DE102014215387B4 - Nitrogen containing compounds suitable for use in the manufacture of polyurethanes - Google Patents

Abstract

Use of at least one nitrogen-containing compound and / or a corresponding quaternized and / or protonated compound in the production of polyurethanes, characterized in that a compound of the formula (III) and / or (IV) is used.

Description

The present invention is in the field of nitrogen-containing compounds, in particular amines, and polyurethanes. In particular, it relates to the use of nitrogen-containing compounds of the formulas (III) and / or (IV), correspondingly quaternized and / or protonated compounds, for the production of polyurethanes, in particular polyurethane foams, and compositions containing these compounds.

The use of tertiary amines in the production of polyurethanes is known. A large number of structurally different amines are used as catalysts.

Polyurethanes are understood here to mean all reaction products based on isocyanates, in particular polyisocyanates, and correspondingly isocyanate-reactive molecules. This also includes, among other things, polyisocyanurates, polyureas and allophanate, biuret, uretdione, uretimine or carbodiimide-containing isocyanate or polyisocyanate reaction products. The use of the tertiary amines in the production of polyisocyanate polyadducts is preferred.

Polyurethane systems are e.g. B. polyurethane coatings, polyurethane adhesives, polyurethane sealants, polyurethane elastomers or polyurethane foams, also referred to as polyurethane foams or PU foams.

Tertiary amines play a particularly important role in the production of polyurethane foams, since here the so-called blowing reaction - water reacts with isocyanate to form carbon dioxide as the blowing gas - and the gel reaction - polyols react with isocyanates to urethanes, which leads to an increase in the molecular weight and corresponding gelling leads - must be precisely coordinated so that a high-quality foam can be created.

Polyurethane foams are cellular and / or microcellular polyurethane materials and can be roughly divided into closed-cell or partially closed-cell rigid polyurethane foams and open-cell or partially open-cell flexible polyurethane foams. Rigid polyurethane foams are mainly used as insulation materials, for example in refrigerator systems or in the thermal insulation of buildings. Flexible polyurethane foams are used in a large number of technical applications in industry and the private sector, for example for noise insulation, for the manufacture of mattresses or for upholstering furniture. A particularly important market for various types of PU foams, such as conventional flexible foams based on ether or ester polyol, cold flexible foams, hereinafter also referred to as cold foams (often also known as “high resilience” (HR) foams), and rigid foams and foams and their properties the automotive industry represents between these classifications. Here, for example, rigid foams can be used as headliners, ester foams for the interior lining of the doors and for punched-out sun visors, cold and soft foams for seating systems and mattresses.

With regard to flexible foams, a distinction can also be made between cold flexible foams and hot flexible foams, such as in EP 2042534 A1 described, to which reference is made here in full.

WO2005111109A1 discloses the use of acid-blocked amine catalysts and their use in the production of polyurethane foams.

There is still a need for further alternative catalysts, preferably nitrogen-containing catalysts, in particular alternative amines, which are suitable for the production of polyurethanes and polyurethane foams, preferably suitable for the production of low-odor, age-resistant polyurethane systems with low amine or other emissions, such as for example formaldehyde and / or dimethylformamide (DMF).

The specific object of the present invention was therefore to provide an alternative catalyst for the production of polyisocyanate reaction products, preferably polyurethanes, in particular polyurethane foams, which are preferably low-odor, age-resistant and / or free of emissions or at most with low amine or other emissions, for example Formaldehyde and / or dimethylformamide (DMF), are afflicted.

Surprisingly, it has been found that compounds of the following formula (III) and / or (IV), the corresponding quaternized and / or protonated compounds solve this problem, ie both the use of the compounds of the formula (III) and / or (IV) as the use of the corresponding protonated compounds and also the use of the corresponding quaternized compounds and also the use of corresponding mixtures in each case achieve the stated object.

eingesetzt wird.The present invention thus relates to the use of at least one nitrogen-containing compound and / or a corresponding quaternized and / or protonated compound in the production of polyurethanes, in particular polyurethane foams, a compound of the formula (III) and / or (IV)

is used.

For the purposes of this invention, the expression “use of at least one nitrogen-containing compound, a corresponding quaternized and / or protonated compound” includes the use of the nitrogen-containing compound in question here and also the use of the corresponding protonated compounds and the use of the corresponding quaternized compounds as also the use of appropriate mixtures.

The nitrogen-containing compounds of the formula (III) and / or (IV) used in accordance with the invention and correspondingly quaternized and / or protonated compounds, and also mixtures of the aforementioned, are suitable as catalysts for the preparation of polyisocyanate reaction products, preferably polyurethanes, in particular polyurethane foams, and can catalyze both the gel reaction and the blowing reaction during foaming, and advantageously further isocyanate reactions, as described below.

The present invention advantageously also enables a reduction or avoidance of the catalytic emissions in the production of polyurethane systems, in particular polyurethane foams.

In particular, an additional advantage of the invention is that the nitrogen-containing compounds of the formula (III) and / or (IV) used in accordance with the invention, correspondingly quaternized and / or protonated compounds, and mixtures of the abovementioned, advantageously low-emission, preferably free with regard to typical undesirable emissions of the resulting polyurethane systems, in particular polyurethane foams, particularly preferably flexible polyurethane foams, namely advantageously low-emission with regard to emissions of nitrogen-containing compounds, also referred to below as amine emissions, advantageously low-emission with regard to emissions of dimethylformamide (DMF), and advantageously low-emission with regard to aldehyde emissions, in particular with regard to formaldehyde emissions.

For the purposes of the present invention, “low-emission” with regard to amines comprises in particular that the polyurethane system, preferably the polyurethane foam, more preferably the flexible polyurethane foam, particularly preferably the flexible polyurethane foam, preferably for producing mattresses and / or upholstered furniture, has an amine emission of 0 0 μg / m ³ and ≤ 40 µg / m ³ , preferably ≤ 10 µg / m ³ , particularly preferably ≤ 5 µg / m ³ , determined accordingly according to the test chamber method based on the DIN standard DIN EN ISO 16000-9: 2008-04 24 hours after loading the test chamber, and / or that the polyurethane system, preferably the polyurethane foam, in particular the flexible polyurethane foam, particularly preferred is the flexible polyurethane cold foam, preferably for the production of polyurethanes for use in the automotive industry, in particular in automobile interiors, for example as a headlining, interior lining of doors, punched-out sun visors, steering wheels and / or seat systems, an amine emission, hereinafter also as a VOC emission or VOC value according to VDA 278 (VOC = Volatile Organic Compounds), of ≥ 0 µg / g and ≤40 µg / g, preferably ≤ 10 µg / g, particularly preferably ≤ 5 µg / g, according to VDA 278 Analysis procedure in the version from October 2011, "Thermal desorption analysis of organic emissions for the characterization of non-metallic automotive materials" (30 minutes at 90 ° C), and / or that the polyurethane system, in particular the flexible polyurethane foam, particularly preferably the flexible polyurethane foam, preferably for the production of polyurethanes for the application in the automotive industry, especially in automobile interiors, for example as headlining, interior lining of doors, punched-out sun visors, steering wheels and / or seating systems, an amine emission, in the following also fog emission or fog value according to VDA 278 (Fog: slightly volatile substances that easily condense at room temperature and are used for fogging fittings windshield)) of ≥ 0 µg / g and ≤ 40 µg / g, preferably ≤ 10 µg / g, particularly preferably ≤ 5 µg / g, according to the VDA 278 analysis procedure in the version from October 2011 (60 minutes at 120 ° C). VDA is the association of the automotive industry (www.vda.de). Depending on the area of application of the polyurethane systems, in particular the polyurethane foams, for example for use in the automotive industry, there may be limits for the total emissions of volatile organic compounds (VOC _tot and / or fog _tot ) depending on the vehicle manufacturer specification, e.g. VOC _tot ≤ 100 µg / g and / or Fog _total ≤ 250 µg / g. It is all the more important that the contribution of the amines to the total emission (VOC _amine and / or fog _amine ) is as small as possible. The determination methods chosen in the sense of the present invention based on the DIN standard DIN EN ISO 16000-9: 2008-04 and the VDA 278 are explained in detail in the example section.

For the purposes of the present invention, “low-emission” with regard to emissions of dimethylformamide (DMF) means in particular that the nitrogen-containing compounds according to the formula (III) and / or (IV) and / or corresponding polyurethane systems, preferably polyurethane foams, in particular flexible polyurethane foams, particularly preferably flexible polyurethane hot foams , produced using the abovementioned compounds, has a DMF emission of 0 0 ppm and ppm 5 ppm, preferably 1 1 ppm, particularly preferably ppm 0.1 ppm. Advantageously, the present invention thus makes it possible, in particular, to provide flexible polyurethane foams, and in particular very flexible flexible polyurethane foams, which are particularly low-emission with regard to emissions of dimethylformamide. For the purposes of the present invention, the “DMF emission” is not a subset of the “amine emission”.

For the purposes of the present invention, “low-emission” with regard to emissions of aldehydes, in particular formaldehyde, means in particular that the polyurethane system, preferably the polyurethane foam, in particular the flexible polyurethane foam, is used by the foam manufacturers and the furniture industry in Europe and the USA as part of the voluntarily imposed program "CertiPUR" specified limits for aldehyde emissions, in particular for formaldehyde emissions and / or that the replacement of conventional catalysts, in particular amines, especially tertiary amines, containing one or more N-methyl or N, N-dimethyl groups, according to State of the art by nitrogen-containing compounds to be used according to the invention in the formulation of a corresponding polyurethane system leads to an improvement in the emissions caused by aldehydes, in particular formaldehyde. According to “CertiPUR”, the limit for formaldehyde emissions for mattresses, for example, is 0.1 mg / m ³ measured according to ASTM method D5116-97 “Small Chamber Test” with conditioning over 16 hours. Different analytical methods for determining aldehyde emissions are known to the person skilled in the art. Examples include VDA 275, VDA 277 or VDA 278, as well as various chamber test methods. VDA is the association of the automotive industry (www.vda.de). "VDA 275", according to the version from July 1994, provides a measurement method for determining the release of aldehydes, in particular formaldehyde, according to the modified bottle method, using 2,4 as the derivatization reagent of aldehydes in addition to the commonly used acetylacetone (via photometric detection) -Dinitrophenylhydrazine (2,4-DNP) (detection via HPLC after external calibration) can be used to determine not only formaldehyde but also acetaldehyde and propionaldehyde. In the context of this invention, both process designs of this VDA 275 are referred to as preferred methods for determining aldehyde, in particular formaldehyde emissions.

