DE102006005938A1 - Low emission polyurethanes - Google Patents

Abstract

The invention relates to polyurethanes, in particular low-emission polyurethanes with good dynamic-mechanical properties after hydrolysis aging, obtainable by reacting an isocyanate component with a polyol component, characterized in that a polyurethane catalyst (i) and a supported catalyst scavenger in deactivated form (ii) are added to the reaction, wherein the supported catalyst trap (ii) can be activated thermally. The invention also relates to a method for producing the polyurethane according to the invention and its use for producing the interior fittings of motor vehicles, furniture, carpets or mattresses.

Description

The Invention relates to polyurethanes, especially low-emission polyurethanes, available through Reaction of an isocyanate component with a polyol component, characterized in that the reaction is a polyurethane catalyst (i) and a carried one catalyst catcher in deactivated form (ii), wherein the supported catalyst scavenger (ii) is added is thermally activated. The invention further relates to a method for the preparation of the polyurethane according to the invention and its Use for the manufacture of the interior of motor vehicles, of furniture, carpets or mattresses and shoe soles.

center The nineties saw growing pressure from automobile manufacturers on the plastic producers, emission-free materials for the automotive industry to deliver. The most important class of issuers was initially predominantly the amine catalysts (tertiary amines) as problematic Substances have been identified as these in addition to the emissions in addition, when PVC films have been combined with polyurethanes, discoloration led. This was very pronounced in light-colored dashboards and in sun visors or door side panels, the longer one Time of exposure to sunlight.

Of the most important focus in the development of new polyurethane materials for the Automotive interior was therefore a significant reduction emissions caused by the amine catalysts too to reach. Size Successes to the solution The emission problem could be achieved by the fact that chemically modified the catalysts such that they have at least one functional reactive group. These functional groups are reactive towards Isocyanate groups and are during the polymerization incorporated into the forming polymer network. In this way, the catalysts in the polyurethane material fixed and can no longer while emissions test from the foam and emissions contribute.

Most of the incorporable catalysts known in the art have primary and / or secondary hydroxyl and / or amino groups which are generally separated from the catalytic center by a short spacer based on an alkyl chain (CH ₂ groups). Examples of incorporable catalysts are in EP 0 747 407 described.

Also are modified, installable catalysts known. So describes WO 94/2525 modified amine catalysts by reacting a reactive tertiary Amines and polyols can be obtained with isocyanate compounds. aim the modification is an increase the catalytic activity.

WHERE 02/40568 also describes modified amine catalysts which to improve the solubility properties by reacting a reactive tertiary amine and polyols with Isocyanate compounds are obtained, wherein as isocyanate a polyisocyanate the diphenylmethane series with a functionality of 2.5 to 4.0 used becomes.

It However, it turns out that many of the known in the art, installable catalysts are incorporated into the polyurethane, under the conditions of the emission tests at higher temperatures (from approx. 100 C), however, are partially rebuilt and thus emissions contribute. Furthermore, the known, installable catalysts the effect that they are very unlike volatile catalysts have a negative impact on the aging properties of PUR materials. By the rebuilding of the catalysts at higher temperatures becomes this obviously favored negative behavior.

As other plastics too are subjected to aging processes by polyurethane, which generally worsens with increasing time of the performance characteristics. Significant aging effects are, for example, hydrolysis, photooxidation and thermooxidation, the to bond breaks lead in the polymer chains. In the case of polyurethanes, it is specifically the action of moisture, in particular in conjunction with increased Temperature, a hydrolytic cleavage of the urethane and urea bonds result.

These Split manifests itself not only in a significant deterioration of the performance characteristics, but leads also for the formation of amines, in particular aromatic amines, such as Toluenediamine (TDA) and diphenylmethanediamine (MDA), and aliphatic Amines such as hexamethylenediamine (HDA) and isophoronediamine (IPDI): The emissions could be achieved by using installable catalysts Although significantly reduced, it was observed that due to the use of these catalysts, the hydrolytic but also the thermal aging behavior deteriorated significantly in comparison to identical built-up polyurethanes, in which Preparation non-installable catalysts were used. The dynamic-mechanical properties after wet-heat aging fell stronger than in the reaction acceleration and control of the polymerization by non-installable catalysts. In addition, when using these catalysts after damp heat aging larger quantities found on aromatic amines.

at Foams with amine catalysts that are not functional In contrast, the amines usually escape already in groups short time after completion, or during the aging of the foam. Lead with such foams z. B. strong hydrolytic loads to much lower Amine contents.

Especially TDI based flexible polyurethane foam, in their manufacture installable catalysts are used, indicate a dramatic Waste of dynamic-mechanical properties after aging simulation tests on.

Based On the observations that many installable catalysts to polyurethane materials with poorer dynamic-mechanical properties after aging tests to lead, it was hypothesized that the installable catalysts, which remain in the material while the hydrolytic or thermal aging the cleavage catalyze the urethane and urea bonds. It should be noted, that a catalyst not only the outward but also the reverse reaction catalyzes and the more intense, the higher the temperature at the Aging is. The catalysts incorporated in the polymer can be used during the hydrolytic aging catalyze their own cleavage. Therefore These catalysts are free to move after release in the plastic and are able to support the cleavage of other bonds. The Polymer network becomes by the freely movable in the plastic catalysts destroyed faster, resulting in poorer dynamic-mechanical properties makes noticeable.

Around For polyurethane materials, the release of aromatic amines to reduce emissions while achieving low emissions it is necessary to find additives containing the catalysts in the foam fix without you can support the split and the above addition, are still capable of forming aromatic amines from the To fix foam or the formation of aromatic amines under climatic conditions To prevent stress completely. This should also be a significant improvement the dynamic-mechanical properties after hydrolysis aging to lead.

The Invention is intended to solve this problem by helping to to produce low-emission or emission-free polyurethanes which good dynamic mechanical properties even after hydrolytic aging demonstrate. Furthermore, the release of aromatic amines from polyurethanes be prevented.

Solutions to Improvement of the dynamic-mechanical properties of polyurethanes After hydrolysis aging were achieved, inter alia, that the compounds are added to compounds which form acid groups by hydrolysis and lead to the protonation of the catalytically active center. The Catalytically active center is usually the lone pair of electrons a tertiary amine, that by this measure is converted into an ammonium salt, that is no longer catalytically active. Solutions that will follow this path for example described in WO 00/011059.

In In this context, however, the authors primarily considered that the aging process liberated aromatic amines and intended a solution to develop, which leads to the reduction of aromatic amines.

It showed, however, that even with these approaches, the dynamic mechanical properties After hydrolysis aging turned out to be worse than identical ones Polyurethane materials produced using non-installable catalysts were. Furthermore, these additives are often already used during the Hydrolyzed, resulting in longer reaction times, the have a negative impact on the production process, because the cycle times To prolong oneself. About that In addition, the short-chain additives contribute to the increase in emissions, so that the emissions problem persists or is exacerbated.

One further solution consisted of the catalyst with more than one installable functional Group to make the expansion even more unlikely allow. Also these approaches did not supply materials whose dynamic mechanical properties After hydrolysis aging identical to those without non-installable catalysts were.

It is also known, the hydrolysis and aging resistance the polyurethanes by addition of inhibitors or co-reactants for the Improve degradation products. As inhibitors or co-reactants can according to WO 00/66643 α, β-unsaturated compounds, Carboxylic acids, Carboxylic acid derivatives, Ketones or aldehydes are used

According to DE-A-199 28 687 can Lactones, lactams and / or cyclic esters, according to DE-A-199 28 688 cyclic sulfonic and / or sulfones, according to DE-A-199 28,675 salts of metals of the I., II. And / or VIII subgroup and according to DE-A-199 28,689 organic molecular weight cyclic compounds be used from 200 to 3000 g / mol as inhibitors.

The compounds mentioned cause in the polyurethanes both blocking the ami niche urethanization catalysts as well as a complexation of amines, which were formed in the hydrolytic cleavage of urethane bonds.

The Inhibitors are usually the polyol component or the isocyanate component added before the reaction in pure form. The disadvantage here is that they are already before or during the preparation of the polyurethanes with the amine catalysts or as chain extenders reacted amines react. This can lead to disruptions in the network structure Polyurethanes and / or lead to a slowing down of the reaction. This leads to longer demolding times of the products and thus to a loss of efficiency.

WHERE 03/99895 describes inhibitors mentioned above, wherein the Release of the inhibitors only after extensive implementation should be made of polyol component with polyisocyanate component. It has been shown that the release of the inhibitors as required largely only after the end of the polyurethane reaction takes place, however the unfolding of the efficacy is still capable of improvement. The inhibitors have within the polymer network still has a great deal of mobility, especially under the high temperatures of the aging simulation tests and emissions test. Since it is interaction between inhibitor and catalysts is about chemical equilibria, especially at higher temperatures shifted the balance to the side of the free connections. The catalysts released in the following can be aged support and are detected in the emissions test.

Of Furthermore, it has been shown that especially in the presence of metals and metal ions in free form (not supported) contribute these metal ions higher temperatures accelerate thermooxidative aging processes rapidly. This initially leads to discoloration and subsequently to break down the polymer network, leaving such free metal inhibitors the thermooxidative stability of the PUR material deteriorate significantly and not used can be. But not only in aging test but also in the production, e.g. of block foams can These metal inhibitors are not used because of the high Temperatures of the foaming process supports thermo-oxidative processes become the core discoloration to lead.

