and 0.04 g (0.01%) compound 1k at 50 ° C in a 500 ml tinplate can (diameter: 85 mm, height: 110 mm) mixed. The tinplate box is located in an oil bath tempered at 50 ° C. The temperature profile is followed by a thermocouple immersed in the reaction mixture.

From the in 20 shown temperature profiles show that the catalytic activity of compound 1k in Formulation B significantly delayed compared to Dabco, ie only begins at higher temperature.

From the in 21 shown temperature curves show that the latent character of compound 1k in Formulation B is at least as pronounced as that of the established, Hg-containing latent catalyst Thorcat 535th

Investigation of casting time (pot life) and demolding time

The Casting time is the time after which the reaction mixture when pouring onto a flat steel plate the flow behavior Significantly changes due to noticeable viscosity increase.

The Deformation time is the time after which the specimen manually pressed out of the steel cylinder without deformation can be.

Comparative example with Dabco as a catalyst

400 g Desmodur ^® MS 192 (. MDI prepolymer from Bayer Material Science AG, 19.2% -NCO) are (with 340 g Baytec ^® VP.PU 20GE12 polyol from Bayer Material Science AG, OH number. 64 mg KOH / g), 60 g 1,4-butanediol and 0.2 g (0.025%) Dabco at 50 ° C in a 1.5 1 tinplate can (diameter: 120 mm, height: 135 mm) mixed. The mixture is poured into a 60 ° C tempered and provided with release agent (Indrosil 2000) hollow steel cylinder (diameter: 40 mm, height: 80 mm). The specimen is removed. The casting time is 75 s, the demolding time 10 min.

Comparative Example with Thorcat 535 as catalyst

400 g Desmodur ^® MS 192 (. MDI prepolymer from Bayer Material Science AG, 19.2% -NCO) are (with 340 g Baytec ^® VP.PU 20GE12 polyol from Bayer Material Science AG, OH number. 64 mg KOH / g), 60 g of 1,4-butanediol and 0.84 g (0.105%) Thorcat 535 at 50 ° C in a 1.5 1 tinplate can (diameter: 120 mm, height: 135 mm) mixed. The mixture is poured into a 60 ° C tempered and provided with release agent (Indrosil 2000) hollow steel cylinder (diameter: 40 mm, height: 80 mm). The specimen is removed. The casting time is 130 s, the demolding time is 20 min.

Example 25 with compound 1k

400 g Desmodur ^® MS 192 (. MDI prepolymer from Bayer Material Science AG, 19.2% -NCO) are (with 340 g Baytec ^® VP.PU 20GE12 polyol from Bayer Material Science AG, OH number. 64 mg KOH / g), 60 g of 1,4-butanediol and 0.16 g (0.02%) compound 1k at 50 ° C in a 1.5 1 tinplate can (diameter: 120 mm, height: 135 mm) mixed. The mixture is poured into a 60 ° C tempered and provided with release agent (Indrosil 2000) hollow steel cylinder (diameter: 40 mm, height: 80 mm). The specimen is removed. The casting time is 120 s, the demolding time 9 min.

in the Compared to Dabco allows compound 1k at slightly shorter demolding time a significantly longer Casting time. Compared to Thorcat 535 allows connection 1k for a slightly shorter casting time a much shorter demolding time.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - EP 989146 A1 [0004]
• - EP 1354903 A1 [0005]
• - WO 2006/030029 A1 [0006]

Cited non-patent literature

• - Mayr, M .; Wurst, K .; Ongania, K.-H .; Buchmeiser, MR Chem. Eur. J. 2084, 10, 1256-1266 [0036]
• - Alder, RW; Blake, ME; Bortolotti, C .; Bufali, S .; Butts, CP; Linehan, E .; Oliva, JM; Orpen, G .; Quayle, MJ Chem. Commun. 1999, 241-242 [0038]
• - Mayr, M .; Wurst, K .; Ongania, K.-H .; Buchmeiser, MR Chem. Eur. J. 2004, 10, 1256-1266 [0043]
• - Arduengo, AJ; Krafczyk, R .; Schmutzler, R. Tetrahedron 55 (1999) 14523-14534 [0045]
• - Arduengo, AJ; Krafczyk, R .; Schmutzler, R. Tetrahedron 55 (1999) 14523-14534 [0047]
• - DIN 53 211 [0068]
• - DIN 53 150 [0068]
• - DIN EN ISO 1522 [0068]
• - DIN 53 211 [0069]
• - DIN 53 150 [0069]
• - DIN EN ISO 1522 [0069]
• - DIN 53 211 [0070]
• - DIN 53 150 [0070]
• - DIN EN ISO 1522 [0070]
• - DIN 53 211 [0075]
• - DIN 53 150 [0075]

Claims (12)

Catalysts for the synthesis of polyurethanes comprising compounds of general formula I:

in which R _{1 is} a radical from the series: C ₁ -C ₁₀ -alkyl, C ₂ -C ₁₀ -alkenyl, C ₃ -C ₁₂ -cycloalkyl, C ₆ -C ₁₀₀ -polyoxyalkylene, C ₅ -C ₁₀ -aryl or C ₅ -C ₁₀ -Hetaryl, preferably a radical methyl, ethyl, n-propyl, iso-propyl, tert-butyl, neo-pentyl, iso-amyl, cyclohexyl, phenyl, 2,6-dimethylphenyl, 2 , 6-diisopropylphenyl, mesityl and particularly preferably iso-propyl, phenyl is 2,6-dimethylphenyl, 2,6-diisopropylphenyl or mesityl, in which R _{2 is} a radical from the series: C ₁ -C ₁₀ -alkoxy, C C ₅ -C ₁₂ -cycloalkoxy, C ₆ -C ₁₀₀ -polyoxyalkylene, C ₅ -C ₁₀ -aryloxy, C ₁ -C ₁₀ -perfluoroalkyl, C ₁ -C ₁₀ -perchloroalkyl, partially fluorinated C ₁ -C ₁₀ -alkyl, partially chlorinated C C ₁ -C ₁₀ -alkyl, perfluorinated C ₅ -C ₁₀ -aryl, partially fluorinated C ₅ -C ₁₀ -aryl, perchlorinated C ₅ -C ₁₀ -aryl, partially chlorinated C ₅ -C ₁₀ -aryl, preferably a methoxy radical, Ethoxy, iso -propoxy, tert -butyloxy, iso-butyloxy, 2-ethylhexyloxy, phenyloxy, cyclohexyloxy, CF ₃ , CCl ₃ , pentafluoro phenyl, tetrafluorophenyl, in which A and D are independently of one another a methylene radical, CHR ₃ , and CR ₃ R ₃ or A and D taken together represent a radical of the series: propylene, 1,2-phenylene or with a C ₁ -C ₁₀ -Alkyl, C ₂ -C ₁₀ -alkenyl, C ₃ -C ₁₂ -cycloalkyl, C ₆ -C ₁₀₀ -polyoxyalkylene, C ₅ -C ₁₀ -aryl or C ₅ -C ₁₀ -Hetarylgruppe substituted 1, 2-phenylene, -CH = N-, -CH ₂ -NR ₃ -, vinylene, -CH ₂ = CHR ₃ -, -CHR ₃ = CH ₂ -, -CHR ₃ = CHR ₃ - are, where the radicals R _{3 are} independent of each other have the meaning given above for R ₁ , and in which X represents oxygen, sulfur or -NR ₃ '-, where R ₃ ' has the meaning given above for R ₁ , or compounds of general formula II:

where R _{4 is} the same as defined above in formula I, R ₁ , X 'is X, A' is A and B 'are as defined for B, or compounds formed by the reaction of a metal salt of the metals magnesium, calcium, yttrium, Lanthanum, titanium, zirconium, manganese, iron, cobalt, zinc, aluminum, tin, with an anion of the series fluoride, chloride, bromide, sulfonate, trifluoromethanesulfonate, methanesulfonate, benzenesulfonate, para-toluenesulfonate, carboxy-C ₁ -C ₁₀ -alkyl Carboxy-C ₃ -C ₁₀ -cycloalkyl, carboxy-C ₂ -C ₁₀ -alkenyl, C ₁ -C ₁₀ -alkoxy, acetylacetonate, trifluoroacetylacetonate or hexafluoroacetylacetonate, with N-heterocyclic compounds of the general structure I; or with N-heterocyclic compounds of general structure II; or with N-heterocyclic compounds of general structure III,

where R _{5 is} the same as in R ₁ above, X 'is X, A' is A and B 'is B, and Y is F, Cl, Br, I, BF ₄ or SbF ₆ . Catalysts according to claim 1, characterized in that in the formulas I, II or III, the radicals R ₁ , R ₃ , R ₄ , and R _{5 are} independently of one another a radical: methyl, ethyl, n-propyl, iso-propyl, tert Butyl, neo-pentyl, iso-amyl, cyclohexyl, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl or mesityl, and R _{2 is} a radical methoxy, ethoxy, iso-propoxy, tert-butyloxy, iso-butyloxy, 2-ethylhexyloxy, phenyloxy, cyclohexyloxy, CF ₃ , CCl ₃ , pentafluorophenyl, tetrafluorophenyl, and A and B and A 'and B' each independently taken together represent an ethylene-vinylene or propylene radical , Catalysts according to claim 2, characterized in that in the formulas I, II or III the radicals R ₁ , R ₃ , R ₄ and R _{5 are} independently of one another iso-propyl, phenyl or mesityl. Catalysts according to one of claims 1 to 3, characterized in that they are reaction products, resulting from the reaction of a metal salt of the series: zirconium, Zinc, aluminum or stannous chloride, bromide, acetate or acetylacetonate with a compound of the general formula I, II or III become. Catalysts according to one of claims 1 to 4, characterized in that they are selected from the series of the compounds of formulas 1a to 1q:

Catalysts according to one of claims 1 to 5, characterized in that the catalysts thermally can be activated. Process for the preparation of polyurethanes by the reaction of polyisocyanates with compounds with Isocyanate-reactive hydrogen atoms, in particular with polyhydroxy compounds in the presence of catalysts and optionally auxiliaries and additives at optionally elevated temperature, characterized that as catalysts, the catalysts according to any one of claims 1 to 6 are used. Method according to claim 7, characterized in that that the reaction temperature is at least 60 ° C. Use of the catalysts according to one of the claims 1 to 6 for the preparation of polyisocyanate polyaddition products. Curable polyisocyanate composition at least having 10 to 90 parts by weight, preferably 20 to 80 parts by weight Polyisocyanates and 90 to 10 parts by weight, preferably 80 to 20 parts by weight of compounds with respect to isocyanates reactive hydrogen atoms, in particular polyhydroxy compounds and 0.001 to 5 parts by weight, preferably 0.01 to 2.5 parts by weight one of the catalysts of claims 1 to 6, in which the sum of all parts by weight must be 100. Use of the composition according to claim 10 for the production of coatings, adhesives, sealants or porous or non-porous moldings, especially foams or paints. Compounds of the formulas 1g, 1j, 1k, 1l, 1m, 1o, and 1p