Advantageously, the present invention thus makes it possible to provide polyurethane systems, preferably polyurethane foams, in particular flexible polyurethane foams, which are particularly low-emission, preferably free of such emissions, with regard to emissions of nitrogen-containing compounds, hereinafter also referred to as amine emissions, even with different requirements.

Advantageously, the present invention thus enables the provision of polyurethane systems, preferably of polyurethane foams, in particular of flexible polyurethane foams, produced using the aforementioned nitrogen-containing compounds which are particularly low-emission, preferably free of such emissions, with respect to emissions of dimethylformamide (DMF) even under different requirements.

The present invention advantageously contributes to the provision of polyurethane systems, preferably polyurethane foams, in particular flexible polyurethane foams, produced using the abovementioned nitrogen-containing compounds which, with regard to emissions of aldehydes, in particular formaldehyde, even with different requirements, are lower in emissions than corresponding nitrogen-containing catalysts or corresponding polyurethane systems, in which conventional catalysts, in particular tertiary amines, containing one or more N-methyl or N, N-dimethyl groups, according to the prior art, are used instead of the nitrogen-containing compounds according to the invention. This is because commercially available amines or PU systems containing commercially available amines may otherwise contain formaldehyde as an impurity, for example because of their industrial production, for example in which formaldehyde or methanol was used as the alkylating agent in the amine production.

The present invention advantageously also contributes to the provision of low-odor polyurethane systems, preferably polyurethane foams, in particular flexible polyurethane foams. Low odor here means that the resulting polyurethane system has the lowest possible product odor, especially when the nitrogen-containing compounds according to the invention are used as alternative catalysts to catalysts according to the prior art, which can be checked in particular by olfactory inspection by a panel of people who have been trained in odor.

Advantageously, the present invention also contributes to improving the aging behavior, in particular the heat resistance and / or aging resistance when tempering (heat aging), of polyurethane systems, preferably polyurethane foams, in particular flexible polyurethane foams. Such aging phenomena are often closely linked to the choice of the catalyst system for the production of the polyurethane systems and generally lead to material fatigue. With the nitrogen-containing compounds according to the invention, the heat resistance and / or durability of the corresponding polyurethane systems compared to polyurethane systems which have been produced using conventional catalysts according to the prior art can advantageously be improved here. This effect can be advantageous, in particular in the case of polyurethane foams, preferably flexible block foams, in particular in the sense of dry heat aging in accordance with the DIN standard DIN EN ISO 2440 / A1: 2009-01 be observed, in particular at a temperature of 70, 100, 120, 125 and / or 140 ° C. and an aging time of 2, 4, 16, 22, 24, 48, 72 and / or 168 hours, preferably at 2, 24 and / or 168 hours if the nitrogen-containing compounds of the formula (III) and / or (IV) according to the invention are used as alternatives to structurally related catalysts according to the prior art in the foaming.

Advantageously, the present invention also enables the provision of preferably discoloration-minimized polyurethane systems, in particular polyurethane foams, preferably polyurethanes for use in the automotive industry, in particular in automobile interiors, for example as headliners, interior linings of doors, punched-out sun visors, steering wheels and / or seating systems, the polyurethane systems provided using nitrogen-containing catalysts according to the invention in particular lead to less discoloration of plastics, in particular plastic covers, in automobile interiors than those polyurethane systems which can be produced using conventional catalysts according to the prior art, in particular amines not according to the invention.

This can be demonstrated in particular by means of a PVC discoloration test in accordance with the Volkswagen test specification VW PV 3937, amine emissions using the indicator method.

Advantageously, the present invention enables a wider processing game in the production of polyurethane systems, in particular semi-hard polyurethane foams (open-cell rigid foams, for example for use as headliners in automobile interiors). This means that a greater range of variation in the use concentration of the nitrogen-containing compounds according to the invention is advantageously possible without adversely affecting the desired material properties, for example the open-cell nature of the foam or the density distribution over the foam block comparable or customarily used for such applications amine catalysts according to the prior art. This means an enormous amount of work for the user.

All reagents known as quaternization reagents can be used for possible quaternization of the compounds of the formula (III) and / or (IV). Alkylating agents, such as, for example, are preferably used as quaternizing agents. B. dimethyl sulfate, methyl chloride or benzyl chloride, preferably methylating agents such as in particular dimethyl sulfate. It is also possible to quaternize with alkylene oxides such as, for example, ethylene oxide, propylene oxide or butylene oxide, preferably with subsequent neutralization with inorganic or organic acids.

The compounds of the formulas (III) and / or (IV), if quaternized, can be single or multiple quaternized. The compounds of the formulas (III) and / or (IV) are preferably only quaternized. In the case of simple quaternization, the compounds of the formulas (III) and / or (IV) are preferably quaternized on a nitrogen atom which is part of a ring, preferably a pyrrolidine ring.

The compounds of the formula (III) and / or (IV) can be converted into the corresponding protonated compounds by reaction with organic or inorganic acids. These protonated compounds can e.g. be preferred if e.g. a slower polyurethane reaction is to be achieved or if the reaction mixture is to have an improved flow behavior when used.

As organic acids, for example, all organic acids mentioned below, for example carboxylic acids with 1 to 36 carbon atoms (aromatic or aliphatic, linear or branched), for example formic acid, lactic acid, 2-ethylhexanoic acid, salicylic acid and neodecanoic acid, or also polymeric acids such as e.g. Polyacrylic or polymethacrylic acids are used. As inorganic acids e.g. Phosphorus-based acids, sulfur-based acids or boron-based acids can be used.

However, the use of compounds of the formula (III) and / or (IV) which are not quaternized or protonated is particularly preferred for the purposes of this invention.

The objects according to the invention are described below by way of example, without the invention being restricted to these exemplary embodiments. If areas, general formulas or classes of compounds are given below, these should not only include the corresponding areas or groups of compounds that are explicitly mentioned, but also all sub-areas and sub-groups of compounds that are obtained by removing individual values (areas) or compounds can be. If documents are cited in the context of the present description, their content, in particular in relation to the facts in the context in which the document was cited, should completely belong to the disclosure content of the present invention. Unless otherwise stated, percentages are percentages by weight. If mean values are given below, then, unless otherwise stated, they are weight means. If parameters are specified below which were determined by measurement, the measurements were carried out, unless otherwise stated, at a temperature of 25 ° C. and a pressure of 101,325 Pa.

In the context of the present invention, polyurethane (PU) is understood in particular to mean a product obtainable by reacting polyisocyanates and polyols or compounds with isocyanate-reactive groups. In addition to the polyurethane, other functional groups can also be formed, such as uretdiones, carbodiimides, isocyanurates, allophanates, biurets, ureas and / or uretimines. PU for the purposes of the present invention is therefore understood to mean both polyurethane and polyisocyanurate, polyureas and uretdione, carbodiimide, allophanate, biuret and uretimine groups containing polyisocyanate reaction products. In the context of the present invention, polyurethane foam (PU foam) is understood to mean foam which is obtained as a reaction product based on polyisocyanates and polyols or compounds with isocyanate-reactive groups. In addition to the name giving polyurethane, other functional groups can also be formed, such as, for example, allophanates, biurets, ureas, carbodiimides, uretdiones, isocyanurates or uretimines. PU foams for the purposes of the present invention are therefore understood to mean both polyurethane foams (PUR foams) and polyisocyanurate foams (PIR foams). Preferred polyurethane foams are flexible polyurethane foams, rigid polyurethane foams and integral polyurethane foams. Conventional flexible polyurethane foams based on ether or ester polyol, highly elastic cold polyurethane foams (often also referred to as “high resilience” (HR) foams), viscoelastic polyurethane foams, semi-rigid are particularly preferred Polyurethane foams and rigid polyurethane foams, as well as foams whose properties lie between these classifications and are used in the automotive industry.

If at least one nitrogen-containing compound of the formula (III) and / or (IV) is mentioned in the context of this invention, then this includes the use of several different nitrogen-containing compounds of the formulas (III) and / or (IV), e.g. the joint use of nitrogen-containing compounds of the formulas (III) and (IV), and the use of the corresponding protonated compounds and also the use of the corresponding quaternized compounds and also the use of corresponding mixtures of all of the aforementioned nitrogen-containing compounds of the formula (III) and / or (IV), corresponding protonated and / or quaternized compounds.

The nitrogen-containing compounds of the formula (III) and / or (IV) according to the invention described above are in principle accessible via customary processes for the preparation of amines. An overview of the production and derivatization of amines, for example with ethylene oxide and. Propylene oxide (alkoxylation), for various processes for the methylation of primary or secondary amines, in particular also for the synthesis of pyrrolidine, is described in the article “Amines, Aliphatic” in Ullmann's Encylopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2012, Vol. 2 , Pp. 647-698 (DOI: 10.1002 / 14356007.a02_001) and the references contained therein.