One further exceedingly problematic disadvantage of said in wax embedded inhibitors in the insufficient Storage stability. If the encapsulated inhibitors are added to a polyol mixture, Thus, these inhibitors diffuse successively due to the concentration gradient through the protective layer into the polyol component. It comes to blocking the catalysts with which the polymerization process influenced so far can be that no specification-compliant material produced more can be.

task The invention was therefore to provide polyurethanes, on the one hand advantageous in terms of emissions, especially in terms of emissions of fleeting Catalyst components such as tertiary amines are. It was further Task to provide polyurethanes, on the other hand advantageous in terms of dynamic and mechanical properties after hydrolytic or thermal aging and not at higher temperatures too discoloration to lead. About that It was another object of the present invention to find a way around during the to fix the hydrolysis formed aromatic amines in the foam. Farther It was an object of the present invention to identify a way the reaction properties of PUR systems in the processing process constantly guaranteed and not affected by the storage conditions. Especially It was an object of the invention to provide polyurethanes which advantageous properties with respect to hydrolytic Aging, favorable dynamic properties, i. Rebound resilience, compression set and / or train and tensile strengths with simultaneous low emission of catalyst components and released aromatic amines. In terms of issue, it was particularly task of the invention to provide polyurethanes which are at elevated temperature are low in emissions. Under increased Temperature here is a residence time of 1 hour at about 80 ° C or higher to understand.

The Tasks have been solved be that the polyurethane reaction, i. preferably the reaction from isocyanate and polyol, a supported catalyst scavenger (ii) is added in a deactivated form, the thermally activated is.

The invention therefore provides a polyurethane obtainable by reacting an isocyanate component with a polyol component, characterized in that the reaction
a polyurethane catalyst (i) and
a supported catalyst scavenger in deactivated form (ii)
is added, wherein the supported catalyst scavenger (ii) is activatable, preferably thermally activated.

The invention further provides a process for preparing the polyurethanes according to the invention by reacting an isocyanate component with a polyol component, characterized in that the reaction is a catalyst (i) and a supported catalyst scavenger in deactivated form (ii) is added, wherein the supported Kata lysator catcher is activated.

Also The invention relates to the use of the polyurethanes according to the invention Production of interior decoration of means of transport, for manufacture of furniture, for the production of carpets, for the production of mattresses or for Production of shoe soles.

Furthermore, the subject matter of the invention is a catalyst system comprising
a polyurethane catalyst (i) and
a supported catalyst scavenger in deactivated form (ii); and its use for the production of low-emission polyurethanes.

Further The invention relates to a catalyst starting material (ii-a), the on a carrier (ii-b) applied and surrounded by a protective layer (ii-c); such as its use for the production of low emission polyurethanes.

Finally, the invention relates to a process for the reduction of emission from polyurethanes, characterized in that already in the preparation of the polyurethane, a polyurethane catalyst (i) and
a supported catalyst scavenger in deactivated form (ii)
the reaction of isocyanate component with polyol component is added,
wherein the deactivated supported catalyst scavenger (ii) is activated during the reaction so that a catalyst-catalyst material complex (iii) is present in the resulting polyurethane foam.

The polyurethane according to the invention is available by reacting an isocyanate component with a polyol component.

• a) Polyisocyanate
• b) Verbindungen mit gegenüber Isocyanate reaktiven Wasserstoffatomen, bevorzugt Polyole,
• c) erfindungsgemäßes Katalysatorsystem, enthaltend ein Polyurethankatalysator (i) und ein geträgerter Katalysatorfänger in deaktivierter Form (ii)
• d) Treibmittel, und
• e) Zusatzstoffe.

Isocyanate component and polyol component may contain the following components:

• a) polyisocyanates
• b) compounds with isocyanate-reactive hydrogen atoms, preferably polyols,
• c) Inventive catalyst system comprising a polyurethane catalyst (i) and a supported catalyst scavenger in deactivated form (ii)
• d) propellant, and
• e) additives.

The Contains isocyanate component preferably polyisocyanates, optionally in the form of isocyanate prepolymers available. The polyol component contains compounds with isocyanate-reactive Groups, preferably polyols. The components c), d) and e) can both the isocyanate and the polyol component added before the reaction become. They are preferred before the reaction of the polyol component added.

at the for the polyurethanes according to the invention used polyisocyanates (a) are common in the polyurethane field Isocyanates. In general, aliphatic, cycloaliphatic, arylaliphatic and aromatic polyfunctional isocyanates.

Prefers become the technically easily accessible used aromatic polyisocyanates. Examples of this are 2,4- and 2,6-tolylene diisocyanate (TDI) and any mixtures thereof isomers; and, where appropriate, in smaller quantities technically produced positional isomers of toluene diisocyanates. Also are 2,2'- and 2,4'- and 4,4'-diphenylmethane diisocyanate and any Mixtures of these isomers, mixtures of 2,2'-2,4'-, 4,4'-diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates (PMDI-MDI) are preferred. Furthermore, naphthylene diisocyanate (NDI) is preferred. Especially preferred are TDI, MDI and / or PMDI. Also possible are mixtures of toluene diisocyanates and crude MDI, mixtures of toluene diisocyanates and isomers of Diphenylmethane diisocyanates.

Also preferred are technically easily accessible aliphatic polyisocyanates. Examples of these are hexamethylene diisocyanate (HDI) and hexamethylene diisocyanate trimers. Furthermore, isophorone diisocyanate (IPDI).

alternative can Other polyisocyanates are used. Examples are tetramethylene diisocyanate, Tetramethylene diisocyanate trimers, 4,4'-methylenebis (cyclohexyl) diisocyanate, Xylylene diisocyanate, dodecyl diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, Isocyanatomethyl-1-methylcyclohexyl isocyanate, 1,4-diisocyanato-4-methylpentane, diisocyanate 2,4'-methylenebis (cyclohexyl) and 4-methylcyclohexane-1,3-diisocyanate (H-TDI).

The Polyisocyanates (a) can also be used in the form of Polyisocyanatprepolymeren. These Prepolymers are known in the art. The production takes place in a manner known per se, for example by the aforementioned polyisocyanates (a), for example at temperatures of about 80 ° C, with below described Polyols (b) are reacted to the prepolymer. The polyol-polyisocyanate ratio becomes generally chosen the NCO content of the prepolymer is 8 to 30% by weight, preferably 10 to 28 wt .-%, particularly preferably 13 to 25 wt .-% is.

Compounds with isocyanate-reactive hydrogen atoms (b) are Ver compounds in question, the reactive groups selected from OH groups, SH groups, NH groups, NH ₂ groups and CH-acidic groups, such as β-diketo groups, carry in the molecule. Thus, depending on the choice of component (b), the term "polyurethanes" in the context of this invention comprises not only compounds which have urethane bonds in a strictly chemical sense, but the term "polyurethanes" generally encompasses polyisocyanate polyaddition products obtained by reacting the constituents (a ) and (b) are available. If component (b) has, for example, NH ₂ groups, polyureas, for example, form as resulting polyisocyanate polyaddition products.

Prefers be as component (b) compounds having a functionality of 1.8 to 8, preferably 2 to 6, and a molecular weight of 100 used to 10,000, preferably from 200 to 7,000. Have proven e.g. Polyether polyamines and / or preferably polyols selected from the Group of polyether polyols, polyester polyols, polythioether polyols and polyester amides; or mixtures thereof. Furthermore, polyacrylate polyols or polyalkylan polyols.

Preferably Polyester polyols and / or polyether polyols are used.

• (b-1) Polyesterpolyole (b-1-PESOL) und/oder Polyetherpolyole (b-1-PEOL),
• (b-2) Polymerpolyole, und
• (b-3) Kettenverlängerungsmittel.

In a preferred embodiment, component (b) comprises one or more of the following parts:

• (b-1) polyester polyols (b-1-PESOL) and / or polyether polyols (b-1-PEOL),
• (b-2) Polymer polyols, and
• (b-3) Chain extender.

suitable Polyester polyols (b-1-PESOL) are mostly obtained by condensation of polyfunctional alcohols, preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, for example hexanediol, with polyfunctional carboxylic acids with 2 to 12 carbon atoms, for example adipic acid and / or phthalic acid. The polyester alcohols used usually have a functionality between 2 and 6, preferably between 2 and 4.

The used polyester polyols usually have a molecular weights from 400 to 8000 g / mol, preferably from greater than 600 to 5000 g / mol, and in particular 1200 to 3500 g / mol.

suitable Polyether polyols (b-1-PEOL) are generally known in the art Process, for example by anionic polymerization of a or more alkylene oxides, preferably selected from propylene oxide (PO) and Ethylene oxide (EO), but also produced butylene oxide. Catalyzed the reaction usually with alkali hydroxides, such as sodium or potassium hydroxide. Furthermore, will the reaction usually at least one starter molecule, which preferably contains 2 to 6 reactive hydrogen atoms bound added.

When Polyetherols (b-1-PEOL) can also so-called low-unsaturated Polyetherols are used. Under low unsaturated Polyols are in the context of this invention, in particular polyether alcohols with a content of unsaturated compounds of less than 0.02 meq / g, preferably less than 0.01 meq / g, understood. Such polyether alcohols are usually obtained by addition of alkylene oxides, in particular ethylene oxide, propylene oxide and mixtures thereof at least difunctional alcohols in the presence of so-called double metal cyanide catalysts produced.