Preferred synthesis building blocks for the purposes of the present invention are, in particular, polyols, preferably diols, for example glycols, amines, polyamines, in particular diamines, or amino alcohols, and also alkyl chlorides bearing amino groups, in particular those synthesis building blocks mentioned above which already contain a pyrrolidine Function. Polyols which are preferably used are, for example, monoethylene glycol (MEG) and 1,2-propylene glycol (PG). Polyamines which are preferably used are, for example, linear or branched, aliphatic diamines each having two terminal primary amino groups, such as, for example, 1,4-butanediamine or 1,6-hexanediamine, preferably ethylenediamine (EDA), trimethylenediamine, 1- (2-aminoethyl) pyrrolidine or 1- (3-aminopropyl) pyrrolidine, which, for example, based on the in WO 2012072441 described procedure or how after Krupka and Jiri et al. in Czechoslovak Chemical Communications, 65 (11), 1805-1819; 2000 described by a cyanoethylation and reduction to the amine or as in SU1421738 (A1) or by Katritzky et al. in Journal of Organic Chemistry (1994), 59, 5206-5214. Amino alcohols used with preference can be obtained, for example, by reacting ammonia or amines with epoxides (alkoxylation), preferably with ethylene oxide (EO) and / or propylene oxide (PO), by reacting alcohols or polyols, preferably diols, in particular glycols, with acrylonitrile ( Michael reaction) and subsequent hydrogenation, as described, for example, in Catalysis Today, 1998, 44, 277-283, and / or by amination of alcohols or polyols, preferably of diols, in particular of glycols with ammonia or amines by known processes, for example by Beller et al. in Chem. Asian J. 2007, 2, 403-410, by Milstein et al. in Angew. Chem. 2008, 120, 8789 -8792, by Watson and Williams in Science 2010, Vol. 329, pp. 635-636 or by Börner et al. described in ChemCatChem 2010, 2, 640-643. Examples include monoethanolamine (MEA), 3-amino-1-propanol, 1- (2-hydroxyethyl) pyrrolidine and 1- (3-hydroxypropyl) pyrrolidine. The polyamines, polyols and amino alcohols precisely described here are all commercially available. Alkyl chlorides bearing amino groups can be obtained, for example, by reacting bischloro-alkyl compounds, for example 1,2-dichloroethane, 1,4-dichlorobutane or 1,6-dichlorohexane, with one equivalent of an amine, in particular with pyrrolidine (nucleophilic substitution) will.

The pyrrolidine groups contained in all compounds can be introduced either at the beginning or at the end, depending on the desired synthesis route. For this purpose it may be preferable to use pyrrolidine itself, for example when pyrrolidine is reacted with alkyl halides, in particular with alkyl chlorides (nucleophilic substitution), such as for example from Aitken et al. in Tetrahedron, 2002, Vol. 58, 29, pp. 5933-5940 or from Tijskens et al. in Journal of Organic Chemistry, 1995, Vol. 60, 26, pp. 8371-8374 described, and / or by reacting pyrrolidine with epoxides (alkoxylation) or epoxy-bearing compounds, in particular with ethylene oxide (EO) - and / or propylene oxide ° (PO) -functionalized amines or amino alcohols, such as, for example, from Reppe et al. in Justus Liebigs Annalen der Chemie, 1955, Vol. 596, p. 1149 or from Moffett et al. in Journal of Organic Chemistry, 1949, Vol. 14, pp. 862-866 and in Org. Synth. Coll., 1963, Vol. IV, pp. 834ff, and / or by reacting pyrrolidine with amino alcohols, for example in a transition-metal-catalyzed embodiment as described by Jenner et al. in Journal of Organometallic Chemistry, 373 (1989), 343-352. Furthermore, the pyrrolidine function can also be reacted with 1,4-butanediol with primary amines or amino alcohols, as described, for example, by Jenner et al. in Journal of Organometallic Chemistry, 373 (1989), 343-352, and / or by reacting 1,4-butanediol with ammonia and hydroxyl-containing organic compounds, preferably polyols, in particular diols, preferably of glycols such as monoethylene glycol (MEG) and / or amino alcohols, in particular containing a primary hydroxyl function, as for example in DE 701825C described, introduced. Depending on the process conditions and the reaction chosen, a wide range of by-products can also be used, for example due to incomplete or only partial conversion of the starting materials, as well as through side reactions, for example between the selected starting materials, for example between polyamines, polyols, in particular 1,4-butanediol, and / or Amino alcohols occur.

For illustration, the preparation and application technology testing of selected compounds according to the invention according to formula (III) and / or (IV) is described in detail in the example section.

The compounds of the formula (III) and of the formula (IV) according to the invention can, for example, in the sense of alkoxylation with propylene oxide (PO), starting from 1- (3-aminopropyl) pyrrolidine (for the compound of the formula (III)) and 1- (2-aminoethyl) pyrrolidine (for the compound represented by formula (IV)). Both pyrrolidine building blocks used here are commercially available. The syntheses of the compounds of the formulas (III) and (IV), and also the synthesis of 1- (3-aminopropyl) pyrrolidine, are described in the example section.

If a methyl group is present in the compounds of the formula (III) and / or (IV) according to the invention, this can be obtained, for example, by reacting the corresponding secondary or primary amine group with formaldehyde as the methylating agent. The reductive methylation of primary and secondary amines using formaldehyde and formic acid is known as Eschweiler-Clarke methylation and is a special case of the Leuckart-Wallach reaction ( R. Leuckart, Ber. 18, 2341 (1885)., O. Wallach, Ann. 272, 99 (1892) ). Descriptions of the Eschweiler-Clarke methylation can be found in W. Eschweiler, Ber. 38, 880 (1905) and HT Clarke, et al., J. Am. Chem. Soc. 55, 4571 (1933) as well as other synthetic applications, eg also in E. Farkas, CJ Sunman, J. Org. Chem. 50, 1110 (1985) or J. Casanova, P. Devi, Synth. Commun. 23, 245 (1993) . Alternative methylation methods include the use of methanol, dimethyl sulfate (DMS), dimethyl sulfoxide (DMSO) or alkyl halides as alkylating agents. With regard to such processes, reference is made to the diverse literature on this subject known to the person skilled in the art.

In addition, a nitrogen-containing compound of the formula (III) and / or (IV) according to the invention which contains methyl groups can be obtained, for example, by using monomethylalmin as the N-methyl unit, for example by transition-metal-catalyzed reaction with hydroxyl-bearing groups Compounds, for example using Raney metals such as Raney cobalt or Raney nickel as catalysts, for example by reacting monomethylamine with 1- (2-hydroxyethyl) pyrrolidine, which can be obtained by alkoxylating pyrrolidine with ethylene oxide (EO) . Such aminations of alcohols with monomethylamine have been widely described in the literature, for example in US 5639916 or DE 4230402 . Depending on the process conditions and the chosen reaction procedure, such reactions can also result in a variety of by-products, for example due to incomplete or only partial conversion of the starting materials, and also through side reactions, for example between the selected starting materials, for example between polyamines, polyols and / or amino alcohols.

Alternatively, the particularly preferred compounds of the formulas (III) and (IV) can also be used, for example, for the amination of alcohols by e.g. heterogeneous, transition metal-catalyzed reaction of the corresponding amino alcohols, for example using Raney metals such as Raney cobalt or Raney nickel as catalysts, for example by reaction with pyrrolidine or with ammonia and 1,4-butanediol.

In the implementation of the synthesis building blocks, as described above, with ethylene oxide (EO) and / or propylene oxide (PO) in the sense of alkoxylation of amine functions, in particular primary aliphatic amines, depending on the choice of process conditions, for example depending on the nature and the amount used of the different starting materials and optionally used solvents, the choice of the catalyst used, the reactor used, and the selected process parameters such as pressure, temperature, reaction time, substrate concentration, an incomplete and / or only partial conversion or none at all Implementation of the synthetic building blocks used with ethylene oxide (EO) and / or propylene oxide (PO) occur. In addition, formation of by-products based on desired compounds according to the invention of the formula (III) and / or (IV), and / or on the basis of the intermediates formed in this sense and / or on the basis of ethylene oxide (EO) and / or propylene oxide ( PO) itself, optionally in the presence of other process additives, for example water and / or ammonia. It may be that technical products of the compounds according to the formula (III) and / or (IV), also referred to below as technical product mixtures, contain, for example, impurities, intermediates and / or by-products as further ingredients. Depending on the quality of the selected process and the number of corresponding purification steps, such a technical product mixture can have, for example, intermediate and / or by-products as secondary components and / or further impurities.

In particular, the use according to the invention, wherein at least one nitrogen-containing compound of the formula (III) and / or (IV), particularly preferably a compound of the formula (III), is used as the technical product mixture, containing impurities, intermediates and / or by-products as further ingredients in a total amount of up to 95% by weight, preferably ≤ 70% by weight, in particular ≤ 30% by weight, preferably ≤ 10% by weight, particularly preferably ≤ 5% by weight, with a lower limit eg are ≥ 0% by weight, or e.g. at 0.1% by weight, in particular comprising pyrrolidine, 1- (3-aminopropyl) pyrrolidine, 1- (2-aminoethyl) pyrrolidine, 1,4-butanediol, monoethylene glycol (MEG), diethylene glycol (DEG), propylene glycol ( PG), dipropylene glycol (DPG), monoethanolamine (MEA) and / or other by-products containing piperazine and / or morpholine groups, in particular 4- (3- (pyrrolidin-1-yl) propyl) morpholine, 4- (2- ( pyrrolidin-1-yl) ethyl) morpholine, 1- (3- (pyrrolidin-1-yl) propyl) piperazine, 1- (2- (pyrrolidin-1-yl) ethyl) piperazine, 2- (4- (3- (pyrrolidin-1-yl) propyl) piperazin-1-yl) ethanol, 2- (4- (2- (pyrrolidin-1-yl) ethyl) piperazin-1-yl) ethanol, 2- (4- (3- (pyrrolidin-1-yl) propyl) piperazin-1-yl) ethanamine, 2- (4- (2- (pyrrolidin-1-yl) ethyl) piperazin-1-yl) ethanamine, 1- (4- (3- (pyrrolidin-1-yl) propyl) piperazin-1-yl) propan-2-ol, 1- (4- (2- (pyrrolidin-1-yl) ethyl) piperazin-1-yl) propan-2-ol, corresponds to a preferred embodiment of this invention. Such a preferred product mix of technical quality can be used with great advantage in the methods and uses according to the invention and enables the problem to be solved.

1. (a) zumindest eine stickstoffhaltige Verbindung der Formel (III) und/oder (IV), besonders bevorzugt eine Verbindung nach der Formel (III), vorteilhafterweise in einer Gesamtmenge von ≥ 5 Gew.-%, bevorzugt 20-95 Gew.-%, insbesondere 30-70 Gew.-%,
2. (b) optional 1-(3-Aminopropyl)pyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20-95 Gew.-%, insbesondere 30-70 Gew.-%,
3. (c) optional 1-(2-Aminoethyl)pyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20-95 Gew.-%, insbesondere 30-70 Gew.-%,
4. (d) optional 1,4-Butandiol, vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
5. (e) optional Monoethylenglycol (MEG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
6. (f) optional Diethylenglycol (DEG) vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
7. (g) optional Propylenglycol (PG) vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
8. (h) optional Dipropylenglycol (DPG) vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%, und/oder
9. (i) optional weitere Piperazin- und/oder Morpholin-Gruppen enthaltende Nebenprodukte, insbesondere 4-(3-(pyrrolidin-1-yl)propyl)morpholin, 4-(2-(pyrrolidin-1-yl)ethyl)morpholin, 1-(3-(pyrrolidin-1-yl)propyl)piperazin, 1-(2-(pyrrolidin-1 -yl)ethyl)piperazin, 2-(4-(3-(pyrrolidin-1-yl)propyl)piperazin-1-yl)ethanol, 2-(4-(2-(pyrrolidin-1-yl)ethyl)piperazin-1-yl)ethanol, 2-(4-(3-(pyrrolidin-1-yl)propyl)piperazin-1-yl)ethanamin, 2-(4-(2-(pyrrolidin-1-yl)ethyl)piperazin-1-yl)ethanamin, 1-(4-(3-(pyrrolidin-1-yl)propyl)piperazin-1-yl)propan-2-ol und/oder 1-(4-(2-(pyrrolidin-1-yl)ethyl)piperazin-1-yl)propan-2-ol, in einer Menge ≤ 95 Gew.-%, vorzugsweise ≤ 70 Gew.-%, insbesondere ≤ 30 Gew.-%, bevorzugt ≤ 10 Gew.-%, besonders bevorzugt ≤ 5 Gew.-%, entspricht einer bevorzugten Ausführungsform dieser Erfindung.

In particular the use according to the invention of a technical product mixture, the technical product mixture containing

1. (a) at least one nitrogen-containing compound of the formula (III) and / or (IV), particularly preferably a compound of the formula (III), advantageously in a total amount of 5 5% by weight, preferably 20-95% by weight , in particular 30-70% by weight,
2. (b) optionally 1- (3-aminopropyl) pyrrolidine, advantageously in an amount ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
3. (c) optionally 1- (2-aminoethyl) pyrrolidine, advantageously in an amount ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
4. (d) optionally 1,4-butanediol, advantageously in an amount 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
5. (e) optionally monoethylene glycol (MEG), advantageously in an amount ≤ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
6. (f) optionally diethylene glycol (DEG) advantageously in an amount of 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
7. (g) optionally propylene glycol (PG) advantageously in an amount of 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
8. (h) optionally dipropylene glycol (DPG) advantageously in an amount ≤ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight, and / or
9. (i) optionally by-products containing further piperazine and / or morpholine groups, in particular 4- (3- (pyrrolidin-1-yl) propyl) morpholine, 4- (2- (pyrrolidin-1-yl) ethyl) morpholine, 1 - (3- (pyrrolidin-1-yl) propyl) piperazine, 1- (2- (pyrrolidin-1-yl) ethyl) piperazine, 2- (4- (3- (pyrrolidin-1-yl) propyl) piperazin- 1-yl) ethanol, 2- (4- (2- (pyrrolidin-1-yl) ethyl) piperazin-1-yl) ethanol, 2- (4- (3- (pyrrolidin-1-yl) propyl) piperazin- 1-yl) ethanamine, 2- (4- (2- (pyrrolidin-1-yl) ethyl) piperazin-1-yl) ethanamine, 1- (4- (3- (pyrrolidin-1-yl) propyl) piperazin- 1-yl) propan-2-ol and / or 1- (4- (2- (pyrrolidin-1-yl) ethyl) piperazin-1-yl) propan-2-ol, in an amount ≤ 95% by weight , preferably 70 70% by weight, in particular ≤ 30% by weight, preferably ≤ 10% by weight, particularly preferably 5 5% by weight, corresponds to a preferred embodiment of this invention.

• mit b), c), d), e), f), g), h), i), mit b) und e), mit b) und f), mit b) und g), mit b) und h), mit c) und e), mit c) und f), mit c) und g), mit c) und h), mit i) und e), mit i) und f), mit i) und g), mit i) und h), mit b) und c), mit b), c) und i), mit b), c) und e), mit b), c), i) und e), mit b), c) und f), mit b), c), i) und f), mit b), c) und g), mit b), c), i) und g), mit b), c) und h) oder mit b), c), i) und h).

For the purposes of the aforementioned preferred embodiment, particularly preferred industrial product mixtures in the context of the present invention are compositions in which at least one nitrogen-containing compound of the formula (III) and / or (IV) and / or a corresponding quaternized and / or protonated compound is used Combination:

• with b), c), d), e), f), g), h), i), with b) and e), with b) and f), with b) and g), with b) and h), with c) and e), with c) and f), with c) and g), with c) and h), with i) and e), with i) and f), with i) and g ), with i) and h), with b) and c), with b), c) and i), with b), c) and e), with b), c), i) and e), with b), c) and f), with b), c), i) and f), with b), c) and g), with b), c), i) and g), with b), c ) and h) or with b), c), i) and h).

The compounds of the formula (III) and / or (IV) and / or corresponding quaternized and / or protonated compounds described above are preferably used in the production of polyurethane systems according to the invention, preferably for the production of polyurethane coatings, polyurethane adhesives, polyurethane sealants, polyurethane elastomers or in particular for the production of Polyurethane foams used as catalysts. The compounds of the formula (III) and / or (IV) and / or the corresponding quaternized and / or protonated compounds can be used in addition to customary catalysts or as a replacement for customary catalysts. In particular, the compounds according to the invention can be used as a replacement for other nitrogen-containing catalysts, hereinafter also referred to as amine catalysts or amines, and depending on the application as a partial or complete replacement for conventional metal-containing catalysts according to the prior art.

It therefore corresponds to a preferred embodiment of the invention if at least one nitrogen-containing compound of the formula (III) and / or (IV), a correspondingly quaternized and / or protonated compound, or mixtures of the nitrogen-containing compound of the formula (III) and / or (IV ) with appropriate quaternized and / or protonated compounds is used as a catalyst in the production of polyurethane systems, in particular polyurethane foams. In particular, the nitrogenous compound mentioned can also be used as a technical product mixture. Suitable technical product mixtures are described in more detail below.

It goes without saying that the person skilled in the art for producing the different polyurethane systems, in particular the different types of polyurethane foams, for example hot, cold, ester flexible polyurethane foams or rigid polyurethane foams, the substances required for this, such as isocyanates, polyols, stabilizers, surfactants, etc. selects accordingly in order to obtain the desired polyurethane type, in particular polyurethane foam type.

In the production of polyurethane systems, in particular polyurethane foams, according to the invention, at least one compound of the formula (III) and / or (IV) and / or a corresponding quaternized and / or protonated compound, at least one polyol component and at least one isocyanate component, are preferably added optionally Presence of water, physical blowing agents, flame retardants, additional catalysts and / or other additives.

Further information on the starting materials, catalysts and auxiliaries and additives used can be found, for example, in the Plastics Handbook, Volume 7, Polyurethanes, Carl Hanser Verlag, Munich, 1st edition 1966, 2nd edition, 1983 and 3rd edition, 1993. The following Compounds, components and additives are only mentioned by way of example and can be replaced and / or supplemented by other substances known to the person skilled in the art.

The compounds of the formula (III) and / or (IV) and / or a correspondingly quaternized and / or protonated compound to be used according to the invention, in total, are preferably in a mass fraction of 0.01 to 20.0 parts (pphp) 0.01 to 5.00 parts and particularly preferably 0.02 to 3.00 parts based on 100 parts (pphp) polyol component used.

It therefore corresponds to a preferred embodiment of the invention if, during the production of the polyurethane system, in particular polyurethane foam, a composition is produced which contains at least one nitrogen-containing compound of the formula (III) and / or (IV) and / or a corresponding quaternized and / or protonated compound, and also has at least one polyol component, at least one isocyanate component and optionally one or more blowing agents, and this composition is reacted. In particular, the nitrogenous compound mentioned can also be used as a technical product mixture. Suitable technical product mixtures are described in more detail below.

One or more organic polyisocyanates with two or more isocyanate functions are preferably used as isocyanate components. One or more polyols having two or more isocyanate-reactive groups are preferably used as polyol components.

Isocyanates suitable as isocyanate components for the purposes of this invention are all isocyanates which contain at least two isocyanate groups. In general, all known aliphatic, cycloaliphatic, arylaliphatic and preferably aromatic polyfunctional isocyanates can be used. Isocyanates are preferably used in a range from 60 to 350 mol%, particularly preferably in a range from 60 to 140 mol%, relative to the sum of the isocyanate-consuming components.