The Alkylene oxides can individually, alternately in succession or as mixtures. The use of an EO / PO mixture leads to a polyether polyol with statistical PO / EO unit distribution. It is possible to enter first Use PO / EO mixture and then only use PO or EO before termination of the polymerization, then receive a polyether polyol with PO or EO endcap.

When starter molecules For example: water, organic dicarboxylic acids, diamines, such as. optionally mono- and dialkyl-substituted ethylenediamine, Diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, and / or 1,3- or 1,4-butylenediamine. As starter molecules further contemplated are: alkanolamines, e.g. Ethanolamine, N-methyl and N-ethylethanolamine, dialkanolamines, e.g. diethanolamine, N-methyl and N-ethyldiethanolamine and trialkanolamines such as e.g. triethanolamine and ammonia. Further used as starter molecules are two-, trihydric or tetrahydric alcohols, such as ethanediol, 1,2-propanediol and -1.3, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, Glycerol, trimethylolpropane and / or pentaerythritol.

The used polyether polyols usually have a molecular weight from 200 to 12,000 g / mol, preferably greater than 400 to 8,000 g / mol, and in particular 800 to 6600 g / mol.

The Polyether polyols are individually or in the form of a mixture two or more of the above-mentioned polyether polyols.

As component (b-2) so-called polymer polyols, which are also often referred to as graft polyols used. These polymer polyols are usually prepared by free-radical polymerization of suitable olefinic monomers, for example styrene, acrylonitrile, acrylates and / or Acrylamide, prepared in a serving as a graft carrier Polyetherol.

In a preferred embodiment are used as monomers acrylonitrile, styrene, in particular styrene and Acrylonitrile in the ratio between 1: 1 to 3: 1, and optionally in the presence of further Monomers, a macromer, a moderator and using a Radical initiator, usually azo or peroxide compounds, in one Polyetherol or polyesterol produced as a continuous phase.

When Trägerpolyetherole come above polyetherols into consideration.

The Polymer polyols (b-2) are preferably mixed with polyether polyols (b-1-PEOL). In a preferred embodiment is the polymer polyol (b-2) in an amount of 5 to 40 wt .-%, preferably from 6 to 28% by weight, more preferably from 8 to 18 Wt .-%, based on the total weight of component (b), before.

When Component (b-3) optionally further comprises chain extenders used. Suitable chain extenders are known in the art. Preference is given to 2-functional Alcohols with molecular weights below 400 g / mol, in particular in Range of 60 to 150 g / mol, used. Examples are ethylene glycol, 1,3-propanediol, diethylene glycol, 1,4-butanediol, pentanediol, hexanediol, glycerol or trimethylolpropane, as well as mixtures thereof. Preference is given to ethylene glycol and butanediol, as well as trimethylolpropane.

The Chain extender becomes common in an amount of from 1 to 20% by weight, preferably from 3 to 15% by weight, particularly preferably from 4 to 10 wt .-%, based on the total weight component (b).

Of the Reaction of isocyanate component and polyol component becomes Inventive catalyst system (c) added. The catalyst system according to the invention contains a polyurethane catalyst (i) and a supported catalyst scavenger in deactivated form (ii).

The Inventive catalyst system (c) contains at least one polyurethane catalyst (i) which is a reaction of Polyisocyanates (a) with compounds having at least two towards isocyanate groups catalyses reactive hydrogen atoms (b).

Prefers be polyurethane catalysts (i), which is a reaction of a Isocyanate group having an OH-functional group to a urethane bond catalyze, so-called crosslinking catalysts, and catalysts, which in particular assist the reaction of water with isocyanate to carbamic acid, so named blowing catalysts used. Furthermore, a mixture from crosslinking catalysts and blowing catalysts are preferred.

It be two groups for preferred embodiments of the polyurethane catalysts. A preferred embodiment contains polyurethane catalysts based on organic amines, in particular based on tertiary Amines. The other preferred embodiment contains organometallic Polyurethane catalysts.

at The organic amines are usually monomolecular Compounds with at least one amino group, preferably at least a tertiary Amino group. Usually the organic amines have not more than 4 amino groups. Prefers they have a molecular weight of 50 to 1400 g / mol, more preferably from 60 to 750 g / mol.

Examples of suitable compounds are triethylamine, triethylenediamine, tributylamine, dimethylbenzylamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N, N ', N'-tetramethylhexane. 1,6-diamine, dimethylcyclohexylamine, pentamethyldipropylenetriamine, pentamethyldiethylenetriamine, 3-methyl-6-dimethylamino-3-azapentol, dimethylaminopropylamine, 1,3-bisdimethylaminobutane, bis (2-dimethylaminoethyl) ether, N, N, N-trimethyl- N-hydroxyethyl bis (aminoethyl ether), N, N, N'-trimethylaminoethylethanolamine, 2, - (2- (n, N-dimethylamino) ethoxy) ethanol, triethylene glycol diamine, N- (2-hydroxyethoxyethyl) -2-azanorbonane, N, N, N-trimethyl-N- (2-hydroxyethyl) -propylenediamine, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, dimethylaminopropyldipropanolamine, bis (dimethylaminopropyl) -2-hydroxypropylamine, N-ethylmorpholine, N- Methylmorpholine, N-cyclohexylmorpholine, 2-dimethylaminoethoxy-ethanol, 6-dimethylamino-1-hexanol, N, N-dimethyl-N ', N'-di (2-hydroxypropyl) -1,3-diaminopropane, N, N '-bis (3-hydroxy-propyl ) -N, N-1,3-propanediamine, N, N-dimethylaminoethanolamine, tetramethylhexamethylenediamine, dimethylamino-N-methylethanolamine, N-methylimidazole, N- (3-aminopropyl) imidazole, N- (3-aminopropyl) -2-methylimidazole , 1- (2-hydroxyethyl) imidazole, N- (2-hydroxypropyl) imidazole; N-formyl-N, N'-dimethylbutylenediamine, N-dimethylaminoethylmorpholine, N, N-diethylethanolamine, N- (dimethyl-3-aminoproyl) -urea (mono- and bis), N, N-bis (3-dimethylaminopropyl) - N-isopropanolamine, 2- (2-hydroxyethoxyethyl) -2-azanorbornane), N, N-ethylcyclohexylamine, 3,3'-bis-dimethylamino-di-n-propylamine and / or 2,2'-dipiparazinediisopropyl ether, dimethylpiparazine, N , N'-bis (3-aminopropyl) ethylenediamine, Tris- (N, N-dimethylaminopropyl) -s-hexahydrotriazine, N-methyl-N-dimethylaminoethylpiperazine, pentamethylenediethylenetriamine, tris (3-dimethylaminopropylamine), tris (dimethylaminopropyl) hexahydrotriazine, N-methyldicyclohexylamine, dimorpholinodiethylether, 1,4-diazabicyclo [ 2,2,2] octane, 4-chloro-2,5-dimethyl-1- (N-methylaminoethyl) -imidazole, 2-aminopropyl-4,5-dimethoxy-1-methylimidazole, 1-aminopropyl-2,4 , 5-tributylimidazole, 1-aminoethyl-4-hexylimidazole, 1-aminobutyl-2,5-dimethylimidazole, 1- (3-aminopropyl) -2-ethyl-4-methylimidazole, 1- (3-aminopropyl) imidazole and / or 1- (3-aminopropyl) -2-methylimidazole, tris (dimethylaminomethyl) phenol, N, N-dimethylaminoethylmorpholine, N, N, N ', N'-tetramethyl-1-butanediamine, 1,8-diazabicyclo5,4, 0-undecane, 1,4-ethylene-piperidine, N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N-dimorpholinodiethyl ether, 1,4-ethylene-piperidine, N, N-dimethyl-N', N '-2-hydroxypropyl-1,3-propylenediamine, 2- (2-hydroxyethoxyethyl) -2-azanorbornane, N-butylmorpholine, N, N, N'-trimethyl-N'-hydroxyethyl-bis (a minoethyl) ether, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-bis (3-dimethylaminopropyl) amino-2-propanol and N-methyl-N '- (2-dimethylamino) ethyl-piperazine, 1, 3,5-tris (3-dimethylaminopropyl) hexahydro-s-triazine; 1-dimethylamino-2-amino-2-methyl-propane; 1,4-bis (2-amino-2-methyl-propyl) -piperazine; 2,2-Dimorpholinodiethylether; and compounds sold under the name DABCO NE200, DABCO NE1060 and all ethoxylated or propoxylated derivatives of the compounds listed here and other amine catalysts not listed here.

Further Mixtures of said amines are possible. Containing mixtures Aliphatic and / or cycloaliphatic amines are preferred.

In the second embodiment organometallic compounds are used. Examples are organic Tin compounds, such as stannous salts of organic carboxylic acids, e.g. acetate, tin (II), Tin (II) octoate, tin (II) ethyl hexoate and tin (II) laurate and the dialkyltin (IV) salts of organic carboxylic acids, e.g. Dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate, monooctyltin tris (2-ethylhexyl thioglycolate), Dioctyltin bis (2-ethylhexyl thioglycolate), dimethyltin dilaurate and / or diproyltin dilaurate. Furthermore, preference may be given to: Bismuth tris (2-ethylhexanate), iron acetylacetonate, potassium acetate, Pb-bis- (2-ethylhexanoate), Nickel acetylacetonate, potassium formate, potassium octoate and / or phenylmercury propionate

Further are mixtures of the organometallic compounds containing possible. Further are mixtures of the organometallic compounds containing and the said amine catalysts possible.