Alkylene diisocyanates with 4 to 12 carbon atoms in the alkylene radical, such as 1,12-dodecane diisocyanate, 2-ethyltetramethylene diisocyanate-1,4, 2-methylpentamethylene diisocyanate-1,5, tetramethylene diisocyanate-1,4, and preferably 1,6-hexamethylene diisocyanate, can be mentioned here as examples (HMDI), cycloaliphatic diisocyanates, such as cyclohexane-1,3- and 1-4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,35-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI for short), 2,4- and 2,6-hexahydrotoluenediisocyanate and the corresponding isomer mixtures, and preferably aromatic di- and polyisocyanates, such as, for example, 2,4- and 2,6-toluenediisocyanate (TDI) and the corresponding isomer mixtures, mixtures of 2,4'- and 2,2 '-Diphenylmethane diisocyanates (MDI) and polyphenylpolymethylene polyisocyanates (raw MDI) and mixtures of raw MDI and toluene diisocyanates (TDI). The organic di- and polyisocyanates can be used individually or in the form of their mixtures.

It is also possible to use isocyanates which have been modified by the incorporation of urethane, uretdione, isocyanurate, allophanate and other groups, so-called modified isocyanates.

Particularly suitable organic polyisocyanates and therefore particularly preferably used are various isomers of toluenediisocyanate (2,4- and 2,6-toluenediisocyanate (TDI), in pure form or as isomer mixtures of different compositions), 4,4'-diphenylmethane diisocyanate (MDI), that so-called "crude MDI" or "polymeric MDI" (contains not only the 4,4'- but also the 2,4'- and 2,2'-isomers of MDI and higher core products) as well as the binuclear product called "pure MDI" from predominantly 2,4'- and 4,4'-isomer mixtures or their prepolymers. Examples of particularly suitable isocyanates are, for example, in EP 1712578 , EP 1161474 , WO 00/58383 , US 2007/0072951 , EP 1678232 and the WO 2005/085310 to which full reference is made here.

For the purposes of the present invention, suitable polyols as polyol components are all organic substances with several groups reactive toward isocyanates, preferably OH groups, and also their preparations. Preferred polyols are all for the production of polyurethane systems, in particular polyurethane foams; Usually used polyether polyols and / or polyester polyols and / or hydroxyl-containing aliphatic polycarbonates, in particular polyether polycarbonate polyols and / or polyols of natural origin, so-called "natural oil based polyols" (NOPs). The polyols usually have a functionality of 1.8 to 8 and number-average molecular weights in the range from 500 to 15000. The polyols with OH numbers in the range from 10 to 1200 mgKOH / g are usually used. The number average molecular weights are usually determined by gel permeation chromatography (GPC), in particular using polypropylene glycol as the reference substance and tetrahydrofuran (THF) as the eluent. The OH numbers can in particular according to the DIN standard DIN 53240: 1971-12 be determined.

Polyether polyols can be prepared by known processes, for example by anionic polymerization of alkylene oxides in the presence of alkali hydroxides, alkyl alcoholates or amines as catalysts and with the addition of at least one starter molecule which preferably contains 2 or 3 reactive hydrogen atoms, or by cationic polymerization of alkylene oxides in the presence of Lewis Acids such as antimony pentachloride or boron trifluoride etherate or by double metal cyanide catalysis. Suitable alkylene oxides contain 2 to 4 carbon atoms in the alkylene radical. Examples are tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide; ethylene oxide and 1,2-propylene oxide are preferably used. The alkylene oxides can be used individually, cumulatively, in blocks, alternately in succession or as mixtures. In particular, compounds with at least 2, preferably 2 to 8 hydroxyl groups or with at least two primary amino groups in the molecule are used as starting molecules. For example, starter molecules can be used. Water, 2-, 3- or 4-valent alcohols such as ethylene glycol, 1,2-and 1,3-propanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, castor oil etc., higher polyfunctional polyols, especially sugar compounds such as glucose, Sorbitol, mannitol and sucrose, polyhydric phenols, resols, such as oligomeric condensation products from phenol and formaldehyde and Mannich condensates from phenols, formaldehyde and dialkanolamines and melamine, or amines such as aniline, EDA, TDA, MDA and PMDA, particularly preferably TDA and PMDA. The choice of the suitable starter molecule depends on the respective field of application of the resulting polyether polyol in the production of polyurethane (e.g. different polyols are used for the production of flexible polyurethane foams than in the production of rigid polyurethane foams).

Polyester polyols are based on esters of polyvalent aliphatic or aromatic carboxylic acids, preferably with 2 to 12 carbon atoms. Examples of aliphatic carboxylic acids are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid and fumaric acid. Examples of aromatic carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and the isomeric naphthalenedicarboxylic acids. The polyester polyols are obtained by condensation of these polyvalent carboxylic acids with polyhydric alcohols, preferably diols or triols with 2 to 12, particularly preferably with 2 to 6, carbon atoms, preferably trimethylolpropane and glycerol.

Polyether polycarbonate polyols are polyols which contain carbon dioxide bound as carbonate. Since carbon dioxide is a by-product of many processes in the chemical industry, the use of carbon dioxide as a comonomer in alkylene oxide polymerizations is of particular commercial interest. A partial replacement of alkylene oxides in polyols with carbon dioxide has the potential to significantly reduce the costs for the production of polyols. In addition, the use of CO ₂ as a comonomer is ecologically very advantageous since this reaction is the conversion of a greenhouse gas to a polymer. The production of polyether polycarbonate polyols by addition of alkylene oxides and carbon dioxide onto H-functional starter substances using catalysts has long been known. Various catalyst systems can be used here: The first generation represented heterogeneous zinc or aluminum salts, such as those in US-A 3900424 or US-A 3953383 are described. Furthermore, mono- and binuclear metal complexes have been successfully used for the copolymerization of CO2 and alkylene oxides ( WO 2010/028362 , WO 2009/130470 , WO 2013/022932 or WO 2011/163133 ). The most important class of catalyst systems for the copolymerization of carbon dioxide and alkylene oxides are the double metal cyanide catalysts, also known as DMC catalysts ( US-A 4500704 , WO 2008/058913 ). Suitable alkylene oxides and H-functional starter substances are those which are also used for the production of carbonate-free polyether polyols, as described above.

Polyols based on renewable raw materials "Natural oil based polyols" (NOPs) for the production of polyurethane foams are of increasing interest in view of the long-term limited availability of fossil resources, namely oil, coal and gas, and against the background of rising crude oil prices, and are already in many of them Applications described ( WO 2005/033167 ; US 2006/0293400 , WO 2006/094227 , WO 2004/096882 , US 2002/0103091 , WO 2006/116456 and EP 1678232 ). A number of these polyols from various manufacturers are now available on the market ( WO2004 / 020497 , US2006 / 0229375 , WO2009 / 058367 ). Depending on the basic raw material (e.g. soybean oil, palm oil or castor oil) and the subsequent processing, polyols with different properties result. Basically, two groups can be distinguished: a) Polyols based on renewable raw materials, which are modified to such an extent that they can be used 100% for the production of polyurethanes ( WO2004 / 020497 , US2006 / 0229375 ); b) polyols based on renewable raw materials, which due to their processing and properties can only replace the petrochemically based polyol to a certain extent ( WO2009 / 058367 ).

Another class of polyols that can be used are the so-called packed polyols (polymer polyols). These are distinguished by the fact that they contain solid organic fillers up to a solids content of 40% or more in disperse distribution. Among others, SAN, PHD and PIPA polyols can be used. SAN polyols are highly reactive polyols that contain a copolymer based on styrene / acrylonitrile (SAN) dispersed. PHD polyols are highly reactive polyols, which also contain polyurea in dispersed form. PIPA polyols are highly reactive polyols which contain a polyurethane, for example by in-situ reaction of an isocyanate with an alkanolamine in a conventional polyol, in dispersed form.
The proportion of solids, which, depending on the application, is preferably between 5 and 40%, based on the polyol, is responsible for improved cell opening, so that the polyol can be expanded in a controlled manner, in particular with TDI, and the foams do not shrink. The solid acts as an essential process aid. Another function is to control the hardness via the solids content, because higher solids contents result in greater hardness of the foam. The formulations with polyols containing solids are significantly less inherently stable and therefore, in addition to chemical stabilization through the crosslinking reaction, also require physical stabilization. Depending on the solids content of the polyols, these can be used, for example, alone or in a mixture with the above-mentioned unfilled polyols.

Another class of polyols which can be used are those which are obtained as prepolymers by reacting polyol with isocyanate in a molar ratio of 100 to 1 to 5 to 1, preferably 50 to 1 to 10 to 1 will. Such prepolymers are preferably prepared in solution in polymer, the polyol preferably corresponding to the polyol used to prepare the prepolymers.

Another class of polyols that can be used are the so-called autocatalytic polyols, in particular autocatalytic polyether polyols. Such polyols are based, for example, on polyether blocks, preferably on ethylene oxide and / or propylene oxide blocks, and also contain catalytically active functional groups, such as nitrogen-containing functional groups Groups, in particular amino groups, preferably tertiary amine functions, urea groups and / or heterocycles containing nitrogen atoms. By using such autocatalytic polyols in the production of polyurethane systems, in particular polyurethane foams, preferably flexible polyurethane foams, the required amount of optionally additionally used catalysts can be reduced depending on the application and / or adapted to the specific desired foam properties. Suitable polyols are for example in WO0158976 (A1 ), WO2005063841 (A1 ), WO0222702 (A1 ), WO2006055396 (A1 ), WO03029320 (A1 ), WO0158976 (A1 ), US6924321 (B2 ), US6762274 (B2 ), EP2104696 (B1 ), WO2004060956 (A1 ) or WO2013102053 (A1 ) and can be obtained, for example, from Dow under the trade names Voractiv ™ and / or SpecFlex ™ Activ.

Depending on the required properties of the resulting foams, appropriate polyols can be used, as described for example in: US 2007/0072951 A1 , WO 2007/111828 , US 2007/0238800 , US 6359022 or WO 96/12759 . Other polyols are known to the person skilled in the art and can be, for example, the EP-A-0380993 or US-A-3346557 are taken to which full reference is made.

According to a preferred embodiment of the invention, in particular for the production of molded and highly elastic flexible foams, bifunctional and / or trifunctional polyether alcohols are used which have primary hydroxyl groups, preferably over 50%, particularly preferably over 80%, in particular those with an ethylene oxide block on Chain end. Depending on the required properties of this preferred embodiment according to the invention, in particular for the production of the foams mentioned above, in addition to the polyether alcohols described here, other polyether alcohols which carry primary hydroxyl groups and are predominantly based on ethylene oxide, in particular with a proportion of> 70% ethylene oxide blocks, are preferably used, preferably> 90%. All polyether alcohols described in the sense of this preferred embodiment preferably have a functionality of 2 to 8, particularly preferably 2 to 5, number-average molecular weights in the range from 2500 to 15000, preferably 4500 to 12000 and usually OH numbers in the range from 5 to 80, preferably 20 up to 50 mgKOH / g.

According to a further preferred embodiment of the invention, in particular for the production of flexible flexible foams, bifunctional and / or trifunctional polyether alcohols are used which have secondary hydroxyl groups, preferably over 50%, particularly preferably over 90%, in particular those with a propylene oxide block or statistical propylene and chain end ethylene oxide block or those based only on propylene oxide blocks. Such polyether alcohols preferably have a functionality of 2 to 8, particularly preferably 2 to 4, number-average molecular weights in the range from 500 to 8000, preferably 800 to 5000, particularly preferably 2500 to 4500 and usually OH numbers in the range from 10 to 100, preferably 20 up to 60 mgKOH / g.

According to a further preferred embodiment of the invention, in particular for the production of polyurethane foams, preferably of flexible polyurethane foams, preferably for the production of molded and highly elastic flexible foams, autocatalytic polyols, as described above, are used.

According to a further preferred embodiment of the invention, in particular for the production of flexible polyurethane polyester foams, polyester alcohols based on diols and / or triols, preferably glycerol and / or trimethylolpropane, and aliphatic carboxylic acids, preferably adipic acid, suberic acid, azelaic acid and / or Sebacic acid used. Such polyester alcohols preferably have a functionality of 2 to 4, particularly preferably 2 to 3, number-average molecular weights in the range from 200 to 4000, preferably 400 to 3000, particularly preferably 600 to 2500 and usually OH numbers in the range from 10 to 1000, preferably 20 - 500, particularly preferably 30 - 300 mgKOH / g.

According to a further preferred embodiment of the invention, in particular for the production of rigid polyisocyanurate (PIR) foams, polyester alcohols based on diols and / or triols, preferably monoethylene glycol, and aromatic carboxylic acids, preferably phthalic acid and / or terephthalic acid, are used. Such polyester alcohols preferably have a functionality of 2 to 4, particularly preferably 2 to 3, number-average molecular weights in the range from 200 to 1500, preferably 300 to 1200, particularly preferably 400 to 1000 and usually OH numbers in the range from 100 to 500, preferably 150 300, particularly preferably 180-250 mgKOH / g.

According to a further preferred embodiment of the invention, in particular for the production of rigid polyurethane foams, two- to eight-functional polyether alcohols are used which have secondary hydroxyl groups, preferably over 50%, particularly preferably over 90%, in particular those with a propylene oxide block or statistical Chain end propylene and ethylene oxide blocks or those based only on propylene oxide blocks. Such polyether alcohols preferably have a functionality of 2 to 8, particularly preferably 3 to 8, number-average molecular weights in the range from 500 to 2000, preferably 800 to 1200 and usually OH numbers in the range from 100 to 1200, preferably 120 to 700, particularly preferably 200 up to 600 mgKOH / g. Depending on the required properties of these foams preferred according to the invention, in addition to the polyols described here, polyether alcohols, as described above with larger number-average molecular weights and lower OH numbers, and / or additional polyester polyols, as described above based on aromatic carboxylic acids, are used.

According to a further preferred embodiment of the invention, in particular for the production of viscoelastic polyurethane foams, mixtures of different, preferably two or three, polyfunctional polyester alcohols and / or polyether alcohols are preferably used. The polyol combinations used here usually consist of a low molecular weight “crosslinker” polyol, for example a rigid foam polyol with high functionality (> 3) and / or a conventional high molecular weight flexible foam or HR polyol and / or a “Hypersoft” Polyether polyol with a high proportion of ethylene oxide blocks and with cell-opening properties.

A preferred ratio of isocyanate and polyol expressed as an index of the formulation, i.e. as the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (for example OH groups, NH groups) multiplied by 100 is in the range from 10 to 1000, preferably 40 to 350, particularly preferably 70 to 140. An index of 100 is given for a molar ratio of the reactive groups of 1 to 1.

Depending on the application, it may be preferred according to the invention that, in addition to the nitrogen-containing compounds of the formula (III) and / or (IV) according to the invention, and / or corresponding protonated and / or quaternized compounds, additional catalysts are used, individually during the foaming or as a catalyst combination premixed with the nitrogen-containing compounds of the formula (III) and / or (IV), and / or corresponding protonated and / or quaternized compounds.

For the purposes of this invention, the expression “additional catalysts” includes, in particular, the use of compounds which are not the same as the nitrogen-containing compounds of the formula (III) and / or (IV) and / or corresponding protonated and / or quaternized compounds according to the invention, and simultaneously in Isocyanate reactions, in particular the reactions mentioned below, are capable of catalyzing and / or are used as catalysts, co-catalysts or activators in the production of polyisocyanate reaction products, in particular in the production of polyurethane systems, particularly preferably in the production of polyurethane foams will.

For the purposes of this invention, the expression “premixed catalyst combination”, hereinafter also referred to as catalyst combination, encompasses, in particular, finished mixtures of nitrogen-containing compounds of the formula (III) and / or (IV) according to the invention, corresponding protonated and / or quaternized compounds, additional catalysts, and optionally further ingredients or additives such as water, organic solvents, acids for blocking the amines, emulsifiers, surfactants, blowing agents, antioxidants, flame retardants, stabilizers and / or siloxanes, preferably polyether siloxanes, which are present as such before the foaming and do not have to be added as individual components during the foaming process.

Any catalysts for the reactions isocyanate-polyol (urethane formation) and / or isocyanate-water (amine and carbon dioxide formation) and / or isocyanate dimerization (uretdione formation) isocyanate can be used as additional catalysts in the context of this invention, for example Trimerization (isocyanurate formation), isocyanate isocyanate with CO ₂ elimination (carbodiimide formation) and / or isocyanate amine (urea formation) and / or “secondary” crosslinking reactions such as isocyanate urethane (allophanate formation) and / or isocyanate-urea (biuret formation) and / or isocyanate-carbodiimide (uretimide formation) can be used.

Suitable additional catalysts for the purposes of the present invention are, for example, substances which catalyze one of the abovementioned reactions, in particular the gel reaction (isocyanate-polyol), the blowing reaction (isocyanate-water) and / or the di- or trimerization of the isocyanate. Such catalysts are preferably nitrogen-containing compounds, in particular amines and ammonium salts, and / or metal-containing compounds.

Suitable nitrogen-containing compounds as additional catalysts for the purposes of the present invention are all nitrogen-containing compounds according to the prior art, unlike the nitrogen-containing compounds according to the invention of the formula (III) and / or (IV) which catalyze one of the above-mentioned isocyanate reactions and / or can be used for the production of polyurethanes, in particular polyurethane foams.

For the purposes of this invention, the expression “nitrogen-containing compounds of the formula (III) and / or (IV)” in each case encompasses the corresponding protonated and / or quaternized compounds and mixtures of these compounds. For the purposes of this invention, the expression “nitrogen-containing compounds of the formula (III) and / or (IV)” in each case includes the corresponding protonated and / or quaternized compounds and mixtures of these compounds. For the purposes of this invention, the expression “at least one nitrogen-containing compound of the formula (III) and / or (IV)” also includes the joint use of such nitrogen-containing compounds, e.g. the joint use of nitrogen-containing compounds of the formula (III) and (IV).