Of the Polyurethane catalyst (i) usually becomes in an amount of 0.001% to 9.0% by weight, preferably 0.01 to 7.0 wt .-% and particularly preferably from 0.1 wt .-% to 4.0 wt .-%, based on the total weight of the polyurethane used.

The catalyst system according to the invention contains a supported catalyst catcher in deactivated form (ii). This initially deactivated, supported catalyst catcher (ii) is activatable. Preferably, the deactivated, supported catalyst scavenger (ii) is thermal enableable. The deactivated, supported catalyst scavenger (ii) is particularly preferred. by the resulting heat of reaction enableable.

The "supported catalyst catcher in deactivated form "(im Also referred to as "deactivated, supported catalyst scavenger" in this application and labeled "(ii)"). contains preferably an active ingredient (ii-a), a carrier component (ii-b) and a Protective component (ii-c). The active ingredient is to the active catalyst material (in the context of this application as (ii-a)), i. the substance that is capable of the polyurethane catalyst (i) bind. In the carrier component it is a carrier, preferably an organic or inorganic macromolecular builder (referred to in this application as (ii-b)). In the protective component (referred to in this application as (ii-c)) is a substance that deactivates the catalyst (ii-a), i.e. the one for it it is responsible that the active ingredient in the deactivated state is unable to bind the polyurethane catalyst (i).

In a preferred embodiment the catalyst scavenger is in deactivated form (ii) a catalyst starting material (ii-a) supported on a carrier (ii-b) applied and surrounded by a protective layer (ii-c).

getters are well known in the art and often do referred to as "getters" or "getters". Under Fang is a substance, preferably a solid, to understand which is able to bind other substances.

in the The scope of this invention is used under a catalyst starting material (ii-a) understood a substance that can do it the polyurethane catalysts (i) to bind, leaving a catalyst-trap-polyurethane catalyst complex (iii) forms. The catalyst-trap-polyurethane catalyst complex (iii) preferably can not emit from the polyurethane of the invention.

Since the polyurethane catalysts are often amines, the catalyst is able fangstoff (ii-a) usually bind amines. The catalyst starting material (ii-a) is therefore preferably an amine scavenger.

In Referring to the catalyst-trap-polyurethane catalyst complex (iii) the term "complex" is wide and not im strictly chemical sense interpreted. The complex formation can, for example, by Adsorption or absorption or reaction take place.

In a first preferred embodiment contains the catalyst scavenger (ii-a) metals in a form that allows to bind the polyurethane catalyst (i). The bond can be covalent be. Further, it may be a complex bond. Likewise, the Binding over Van der Waals force respectively.

Prefers the metal-containing catalyst precursors (ii-a) are as Metal, metal salt or organometallic compound.

The Metals used are preferably characterized in that these Complexes with primary, secondary or tertiary Amines can enter.

Examples of suitable metals are Li ⁺ , Na ⁺ , K ⁺ , Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ , Cr ³⁺ , to Cr ⁵⁺ , Ce ³⁺ , Cu, Cu ¹⁺ , Cu ²⁺ , Co, Co ⁺ , Co ²⁺ , Co ³⁺ , Co ⁴⁺ , Ni, Ni ⁴⁺ , Ni ²⁺ , Ni ³⁺ , Ni ⁴⁺ , Mn, Mn ¹⁺ , Mn ²⁺ , Mn ³⁺ , Mn ⁴⁺ , Fe, Fe ²⁺ , Fe ³⁺ , Zr, Zr ⁺ , Zr ²⁺ Zn, Zn ²⁺ , Sn ⁰ to Sn ⁴⁺ , V ⁰ to V ⁵⁺ Ag, Ag ⁺ , Ag ²⁺ ,, In and / or Ti ⁰ to Ti ⁴⁺ , Mo ⁰ to Mo ⁶⁺ , (La, Sc, Y, W, Ge, Hf, Gd, Eu, Sm, Tb, Ho, Er, Nd, Pr, Ce for the last 15 elements, the elements can be used in the neutral state as well as all important oxidation states)

When Anions can the common anions be used. Examples of these are halides and pseudohalides such as chloride, bromide, iodide, fluoride, chlorates, bromates, iodates; Phosphate and polyphosphates, sulphate and polysulphates, sulphite, nitrate, Nitrite, oxide, peroxide, cyanides, thiocyanides, silicates, borates, polyborates, Thiosulphates, polythionates, carbonates, and or carboxylates with 1 to 10 carbon atoms, preferably having 2 to 6 carbon atoms.

preferred Metal salts are copper (II) sulfate, copper (II) chloride, nickel (II) sulfate, Cobalt (II) chloride, iron (II) chloride and / or iron (III) chloride, Copper carbonates, iron carbonates, zirconium carbonates, manganese carbonates, Vanadium carbonates, copper borates, iron borates, vanadium borates, vanadium halides, copper nitrates, Iron nitrates, vanadium and manganese nitrates, titanium carbonates, titanium borates, Titanium carbonates, titanium halides, titanium oxides, iron oxides, vanadium oxides, Manganese oxides, copper oxides and the carboxylates of all the above Metals.

Further All the above metals are in the elemental state (Oxidation state zero) is preferably used.

These first preferred embodiment the catalyst starting material (ii-a) finds particular application, when the polyurethane catalyst (i) is amines. This means, it will be metal compounds or metals as a catalyst (ii-a), the good complexing properties to amines, in particular to tertiary Have amines. Thus, it is in this embodiment in the catalyst scavenger, preferably an amine scavenger.

In a second preferred embodiment contains the catalyst scavenger (ii-a) compounds that are resistant to metal catalysts have reactive groups. For the catalyst starting material (ii-a) these are preferably compounds which are reactive Have groups which organometallic polyurethane catalysts (i) can complex.

The Compounds of the second preferred embodiment of the catalyst starting material (ii-a) preferably have a molecular weight of 50 to 1400 g / mol, more preferably from 60 to 750 g / mol. It is preferred non-polymeric compounds (especially monomolecular compounds), the on the carrier (ii-b) can be applied.

Examples for suitable reactive groups containing organometallic polyurethane catalysts (i) can complex are amino groups or hydroxy groups. Further, crown ethers or cyclodextrins. Likewise are sulfur ligands, like for example, thiols, suitable. Further suitable are cyano groups, Thiogyanogroups, cyanuric acid groups .. Also suitable are hydrazines, triazines or tetrazines, polysulfanes. Also suitable are ligands with phosphorus or sulfur, such as phosphanes, Thiophosphoric.

Further suitable groups are acid groups like sulfuric acid, Phosphoric acid, Nitric acid, boric acid, or the organic carboxylic acid groups in their most diverse combinations and more functional Groups.

Farther is any combination of these catalyst starting materials (ii-a) the second embodiment possible.

In a third preferred embodiment, the catalyst starting material (ii-a) contains compounds which are reactive groups with respect to amine groups exhibit. These reactive groups are particularly preferably able to protonate the catalytically active center of the amine polyurethane catalyst or to react with aromatic amine groups. The reactive groups are either present in free form in the catch or be converted eg by aging in the active form.

The Compounds of the third preferred embodiment of the catalyst starting material (ii-a) preferably have a molecular weight of 50 to 1400 g / mol, more preferably from 60 to 750 g / mol. It is preferred non-polymeric compounds (especially monomolecular compounds), the on the carrier (ii-b) can be applied.

Examples for such reactive groups carboxylic acid groups, Sulfuric and phosphoric acid groups, Nitric acid groups, Halogen acids.

Further suitable are organic and inorganic acid anhydrides and acid esters, Like carboxylic acid anhydrides, Carbonsäureester or sulfuric acid ester, organophosphate and the corresponding anhydrides.

Of the However, catalyst tangent (ii-a) generally does not comprise any components which have been mentioned above as polyurethane catalysts (i).

Of the Catalyst starting material (ii-a) is applied to a carrier (ii-b). Under carriers (ii-b) are basically all solid, preferred macromolecular, substances that understand are able to bind the catalyst tangent (ii-a). The Binding can be done via adsorption or absorption. Prefers the binding of the catalyst tangent (ii-a) takes place via the carrier Adsorption.

The excipients (ii-b) are common inorganic, organic or organically modified inorganic Materials. these can particulate, porous or be compact.

at the carriers (ii-b) are preferably particles with an average diameter from 1 nm to 2 mm, preferably 15 nm to 1000 nm, more preferably 40 nm to 800 nm and most preferably from 80 nm to 500 nm. The carriers (ii-b) be round or irregular depending on the manufacturing process.

Porous carriers (ii-b), in the process according to the invention Close the application organic or inorganic materials. The carriers, the above a suitable porosity feature are generally nanoporous, microporous, mesoporous and / or macroporous.

Of the Term "porosity" refers to below the entire arrangement of pores and channels and cages. These solids can be amorphous or have a periodically crystalline structure or both features to unify. The arrangement of pores and channels and cages can be irregular, i. not be periodic. Alternatively, they can be regular or be periodic. The pores or channels can be isolated or connected be and can one or two-dimensional.