Examples of suitable additional nitrogen-containing compounds as catalysts for the purposes of the present invention are the amines triethylamine, N, N-dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, N, N-dimethylaminoethylamine, N, N, N ', N'-tetramethylethylene-1, 2-diamine, N, N, N ', N'-tetramethylpropylene-1,3-diamine, N, N, N', N'-tetramethyl-1,4-butanediamine, N, N, N ', N'- Tetramethyl-1,6-hexanediamine, N, N, N ', N ", N" -pentamethyldiethylenetriamine, N, N, N'-trimethylaminoethylethanolamine, N, N-dimethylaminopropylamine, N, N-diethylaminopropylamine, 1- (2-aminoethyl ) pyrrolidine, 1- (3-aminopropyl) pyrrolidine, N, N-dimethylaminopropyl-N ', N'-dipropan-2-olamine, 2 - [[3- (dimethylamino) propyl] methylamino] ethanol, 3- (2- Dimethylamino) ethoxy) propylamine, N, N-bis [3- (dimethylamino) propyl] amine, N, N, N ', N ", N" -pentamethyldipropylenetriamine, 1- [bis [3- (dimethylamino) propyl] amino ] -2-propanol, N, N-bis [3- (dimethylamino) propyl] -N ', N'-dimethylpropane-1,3-diamine, triethylene diamine, 1,4-diazabicyclo- [2.2.2] octane-2 -methanol, N, N'-dimethylpi perazin, 1,2-dimethylimidazole, N- (2-hydroxypropyl) imidazole, 1-isobutyl-2-methylimidazole, N- (3-aminopropyl) imidazole, N-methylimidazole, N-ethylmorpholine, N-methylmorpholine, 2,2, 4-trimethyl-2-silamorpholine, N-ethyl-2,2-dimethyl-2-silamorpholine, N- (2-aminoethyl) morpholine, N- (2-hydroxyethyl) morpholine, 2,2'-dimorpholinodiethyl ether, N, N '-Dimethylpiperazine, N- (2-hydroxyethyl) piperazine, N- (2-aminoethyl) piperazine, N, N-dimethylbenzylamine, N, N-dimethylaminoethanol, N, N-diethylaminoethanol, 1- (2-hydroxyethyl) pyrrolidine, 3 -Dimethylamino-1-propanol, 1- (3-hydroxypropyl) pyrrolidine, N, N-dimethylaminoethoxyethanol, N, N-diethylaminoethoxyethanol, bis (2-dimethylaminoethyl ether), N, N, N'-trimethyl-N '- (2nd -hydroxyethyl) bis (2-aminoethyl) ether, N, N, N'-trimethyl-N-3'-aminopropyl (bisaminoethyl) ether, tris (dimethylaminopropyl) hexahydro-1,3,5-triazine, 1,8- Diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, N-methyl- 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1,4,6-triazabicy clo [3.3.0] oct-4-ene, 1,1,3,3-tetramethylguanidine, tert-butyl-1,1,3,3-tetramethylguanidine, guanidine, 3-dimethylaminopropyl urea, 1,3-bis [3- (dimethylamino) propyl] urea, bis-N, N- (dimethylaminoethoxyethyl) isophoronedicarbamate, 3-dimethylamino-N, N-dimethylpropionamide and 2,4,6-tris (dimethylaminomethyl) phenol. Suitable additional nitrogen-containing catalysts according to the prior art can be obtained, for example, from Evonik under the trade name TEGOAMIN ^® .

Suitable metal-containing compounds as additional catalysts for the purposes of the present invention are all metal-containing compounds according to the prior art which catalyze one of the abovementioned isocyanate reactions and / or for the production of polyurethanes, in particular polyurethane foams, in addition to the nitrogen-containing compounds of the formula ( III) and / or (IV) can be used. For example, they can be selected from the group of organometallic or organometallic compounds, organometallic or organometallic salts, organic metal salts, inorganic metal salts and from the group of charged or uncharged metal-containing coordination compounds, in particular metal-chelate complexes.

For the purposes of this invention, the term “organometallic or organometallic compounds” encompasses in particular the use of metal-containing compounds which have a direct carbon-metal bond, here also as metal organyls (eg tin organyls) or organometallic or organometallic compounds (eg organotin compounds) ) designated. For the purposes of this invention, the expression “organometallic or organometallic salts” includes in particular the use of organometallic or organometallic compounds with salt character, ie ionic compounds in which either the anion or cation is of organometallic nature (eg organotin oxides, organotin chlorides or organotin carboxylates). For the purposes of this invention, the term “organic metal salts” encompasses in particular the use of metal-containing compounds which have no direct carbon-metal bond and at the same time are metal salts in which either the anion or the cation is an organic compound (for example tin (II ) Carboxylates). For the purposes of this invention, the term “inorganic metal salts” encompasses in particular the use of metal-containing compounds or metal salts in which neither anion nor cation is an organic compound, for example metal chlorides (for example tin (II) chloride), pure or mixed, thus metal oxides containing several metals (eg tin oxides) and / or metal silicates or aluminosilicates. For the purposes of this invention, the term “coordination compound” encompasses in particular the use of metal-containing compounds which are composed of one or more central particles and one or more ligands, the central particles being charged or uncharged metals (for example metal or tin-amine complexes ). For the purposes of this invention, the term “metal-chelate complexes” encompasses in particular the use of metal-containing coordination compounds which have ligands with at least two coordination or binding sites to the metal center (for example metal or tin-polyamine or metal or tin Polyether complexes).

Suitable metal-containing compounds, in particular as defined above, as additional catalysts for the purposes of the present invention can be selected, for example, from all metal-containing compounds containing lithium, sodium, potassium, magnesium, calcium, scandium, yttrium, titanium, zirconium, vanadium, niobium, chromium , Molybdenum, tungsten, manganese, cobalt, nickel, copper, zinc, mercury, aluminum, gallium, indium, germanium, tin, lead, and / or bismuth, in particular sodium, potassium, magnesium, calcium, titanium, zirconium, molybdenum, tungsten , Zinc, aluminum, tin and / or bismuth, particularly preferably tin, bismuth, zinc and / or potassium.

Suitable inorganic metal salts, in particular as defined above, as additional catalysts for the purposes of the present invention can be selected, for example, from the group of the salts of inorganic acids such as, for example, hydrochloric acid, carbonic acid, sulfuric acid, nitric acid and phosphoric acid and / or of further halogen-containing acids. The resulting inorganic metal salts, for example metal chlorides, metal sulfates, metal phosphates, preferably metal chlorides such as tin (II) chloride, can generally only be used in combination with in the production of polyurethane systems, in particular polyurethane foams other organometallic salts, organic metal salts or nitrogenous catalysts and not as the only catalysts, in pure form or mixed in a solvent.

Suitable charged or uncharged metal-containing coordination compounds, in particular the metal-chelate complexes, in particular as defined above, as additional catalysts for the purposes of the present invention can be selected, for example, from the group of mono- or polynuclear metal-amine, metal-polyamine , Metal-polyether, metal-polyester and / or metal-polyamine-polyether complexes. Such complexes can either be formed upstream in situ during the foaming and / or the foaming, or can be used as isolated complexes, in pure form or mixed in a solvent. Suitable complexing agents, ligands and / or chelate ligands are, for example, acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, salicylaldehyde, salicyladehydimine and other Schiff bases, cyclopentanone-2-carboxylate, pyrrolidones such as N-methyl-2-pyrrollidone, N- Ethyl-2-pyrrolidone and polyvinylpyrrolidones (of different molecular weight distributions), polyethers of different molecular weights, cyclic polyethers such as, for example, crown ethers and diamines and polyamines containing primary, secondary and / or tertiary amines.

Suitable metal-containing coordination compounds are, for example, all metal acetylacetonates such as nickel (II) acetylacetonate, zinc (II) acetylacetonate, copper (II) acetylacetonate, molybdenum dioxo acetylacetonate, all iron acetylacetonates, all cobalt acetylacetonates, all zirconium acetylacetonates, all Titanium acetylacetonates, all bismuth acetylacetonates and all tin acetylacetonates.

Suitable organometallic salts and organic metal salts, in particular as defined above, as additional catalysts for the purposes of the present invention can be selected, for example, from the group of salts of organic acids.

For the purposes of this invention, the term “organic acids” encompasses all organic chemical, that is to say carbon-containing, compounds which have a functional group which is combined with water and other protonatable solvents can enter into an equilibrium reaction in the sense of an acid-base reaction.

Suitable organic acids can, for example, be selected from the group of carboxylic acids, ie organic compounds which carry one or more carboxy groups (* -COOH), so-called carboxylates, and / or alcohols, ie organic compounds one or more hydroxyl groups (* - OH), so-called alcoholates, and / or of thiols, ie organic compounds which carry one or more thiol groups (* -SH, also referred to as mercapto groups in the case of molecules with a functional group of higher priority), so-called thiolates (or mercaptides ), and / or of mercaptoacetic acid esters as a special case of the thiols, ie organic compounds which carry one or more mercaptoacetic acid ester groups (* -O-CO-CH ₂ -CH ₂ -SH), so-called mercaptoacetates, and / or of sulfuric acid esters, ie organic compounds which carry one or more sulfate groups (* -O-SO ₃ H), so-called sulfates, and / or of sulfonic acids, ie organic compounds which have one or more Carrying sulfonic acid groups (* -SO ₂ -OH), so-called sulfonates, and / or of phosphoric acid esters (alkyl phosphates), ie organic compounds which are mono- or divalent alkyl esters of orthophosphoric acid (* -O-PO (OH) ₂ or * -O-PO (OR) OH), so-called phosphates, and / or of phosphonic acids, ie organic compounds which carry one or more phosphonic acid groups (* -PO (OH) ₂ ), so-called phosphonates, and / or phosphorous acid esters, organic compounds which are alkyl esters of phosphonic acid (* -P (OR) ₂ (OH) or * -P (OR) (OH) ₂ ), so-called phosphites.

Suitable carboxylic acids for the purposes of the present invention are, for example, all linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally with one or more heteroatoms, preferably with hydroxyl groups (* -OH), primary, secondary or tertiary amino groups (* -NH) ₂ , * -NHR, * -NR ₂ ) or mercapto groups (* -SH), substituted, or interrupted by one or more heteroatoms mono-, di- or poly-carboxylic acids. Particularly suitable for the purposes of the present invention are carboxylic acids whose carbobnyl carbon atom is a hydrogen atom or a linear, branched or cyclic, aliphatic saturated or unsaturated, optionally with one or more heteroatoms, preferably with hydroxyl groups (* -OH), primary, secondary or tertiary amino groups (* -NH ₂ , * -NHR, * -NR ₂ ) or mercapto groups (* -SH), substituted, or hydrocarbon radical interrupted by one or more heteroatoms. Particularly suitable for the purposes of the present invention are those aliphatic carboxylic acids which have disubstituted (tertiary) or trisubstituted (quaternary) carbons or corresponding hydrocarbon radicals in the 2-position, ie on the carbon atom in addition to the carbonyl function. For the purposes of the present invention, preference is given to those aliphatic carboxylic acids which have one or two methyl, ethyl, n-propyl, iso-propyl, n-butyl and / or iso-butyl branching (s) in the 2-position. For the purposes of the present invention, particular preference is given to those aliphatic carboxylic acids, in particular monocarboxylic acids, which, in addition to the branching described in the 2-position, have a saturated or unsaturated, linear or branched alkyl chain and optionally with one or more heteroatoms, preferably with hydroxyl groups (* -OH) , primary, secondary or tertiary amino groups (* -NH ₂ , * -NHR, * -NR ₂ ) or mercapto groups (* -SH), are substituted. In particular, suitable carboxylic acids can be selected from the group of neo acids or cooking acids.