To the For purposes of this invention, a "nanopore" is defined as a pore with a radius from 100 pm to 10 nm, a "micropore" is defined as one Pore in the range of 10 nm to 100 nm, a "Mesopore is to be defined as a pore of 100 nm to 10 nm and as "macropores" are all pores greater than 10 nm To be defined.

The excipients (ii-b), can in general, metals or metal ions by complex formation or fix chemical bond. For this purpose, preferably have the excipients (ii-b) a sufficient amount of surface sites.

The porous excipients (ii-b) preferably have a surface area greater than 1 square meter per gram and less than 20,000 square meters per gram, more preferably from larger 10 square meters per gram and less than 10,000 square meters per gram, in particular of more than 100 square meters per gram and less than 8000 square meters per gram.

The inorganic carriers (ii-b) include amorphous (non-crystalline) metal oxide materials. Also crystalline inorganic carriers (ii-b), such as molecular sieves, are included as carriers. These molecular sieves are preferably ordered, porous, crystalline material with a defined crystalline structure. Within this structure, there are a large number of smaller cavities through be connected to a number of even smaller channels or pores can.

The Dimensions of these channels or pores are such that adsorption of molecules with certain dimensions allows while excluding those with larger dimensions turn.

molecular sieves can into different groups by their chemical composition and their structure will be classified. A group of molecular sieves becomes common referred to as zeolites. In a preferred embodiment it is the carrier (ii-b) a molecular sieve, in particular a zeolite.

Zeolites are from a grid of silicon di oxide and optionally composed of alumina, preferably with exchangeable cations such. B. alkali or alkaline earth metal ions is combined.

Even though the term "zeolites" includes materials that Silica and optionally contain alumina, the Silica and alumina shares completely or preferably partially by other oxides are replaced.

For example can Germanium oxide, titanium oxide, tin oxide, phosphorus oxide and mixtures thereof replace the silica content. Boron oxide, iron oxide, titanium oxide, Gallium oxide, indium oxide and mixtures thereof can be used Replace alumina content. Accordingly, the terms "zeolite", "zeolites" and "zeolite material" as used herein for crystalline and / or amorphous porous Molecular sieves are the silicon and / or optionally aluminum and / or titanium atoms and oxygen in the crystal lattice structure same or structures in which a proportion of these Atoms was replaced by other elements of the periodic table.

Of the Term carrier (ii-b) continues to refer to inorganic in the context of this application Oxides and mixed oxides, e.g. Silica, alumina, magnesia, Titanium oxide, aluminum silicates, silicon carbide, minerals, aluminum, magnesium included, such as Talc and kaolin, alumina or magnesia, Bentonites or modified bentonites, montmoriolinites and modified Monmoriolinites and the like Minerals.

Of the Term carrier (ii-b) continues to refer to organic carriers in the context of this application (Ii-b). For organic carriers (ii-b) it can be polymer structures. The surface of the Polymer structures may have been modified. Preferred is it is a natural one or synthetic polymer composed of monomers, which are preferably functional Containing groups or ligands.

The polymeric materials can compact or porous be. A selection of possible excipients (ii-b) based on different polymers is hereafter presented.

at Synthetic polymers may be emulsion polymers and / or Latices that contain at least one monomer with functional groups contain.

Examples for natural polymers are polysaccharides, such as cellulose, starch or chittosan, which are partial be etherified with C1-C4-alkyl or esterified with C1-C8-acyl.

Synthetic polymers with functional groups are known and can be prepared by known methods. The following are some examples of synthetic polymers: polyvinyl alcohol and copolymers of vinyl alcohol with unsubstituted or substituted olefins as comonomers; Polymethacrylic acid, polyacrylic acid and polymaleic acid and copolymers of methacrylic acid / acrylic acid and / or maleic acid with unsubstituted or substituted olefins as comonomers; Polyhydroxyalkyl acrylates, polyhydroxyalkyl methacrylates and polymaleic acid hydroxyalkyl esters, and copolymers of hydroxyalkyl esters of methacrylic acid, acrylic acid and / or maleic acid with unsubstituted or substituted olefins as cormonomers; Polyacrylamide and polymethacrylamide and copolymers of acrylamide, methacrylamide or both with unsubstituted or substituted olefins as comonomers; Polyaminoalkyl acrylates, methacrylates and maleic acid esters and copolymers of aminoalkyl acrylates; methacrylates, maleic acid esters or of two or three constituents thereof with unsubstituted or substituted olefins as comonomers; Polyhydroxyalkyl or polyaminoalkylvinyl alcohol and copolymers of hydroxyalkylvinylethers, aminoalkylvinylethers or both with unsubstituted or substituted olefins as comonomers, polybutadienes, hydroxylated polybutadienes; Hydroxy or aminopolystyrene, chloromethyl polystyrene and polystyrenesulfonic acid and copolymers of hydroxystyrene, aminostyrene, chloromethylstyrene, polystyrene sulfonic acid or two or more of these monomers with unsubstituted or substituted olefins as comonomers; Polyglycidyl ethers and hydroxyalkylated or aminoalkylated polyglycidyl ethers; and _r polyester polyamides and polyurethanes from hydroxyl or amine-containing monomers and di- or polyisocyanates and subsequently modified polyurethanes, polyamides, and polyimides as well as mixed forms of all of the above polymers or dendrimers or hyperbranched polymers.

The Polymer for the carrier (ii-b) may also be thermosetting Resins include, for example, epoxy resins, melamine-formaldehyde resins and phenol-formaldehyde resins.

The described polymers can by complexing functional groups either at the surface of the excipient (ii-b) or modified as a polymer by functional groups be.

The Modification can be done either after the preparation of the carrier (ii-b) or already carried out in the synthesis of the polymer. The Modification involves the introduction of functional groups, wherein These functional groups are capable of neutralizing metals or charged form to bind or complex and thus on the carrier too fix.

Also Organic ion exchange resins can be used as carrier (ii-b) become. The organic ion exchange resins used as carriers (ii-b) are organic, porous materials having a surface charge and ion exchange capacity for anions or cations.

Preferably are the organic polymer-based ion exchangers. Ion exchanger on Polymer base are commercially available or can be light from resins which are commercially available.

Examples close such resins Resins from the Röhm and Haas Company offered under the registered trademark Amberlyst and resins registered by the Dow Chemical Co. under the Brand "Dowex" are offered. These exchangers cover a wide range of different types Cation and anion exchangers with varying ion exchange capacity, porosity, pore size and particle size.

The number average molecular weight of the polymers used as the carrier (ii-b) is usually in the range of 10 ³ to 8 × 10 ⁶ , preferably 10 ⁴ to 2 × 10 ⁶ , especially 2 × 10 ⁴ to 10 ⁶ g / mole Preferably, the determination is by gel permeation chromatography using polystyrene standards for calibration.

Examples for organic modified inorganic carriers are materials that are typically used for separation in the high Performance Liquid Chromatography can be used. Be on the silicate surfaces preferably applied organic structures, with a connection via silanization he follows. The organic functional groups can be formed by non-polar spacers from the silicate surface be separated. Typical functional groups are the amino, Hydroxy, cyano-thiocyno, nitro, sulfo, thio and other groups. These groups are able to fix metals.

It This may be compact or porous materials. Examples for porous materials are the known chromoliths.

The Application of the catalyst starting materials (ii-a) to the carriers (ii-b) can be carried out by known methods. Examples of suitable Methods of application are e.g. in the case of metals as catalyst starting material (ii-a) application by precipitation from an aqueous solution water Salts of metals, e.g. B. by adjusting the pH.

One another method for applying a metallic catalyst material, consists in the adsorption of a catalyst starting material precursor, such as z. As a cation or metalate of a transition metal and subsequent reduction or oxidation of the precursor, z. B. to metal or metal oxide.

Of the Catalyst starting material (ii-a) can also be used simultaneously with another Material on the carrier (ii-b) precipitated become.

Of the Catalyst starting material (ii-a) can be removed from the carrier (ii-b) by deposition, e.g. the ion exchange can be applied. For this purpose will be the specific carriers, those with exchange groups or complexing ligands in one Pillar given and a solution the catalyst starting material (ii-a) to be applied in this case metals or metal ions are continuously attached to the carrier (ii-b) passed, where it is to absorb the desired Metal or metal ions on the carrier (ii-b) comes. Subsequently there is still the possibility by heating or reducing the properties of the catalyst starting material to optimize.

The application of the Fangstoffs (ii-a) can be further carried out by applying a metal salt to an organic ion exchanger. Then the ion exchanger is washed with distilled water, dried thereon and this dried loaded ion exchanger to give a mixture of which thereon by known methods a carrier (ii-b) such as a zeolite produces (eg Na ₂ O, TPAOH, Al ₂ O ₃ , SiO ₂ and H ₂ O).

These (ii-a) are functional groups that are: are able to protonate the amine catalysts and so on the surface to be able to fix so these are applied, for example, as follows.

By Soak of the carrier with organic compounds containing acid groups or in Acid groups are transferred can. After this a surface assignment is achieved, the preferred catching agent (ii-a) is not the surface was adsorbed, removed by a washing process. Depending on the applied Substance may be in an optional subsequent polymerization step a fixation on the carrier material (ii-b). has the catch (ii-a) itself over polymerizable functional groups so they can react with each other the various possibilities the polymerization linked together become. Also, the optional polymerization step by Addition of a co-monomer done. By adding the co-monomer becomes the original one monomeric entanglement in a polymeric network.

Of others can the capture agents (ii-a) are provided with reactive groups, see above that are capable of reacting with the surface of the carrier (ii-b) and to be fixed there (usual Technique in the preparation of functionalized carrier materials for HPLC).

Farther can the carrier (ii-b) contain functional groups capable of functional Groups of the Fangstoff (ii-a) to react, for example, substitution reactions enter into. So can the catch (ii-a) by soaking on the surface of the carrier (ii-b) are applied and subsequently - preferably by supplying energy (Warmth, Light etc.) excited - with the carrier polymer (ii-b) react and so are fixed to the polymer.

Farther can the organic polymer carrier substances (ii-b) change or make that over any ligands and functional groups for complexing or fix other forms of bonding metals than catchers (ii-a) can. The Applying the metals is carried out similarly to the one described above Procedure for inorganic carriers (Ii-b).

The weight ratio of carrier (ii-b) to catalyst starting material (ii-a) is usually from 0.1 to 1000: 1, preferably from 0.5 to 100: 1, more preferably from 0.5 to 10: 1 and in particular from 1: 1 to 10: 1.

The supported Catalyst scavengers (i.e., those already on the carrier (ii-b) applied catalyst scraps (ii-a)) are usually as a particle before. In a preferred embodiment, these particles have an average particle diameter of 10 nm to 1 mm, more preferably of 1 μm up to 500 μm, in particular of 5 μm up to 250 μm.

The average particle diameter, which is also referred to as the D ₅₀ value of the integral mass distribution, is defined in the context of this invention as the particle diameter at which 50% by weight of the particles have a smaller diameter than the diameter which corresponds to the D ₅₀ value equivalent. Likewise, then 50 wt .-% of the particles have a larger diameter than the D ₅₀ value. The determination of the particle diameter was carried out by the dynamic light scattering whereby ball-like particles are estimated to the equivalent spherical diameter.

The heard dynamic light scattering to the standard methods for determining the mean particle size in the submicron range. The particle size distribution can be controlled by various distribution functions such as length, area, volume or mass distribution. In dynamic light scattering in the context of this invention, the volume distribution is shown. The characteristic size for the distribution function is often the Diameter D.

Of the Active ingredient of the supported Catalyst scavenger, i.e. the catalyst starting material (ii-a) is as described above the protective component (ii-c) first disabled. The protective component can however be removed so that the active ingredient can develop the desired effect. The at least partial removal of the protective component (ii-c) thus leads to activate the carrier catalyst catcher (Ii).

As As described above, it is preferable for the supported catalyst scavenger to be deactivated Shape (ii) around a supported one Catalyst starting material (ii-a), which is surrounded by a protective layer (ii-c).

When Protective layer are basically all substances suitable, on the one hand, the catalyst starting material (ii-a) first so can surround that it does not react with the polyurethane catalyst (i) can be activated on the other hand in the course of the reaction, i. so removable are that the catalyst starting material (ii-a) with the polyurethane catalyst (i) can react.

In an embodiment contains the protective layer (ii-c) is a polymer, preferably a polymer having a melting temperature or melting range between 40 and 200 ° C. Examples of suitable Polymers are polyesters, polyethylene oxides, polypropylene oxides, polybutylene oxides, Polyacrylates, polyether esters, polyvinyl alcohols, polytetrahydrofuran, Polystyrenes and any copolymers containing styrene, polybutadienes and / or Polyolefins.

The Protective layer hereby preferably surrounds the catalyst starting material (ii-a) Completely. The catalyst scavenger is thus preferably encapsulated in a polymer.

The Encapsulation of substances is well known and has been on the field of polyurethane chemistry for other uses already used.

So GB-B-1,035,903 describes a process for producing polyurethane foams wherein in a protective case encapsulated catalyst is used. The protective case has a melting point of 30 to 40 ° C serves to improve the storage stability of the system before implementation and is preferred by shear forces when mixing, dielectric heating or ultrasonic waves away.

Further GB-B-1,053,500 discloses a process for the production of polyurethanes by use of isocyanates encapsulated in a protective layer.

Finally reveal WO 02/31013 and WO 03/085021 that the encapsulation of catalysts with wax the curing behavior can be significantly accelerated by polyurethane reactions, and Although without the start time is adversely affected.

In The present invention may include the encapsulated catalyst scavenger be activated in different ways. In one embodiment the capsules by shear forces opened during mixing. In a further embodiment the capsules by irradiation of ultrasonic waves or microwaves open.

In a preferred embodiment the protective layer is chosen that the encapsulation is opened by the heat of reaction. In a special preferred embodiment For example, the protective layer (ii-c) has a melting temperature of 50 ° C to 200 ° C, more preferably from 60 ° C up to 150 ° C, still more preferably from 70 ° C up to 130 ° C and in particular of 75 ° C up to 120 ° C on.

In a preferred embodiment the protective layer (ii-c) is a wax which is preferred by the heat of reaction can be melted. Thus, it is in the Supported catalyst scavengers in deactivated form (ii) in a preferred embodiment around a wax encapsulated supported catalyst scavenger.

in the For the purposes of this invention, "wax" is understood to mean natural or artificial recovered substance. The waxes of the present invention are included 20 C generally in solid form. In solid form they are preferably kneadable or solid to brittle hard, but not glassy. In general, the waxes of the present invention are already few above the melting point relatively low viscosity and preferably not stringy. Preferably, they are above 10 ° C the melting point is a viscosity of less than 20,000 mPas, measured according to DIN 53019, on. These relatively low viscosity just above the melting point, wax differs from "classic" plastics.

Of the Term waxes includes natural waxes, chemically modified waxes and synthetic waxes, provided they meet the above criterion of the polar groups. Include natural waxes vegetable waxes such as montan wax, animal waxes such as beeswax, mineral waxes and petrochemical waxes such as petrolatum. Include chemically modified waxes For example, hard waxes such as montan ester waxes. Synthetic waxes include, among others, polar alkane waxes, such as wax alcohols, in particular higher molecular weight water Fatty alcohols preferably having more than 12 carbon atoms, such as Lignocerlalkohol, Cerlalkohol, Myricylalkohol, Melissylalkohol and Polyalkylene oxides such as polyethylene oxide, poly-THF, polyvinyl ether waxes, Polyolefin copolymer waxes and oxidized polyolefin waxes. Further The term wax includes higher molecular weight fatty acids, preferably having at least 9 carbon atoms, such as behenic acid, tetracosanoic acid and cerotic, which may optionally be esterified with alcohols and high molecular weight polyesters having a molecular weight of> 1000 g / mol, preferably> 1500 g / mol, by Reaction of di- or polycarboxylic acids having 2 to 20 carbon atoms are obtainable with di- or polyalcohols having 2 to 30 carbon atoms, wherein the corresponding acids or Alcohols contain aliphatic and / or aromatic structural units can. Likewise Mixtures of the aforementioned waxes are used.

In a preferred embodiment For example, the wax used has a melting temperature of 50 ° C to 200 ° C, more preferably from 60 ° C up to 150 ° C, still more preferably from 70 ° C up to 130 ° C and in particular of 75 ° C up to 120 ° C on.

It may be beneficial if the waxes used one or more contain polar groups, thus the compatibility between wax and Catalyst tracer (ii-a) increased becomes. Polar groups are groups that are compared to a pure Hydrocarbon group has a different electronegativity over this exhibit. In general, you can Oxygen atoms, nitrogen atoms, sulfur atoms and optionally Halogen atoms as a basis for serve polar groups. Pure alkane or paraffin waxes are preferred not used as a protective layer (ii-c) because they are not polar groups in the sense of the preferred embodiments described above exhibit.

at The waxes are generally polymeric substances. The polar groups can at the end and / or within the polymer. Examples of polar Groups are acid, Amine, imine, amide, ether, ester, acetate, keto, aldehyde, optionally Urethane, urea, thiol or alcohol group.

The waxes used in the present invention have a heat of fusion of 45 to 260 joules / gram, preferably from 80 to 220 Joule / gram, in particular from 130 to 180 joules / gram. The heat of fusion is measured according to the ISO 11357-3 by the DSC method (differential scanning calorimetry).

In a preferred embodiment, polar polyolefin waxes are used. Polyolefins which are preferably used are: polyethylene, polypropylene, polybut-1-enes and copolymers of ethylene with 0 to 20 mol% of propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1- undecene. Preference is given to polyethylene wax with 0 to 10 mol% of propene, 1-butene, 1-pentene or 1-hexene. The average molecular weight M _{w of} these polyolefin waxes is from 500 to 20,000 g / mol, preferably from 2,000 to 15,000 g / mol and more preferably from 3,000 to 10,000 g / mol.

Polar groups can generally be introduced into a wax by different process steps. A preferred method is to partially degrade the wax, for example, by atmospheric oxygen or peroxide compounds, thereby obtaining so-called oxidized polyolefin waxes. As peroxide compounds, for example, hydrogen peroxide (H ₂ O ₂ ) or dialkyl peroxides can be used. By partial degradation methods, hydroxyl groups and carboxyl groups are introduced as polar groups in the macromolecules.

Prefers used are oxidized polyolefin waxes having an acid number of not more than 50, preferably from 10 to less than 50.

A Another preferred method is polar comonomers such as Acrylic acid, methacrylic acid, acrylate, Methacrylic acid ester or Vinyl acetate, which can be optionally saponified to use, thereby receives so-called copolymer polyolefin waxes.

Preference is given to ethylene-vinyl acetate waxes having an M _{w of} from 2,000 to 15,000 g / mol, in particular from 3,000 to 10,000 g / mol, and a content of from 0.1 to 25% by weight of vinyl acetate, particularly preferably from 1 to 15 % By weight of vinyl acetate, based on the total weight of the copolymer.

Preference is furthermore given to using ethylene-acrylic acid waxes having an M _{w of} from 2,000 to 15,000 g / mol, in particular from 3,000 to 10,000 g / mol, and a content of from 0.1 to 20% by weight of vinyl acetate, more preferably of 1 to 15% by weight of acrylic acid, based on the total weight of the copolymer.

In a further preferred embodiment become ethylene-acrylic acid-acrylate terpolymer waxes used. These have an acrylic acid content of 0.1 to 20 wt .-%, preferably from 1 to 5 wt .-% and a content of acrylate of 0.1 to 40 wt .-%, preferably from 1 to 20 wt .-%, with the proviso that the total content of acrylate and acrylic acid below 50 wt .-%, preferably less than 40% by weight, based on the total weight of the terpolymer, lies.

In a particularly preferred embodiment, polyether waxes are used. These generally have a molecular weight M _w of 10,000 to 50,000 g / mol, preferably from 15,000 to 35,000 g / mol. Polyvinyl ether waxes, for example poly-octadecyl vinyl ethers or corresponding polyethers which have a C16, C17, C19, C20, C21 or C22 radical instead of an octadecyl radical are particularly suitable.

In a further preferred embodiment montan waxes and montan ester waxes are used. These are based on long-chain fatty acids, generally composed of hydrocarbon chains with 20 to 40 C atoms, preferably having 30 to 36 carbon atoms.

In a further preferred embodiment be polyethylene oxide or polypropylene or polybutylene oxides or mixed polymers composed of ethylene oxide, and / or propylene oxide and / or Butylene oxide and other alkylene oxides used.

In In another preferred form, the waxes have installable functional groups. After melting, they are able to react with the remaining isocyanate groups and so can be incorporated into the polymeric network.

to Production of the supported catalyst catcher in deactivated form (ii) will generally be the supported catalyst scavengers (ii-a) (i.e., the catalyst scavengers (ii-a) acting on the carrier (ii-b) as described above) in liquid wax or polymers dissolved or suspended. Optionally, a solubilizer may be added the better solution of the carrier Catalyst starting material (ii-a and ii-b) in the wax. The mixture from liquid Wax and supported Catalyst starting material (ii-a and ii-b) is now preferably in a polar liquid chilled and dispersed. Optionally, before this step, the melt a dispersing agent is added, which leads to a beneficial Dispersion leads.

As a polar liquid is generally suitable any liquid in which the wax is insoluble. Water or a compound having at least two isocyanate-reactive hydrogen atoms is preferably used. It is preferred while a polyol, in particular a polyetherol, used as a component, particularly preferably the polyol is used, which is used in the preparation of the polyurethanes according to the invention. The use of this polyol is advantageous since it does not introduce any foreign matter into the system and, in the case of cellular products, a possible destabilization of the foam by foreign substances can be avoided.

When solubilizers can in general, compounds are used which are e.g. Hydrogen bonds to build up the catalyst (ii-a) and thus the compatibility to the surface of the carrier Catalyst starting material can improve. Consider, for example polar polymers, e.g. Polyethylene oxide or polypropylene oxide or mixed polyethers of ethylene oxide and propylene oxide, polyester Polyvinyl alcohols polyimines. The solubilizer usually becomes in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the weight of wax and catalyst starting material used.

When Dispersants are generally suitable amphiphilic molecules, which have a hydrophobic part compatible with the wax, and a hydrophilic, with the polar liquid compatible part to have. For example, stearic acid can be used. The dispersant usually becomes in an amount of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the weight of wax and catalyst starting material used.

In a particularly preferred embodiment for the preparation of the catalyst systems of the invention can the liquid Mixture of catalyst and heated wax directly by spraying in one Airflow, preferably a cold airflow, into a suitable, particulate form be brought, so that a, preferably granular, powder is obtained. Processually, an apparatus is similar to a spray dryer suitable, but preferably operated with a cold air flow becomes. Furthermore, the catalyst system dispersed in the polar liquid also be freeze-dried. In the process, the catalyst dispersion becomes first frozen and the dispersant removed in vacuo. You get a dry one Powder. By varying the temperature and thus the viscosity and the nozzle pressure the average particle diameter of the resulting deactivated supported catalyst scavenger (ii) be set.

As illustrate the above methods, it is in the Term "encapsulate" or "encapsulate" in the context of this Invention to encapsulate or encapsulate in the strict sense, i. in the middle of the particulate Katalysatorfangstoffteilchens is exclusively supported catalyst tangent (ii-a) surrounded by a layer (ii-c) which is preferred made of wax. It is contrary to some of the Prior art "encapsulated" inhibitors are known in the art The present invention preferably does not favor "embedding" the supported catalyst scavenger Solve or Dispersing in a wax. That a particle of the supported catalyst scavenger of the invention (ii) can usually through a catalyst core wax wrap model and preferably does not consist of a wax matrix, in which of the supported Catalyst is dispersed.

Of the supported catalyst catcher in deactivated form (ii) becomes common in an amount of 0.001 wt% to 20.0 wt%, preferably 0.01 up to 10.0% by weight and more preferably from 0.1% by weight to 8.0% by weight, based on the total weight of the polyurethane used.

In a preferred embodiment is the molar ratio of polyurethane catalyst (i) to catalyst starting material (ii-a) 1 to 80,000, preferably 1 to 15,000, more preferably from 1 to 7500, particularly preferably 1 to 1000 and in particular 1 to 500.

above were now the ingredients polyisocyanates (a), compounds with across from Isocyanate-reactive hydrogen atoms (b) and the catalyst system according to the invention (c) containing polyurethane catalyst (i) and supported catalyst scavenger in deactivated form (ii) described. The isocyanate component and / or Polyol component can also propellant (d) and additives (e) included.

The Reaction of components (a) and (b) takes place optionally in Presence of propellants (d). As blowing agents can general used known chemically or physically acting compounds become. As a chemical blowing agent may preferably water be used. examples for physical blowing agents are inert (cyclo) aliphatic hydrocarbons having from 4 to 8 carbon atoms which are under the conditions of polyurethane formation evaporate. The amount of blowing agent used depends according to the desired density of the foams.

In an embodiment is the blowing agent in an amount of 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-%, more preferably from 0.3 to 10 wt .-% and in particular from 0.5 to 5% by weight, based on the weight of the components (a) and (b) used.

Possibly can in for the preparation of the polyurethanes additives of the invention (e) be added.

When Additives (e) find, for example, surface-active substances, foam stabilizers, Cell regulators, outer and internal release agents, dyes, pigments, flame retardants, hydrolysis stabilizers, Oxidation inhibitor, Abrasion improver, fungistatic and bacteriostatic acting substances, light stabilizers, called plasticizers. The These substances are commonly used in in an amount of 0.01 to 10 wt .-%, particularly preferably of 0.1 to 5 wt .-%, based on the total weight of the polyurethane used.

Also can as component (s) filling and Reinforcing materials, such as glass fibers, chalk, barite can be used. These are usually in an amount of from 1 to 50% by weight, more preferably from 5 to 30 wt .-%, based on the total weight of the polyurethane used.

The polyurethanes according to the invention are thus available by reacting components (a) and (b) in the presence of (c) and optionally (d) and (e).

The polyurethanes according to the invention are preferably low emissions, in particular low emissions at elevated temperature. In a preferred embodiment have the polyurethanes according to the invention according to the thermal desorption method according to DaimlerChrysler (PB VWT 709) an emission level of less than 40 ppm, more preferably less than 20 ppm, in particular between 1 and 15 ppm.

Furthermore the resulting polyurethanes are characterized in that they favorable dynamic mechanical properties after hydrolysis aging exhibit.

In a preferred embodiment have the polyurethanes according to the invention with equally good emission properties, more than 20% better tear- and tensile strengths compared to polyurethane flexible foams, the with embeddable catalysts such. For example, 2-dimethylamino-ethoxy-ethanol or N- (2-hydroxyethoxyethyl) -2-azanorbornane) were manufactured.

The Compression set residues after hydrolysis aging are in use this supported catalyst catcher and Use of non-installable catalysts as over 40% better than comparable foams with built-in catalysts such as 2-dimethylamino-ethoxy-ethanol or N- (2-hydroxyethoxyethyl) -2-azanorbornane.

Furthermore are the rebound resilience after Hydrolysealterung using this supported catalyst catcher below Use of non-installable catalysts by more than 50% better than identical foams the installable catalysts such as 2-dimethylamino-ethoxy-ethanol or N- (2-hydroxyethoxyethyl) -2-azanorbornane use.

Of the Content of aromatic amines especially 2,4-MDA is in use these substances and catalysts such as Bisdimethylaminoethylether order up to 500% better than comparable foams the installable catalysts such as 2-dimethylamino-ethoxyethanol or N- (2-hydroxyethoxyethyl) -2-azanorbornane use.

object The invention further provides a process for the preparation of the polyurethanes according to the invention by reacting an isocyanate component with a polyol component, characterized in that the reaction comprises the catalyst system according to the invention, containing catalyst (i) and supported catalyst scavenger (ii) in deactivated form with the catalyst scavenger activated becomes.

in the inventive method the polyisocyanate component and polyol component are in such Quantities brought to implementation that the equivalence ratio of NCO groups of (a) polyisocyanates to the sum of the reactive hydrogen atoms of components (b) 1: 0.5 to 1: 3.50 (corresponding to an isocyanate index from 50 to 350), preferably 1: 0.65 to 1: 1.30, and more preferably from 1: 0.9 to 1: 1.15.

The Starting components are usually at a temperature of 0 C to 80 C, preferably 15 to 60 C mixed and reacted. The output components can be, for example be reacted in a mold. The mixing For example, mechanically by means of the low pressure technique or the High pressure technology, or by other mixing methods, the at usual PUR processing machines are used, done.

All Descriptions of preferred embodiments above for the polyurethanes according to the invention are also found for the inventive method for the preparation of the polyurethanes according to the invention.

The polyurethanes according to the invention can be compact or cellular depending on the choice of components (a) to (e). In a preferred embodiment, the polyurethanes are Soft, hard, semi-rigid or integral foams or compact, preferably thermoplastic polyurethanes and / or cast elastomers. The polyisocyanate polyaddition products can be prepared as moldings, for example as dashboards, seat foam, carpet backing foam, etc.

The Classification of the foams according to the invention in flexible foam, semi-rigid foam and rigid foam takes place according to DIN 7726.

object The invention further relates to the use of the polyurethane according to the invention for the production of interiors of transport. preferred Means of transport are motor vehicles, ships, trains and aircraft. Examples for the Interior fittings are seats, instrument panels, side and door side panels, Center consoles armrests and glove boxes, headliner, acoustic foams, carpet backing foams.

Also the invention relates to the use of the polyurethane preparation of the invention of furniture, such as a couch, for making carpets or for the production of mattresses.

object The invention is therefore also a dashboard, car seat, Carpet or mattress containing polyurethane according to the invention.

The Inventive instrument panel is constructed from an outer layer, a polyurethane foam according to the invention, and optionally a carrier element. In the field dashboard are often also as instrument panels designated.

When outer layer become common Used materials that give the dashboard a decorative appearance, such as plastic films, plastic skins, textiles and / or leather. The Thickness of the outer layer is generally 0.5 to 3 mm, preferably from 0.7 to 1.4 mm.

When Polyurethane foam are the polyurethane foams of the invention for use. The layer of polyurethane foam usually has a thickness of 0.5 millimeters (mm) to 60 mm, preferably 5 mm up to 18 mm. In this embodiment If the polyurethane according to the invention is preferably around a semi-rigid polyurethane foam.

When support element usually everybody comes Materials in question, which the mechanical properties of positively influence the resulting composite element. Examples of this are wood fiber carrier parts, glass fiber reinforced Thermoplastics, or duromer support parts. The carrier elements usually a thickness of 1.0 mm to 15 mm, preferably from 1.5 mm to 4 mm.

object The invention further relates to a car seat containing a polyurethane foam according to the invention. This is preferably a flexible polyurethane foam, the one with an outer skin connected is. Alternatively, it can also be a polyurethane integral foam act. The foam according to the invention in this case preferably has a density of 20 to 250 g / l, preferably from 40 g / l to 200 g / l, on. Below the density of the polyurethane foam is in the context of this invention, the average density over the overall resulting foam, i. in molded foams this figure refers to the average density of the entire foam including core and outer layer.

object The invention further relates to a carpet or a mattress containing a polyurethane foam according to the invention. This is preferably a flexible polyurethane foam. The foam according to the invention has in this case preferably a density of 15 to 200 g / l, preferably from 20 g / l to 130 g / l, on.

For all above Uses mentioned apply to the polyurethane of the invention described preferred embodiments.

In In the polyurethane industry, it is common for the starting materials described as components (a) to (e) of produced by different producers. Consequently, can the catalyst system (c) containing the polyurethane catalyst (i) and a supported one catalyst catcher in deactivated form (ii) also individually and independently of the Components (a) and (b), and optionally (d) and (e) distributed become.

The invention therefore relates to a catalyst system comprising
a polyurethane catalyst (i) and
a supported catalyst scavenger in deactivated form (ii);
and its use for the production of low-emission polyurethanes.

The above for the polyurethanes according to the invention described preferred embodiments also find for the catalyst system according to the invention Application.

Preferably, the supported catalyst scavenger in deactivated form (ii) as described above is a supported catalyst scavenger which is converted from a protective layer ben is. The subject of the invention is therefore also a supported Katalysatorangstoff, which is surrounded by a protective layer. Surrounding with a protection view is also referred to as "encapsulating" or "encapsulating".

In a preferred embodiment is the carrier Catalyst ingredient (ii-a) in a fabric having a melting temperature encapsulated from 50 to 200 ° C. In particular, the supported Catalyst tangent (ii-a) in a wax having a melting temperature from 50 to 200 ° C encapsulated. The encapsulated, supported Catalyst is used to produce low-emission polyurethanes Use. Thus, the foregoing description is preferred embodiments the polyurethane according to the invention also for the encapsulated according to the invention Catalyst trap application.

Finally, the invention relates to a process for the reduction of emission from polyurethanes, characterized in that already in the preparation of the polyurethane, a polyurethane catalyst (i) and
a supported catalyst scavenger in deactivated form (ii) is added to the reaction of isocyanate component with polyol component,
wherein the deactivated supported catalyst scavenger (ii) is activated during the reaction so that a catalyst-catalyst complex (iii) is present in the resulting polyurethane foam. Preferably, the catalyst-catalyst-starting complex (iii) is such that it can not substantially be emitted from the polyurethane.

For this inventive method apply the above for the polyurethanes according to the invention described preferred embodiments.

The Procedure allows the provision of polyurethanes, on the one hand low in emissions and on the other hand advantageous properties with respect to hydrolytic Have aging. Advantageous mechanical and dynamic properties are, for example, resilience, compression set, Tear resistance, Tensile strength, hardness and / or E-modules.

Claims (19)

Polyurethane obtainable by reacting an isocyanate component with a polyol component, characterized in that a polyurethane catalyst (i) and a supported catalyst scavenger in deactivated form (ii) are added to the reaction, the supported catalyst scavenger (ii) being activatable. Polyurethane according to claim 1, characterized that it is the carrier catalyst catcher in deactivated form (ii) around a catalyst tangent (ii-a) acting on a carrier (ii-b) is applied and surrounded by a protective layer (ii-c). Polyurethane according to claim 1 or 2, characterized the protective layer (ii-c) has a melting temperature of 50 ° C to 200 ° C. Polyurethane according to one of claims 1 to 3, characterized that the catalyst (ii-a) is a metal, a metal salt or an organometallic compound. Polyurethane according to one of claims 1 to 3, characterized that the catalyst (ii-a) is a compound which have reactive groups which are organometallic Polyurethane catalysts (i) can fix. Polyurethane according to one of claims 1 to 3, characterized that the catalyst (ii-a) is a compound which have reactive groups which protonate amine groups can. Polyurethane according to one of Claims 1 to 6, characterized that it is the carrier (ii-b) a scaffold silicate, preferably a zeolite, acts. Polyurethane according to one of claims 1 to 7, characterized that it is the carrier (ii-b) is a polymer particle Polyurethane according to one of claims 1 to 8, characterized that the carrier catalyst catcher in deactivated form (ii) in an amount of 0.01 to 15% by weight, based on the total weight of the polyurethane. Polyurethane according to one of claims 1 to 9, characterized that the polyurethane after the Thermodesorptionsmethode after DaimlerChrysler (PB VWT 709) has an emission value of less than 20 ppm. Use of a polyurethane according to any one of claims 1 to 10 for the manufacture of interiors of transport, to Production of furniture, for the production of carpets or for the production of mattresses. Dashboard, car seat, carpet or mattress, containing a polyurethane according to any one of claims 1 to 10. Process for the preparation of a polyurethane by reacting an isocyanate component with a polyol component, characterized in that a catalyst (i) and a supported catalyst scavenger (ii) in deactivated form are added to the reaction, the catalyst scavenger being activatable. Catalyst system comprising a polyurethane catalyst (i) and a supported one catalyst catcher in deactivated form (ii). Catalyst starting on a carrier applied and surrounded by a protective layer. Catalyst starting material according to claim 14, characterized in that that the carrier Catalyst starting material (ii-a) from a substance (ii-c) having a melting temperature from 50 to 200 ° C is surrounded. Use of a catalyst system according to claim 14 for the production of low-emission polyurethanes. Use of a catalyst starting material according to claim 15 or 16 for the production of low-emission polyurethanes. Method of reducing emission from polyurethanes, characterized in that already in the production of the polyurethane a polyurethane catalyst (i) and a supported catalyst catcher in deactivated form (ii) the reaction of isocyanate component is added with polyol component, wherein the deactivated supported catalyst scavenger (ii) while the reaction is activated, so that in the resulting polyurethane foam one Catalyst catalyst starting material complex (iii) is present.