Examples of suitable mono-, di- and polyvalent, saturated and unsaturated substituted and unsubstituted carboxylic acids, fatty acids and neo acids or cooking acids are carboxylic acids such as formic acid, acetic acid, propionic acid, propionic acids, acrylic acid, butyric acid, isobutyric acid, 2,2- Dimethylbutyric acid, valeric acid, isovaleric acid, 2-methylvaleric acid, 2,2-dimethylvaleric acid (iso-heptanoic acid), pivalic acid, caproic acid, 2-ethylhexanoic acid (iso-octanoic acid), oenanoic acid, caprylic acid, pelargonic acid, iso-nonanoic acid, 3,5,5- Trimethylhexanoic acid, 2,5,5-trimethylhexanoic acid, 4,5,5-trimethylhexanoic acid, 2,2,4,4-tetramethylpentanoic acid, 6,6-dimethylheptanoic acid, capric acid, neodecanoic acid, 7,7-dimethyloctanoic acid, 2,2-dimethyloctanoic acid, 2,4-dimethyl-2-isopropylpentanoic acid, 2,2,3,5-tetramethylhexanoic acid, 2,2-diethylhexanoic acid, 2,5-dimethyl-2-ethylhexanoic acid, undecanoic acid, lauric acid, tridecanoic acid, neotridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, Margaric acid, Ste aric acid, oleic acid, linoleic acid, alpha-linolenic acid phytic acid, icosenic acid, erucic acid, ricinoleic acid, vernolic acid, arachic acid, arachidonic acid, oxalic acid, glycolic acid, glyoxalic acid, malonic acid, lactic acid, citric acid, succinic acid, fumaric acid, maleic acid, malic acid, malic acid, tartaric acid, tartaric acid, tartaric acid , Cinnamic acid, salicylic acid, benzoic acid, terephthalic acid, phthalic acid, isophthalic acid, nicotinic acid, carbamic acid, pyrrolidine-2-carboxylic acid and cyclohexane carboxylic acid.

Suitable alcohols are all linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally with one or more heteroatoms, preferably with primary, secondary or tertiary amino groups (* -NH ₂ , * -NHR, * -NR ₂ ) or mercapto groups (* -SH), substituted or monohydric alcohols interrupted by one or more heteroatoms, dihydric alcohols (diols) and / or polyhydric alcohols (polyols). Suitable for this are, for example, methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, neopentyl alcohol, phenols and / or nonylphenol.

Suitable thiols, mercaptoacetic acid esters, sulfuric acid esters, sulfonic acids, phosphoric acid esters (alkyl phosphates), phosphonic acids and / or phosphorous acid esters are, for example, all linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more heteroatoms, or by one or more several heteroatoms interrupted organic compounds containing one or more corresponding functional groups as defined above. Suitable for this are, for example, dialkyl phosphites, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, dodecylbenzylsulfonic acid, taurine, isooctylmercaptoacetate, 2-ethylhexylmercaptoacetate, ethanediol and / or n-lauryl mercaptide.

Particularly suitable organometallic salts and organic metal salts, as defined above, as additional catalysts for the purposes of the present invention are, for example, organotin, tin, zinc, bismuth and potassium salts, in particular corresponding metal carboxylates, alcoholates, thiolates and mercaptoacetates such as dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate (DBTDL), dioctyltin dilaurate (DOTDL), dimethyltin, Dibutylzinndineodecanoat, Dioctylzinndineodecanoat, dibutyltin dioleate, dibutyltin-bis-n-laurylmercaptid, dimethyltin-bis-n-laurylmercaptid, monomethyltin tris-2-ethylhexyl, Dimethyltin-2-ethylhexylmercaptoacetate, dibutyltin-bis-2-ethylhexylmercaptoacetate, dioctyltin-bis-isooctylmercaptoacetate, tin (II) acetate, tin (II) -2-ethylhexanoate (tin (II) octoate), tin (II) -isononanoate (tin (II) -3,5,5-trimethylhexanoate), tin (II) -neodecanoate, tin (ll) -ricinoleate, zinc (II) acetate, zinc (II) -2-ethylhexanoate (zinc (ll ) -oct oat), zinc (II) isononanoate (zinc (II) -3,5,5-trimethylhexanoate), zinc (II) neodecanoate, zinc (II) ricinoleate, bismuth acetate, bismuth 2-ethylhexanoate, bismuth octoate, bismuthisononanoate, Bismuth neodecanoate, potassium formate, potassium acetate, potassium 2-ethylhexanoate (potassium octoate), potassium isononanoate, potassium neodecanoate and / or potassium ricinoleate.

In the production of polyurethanes according to the invention, depending on the type of application, in particular in the production of polyurethane foams, it may be preferred to exclude the use of organometallic salts such as, for example, dibutyltin dilaurate.

Suitable additional metal-containing catalysts are generally preferably selected so that they have no intrinsic odor, are essentially toxicologically harmless and that the resulting polyurethane systems, in particular polyurethane foams, have the lowest possible catalyst-related emissions.

In addition to additional amines and metal-containing compounds, ammonium salts can also be used as additional catalysts. For example, ammonium formate and / or ammonium acetate are suitable.

Suitable additional catalysts are for example in DE 102007046860 , EP 1985642 , EP 1985644 , EP 1977825 , US 2008/0234402 , EP 0656382 B1 and US 2007/0282026 A1 and the patents cited therein.

Suitable amounts of additional catalysts depend on the type of catalyst and are preferably in the range from 0.01 to 10.0 pphp, particularly preferably in the range from 0.02 to 5.00 pphp (= parts by weight based on 100 parts by weight of polyol) or 0.10 to 10.0 pphp for potassium salts.

Depending on the application, it may be preferred according to the invention if, when using additional catalysts and / or premixed catalyst combinations, as defined above, from the sum of all nitrogen-containing compounds used, that is to say the sum of the nitrogen-containing compounds of the formula (III) and / or (IV) and the additional nitrogen-containing catalysts according to the prior art, compared to the sum of the metal-containing catalysts, in particular potassium, zinc and / or tin catalysts, a molar ratio of 1: 0.05 to 0.05: 1 , preferably 1: 0.07 to 0.07: 1 and particularly preferably 1: 0.1 to 0.1: 1 results.

It can be preferred according to the invention that additional catalysts and / or premixed catalyst combinations, as defined above, are free of dimethylamine-bearing nitrogen-containing compounds. Combinations of catalysts are free from dimethylamine-bearing nitrogen-containing compounds For the purposes of this invention, preferably when less than 75% by weight, in particular less than 50% by weight, preferably less than 30% by weight, particularly preferably less than 10% by weight, of the catalysts in the catalyst mixture contain nitrogen-containing compounds containing dimethylamine . Particular preference is given to catalyst combinations which contain no, ie 0% by weight, dimethylamine-bearing, nitrogen-containing compounds.

In order to avoid a reaction of the components with one another, in particular reaction of nitrogen-containing compounds of the formula (III) and / or (IV) and / or additional nitrogen-containing catalysts used with additional metal-containing catalysts, in particular potassium, zinc and / or tin catalysts , it may be preferred to store these components separately and then to feed the isocyanate and polyol reaction mixture simultaneously or in succession.

1. a) einer oder mehreren zusätzlichen (also nicht erfindungsgemäßen) stickstoffhaltigen Verbindungen als zusätzliche Katalysatoren, vorzugsweise wie oben definiert und beispielhaft beschrieben,
2. b) einem oder mehreren zusätzlichen metallhaltigen Katalysatoren, insbesondere einer oder mehrerer Zinn-, Zink-, Bismuth- und/oder Kaliumverbindungen, vorzugsweise wie oben definiert und beispielhaft beschrieben,
3. c) einer oder mehrerer Säuren zur Blockierung der enthaltenden Amine, vorzugsweise wie oben beschrieben,
4. d) Wasser
5. e) einem oder mehreren organischen Lösungsmitteln, vorzugsweise wie im Folgenden definiert und beispielhaft beschrieben,
6. f) einem oder mehreren chemischen oder physikalischen Treibmitteln, vorzugsweise wie im Folgenden beschrieben,
7. g) einem oder mehreren Stabilisatoren gegen oxidativen Abbau, beispielsweise Antioxidantien, vorzugsweise wie im Folgenden beschrieben,
8. h) einem oder mehreren Flammschutzmitteln, vorzugsweise wie im Folgenden beschrieben, und/oder
9. i) einem oder mehreren Schaumstabilisatoren auf der Basis von Siloxanen und/oder Polydialkylsiloxan-Polyoxyalkylen-copolymeren, vorzugsweise wie im Folgenden definiert und beschrieben, und/oder
10. j) einem oder mehreren weiteren Zusatzstoffen, zum Beispiel ausgewählt aus der Gruppe der Tenside Biozide, Farbstoffe, Pigmente, Füllstoffe, Antistatik-Additive, Vernetzer, Kettenverlängerer, Zellöffner, und/oder Duftstoffe

eingesetzt wird, wobei vorteilhafterweise vor der Herstellung des Polyurethans, insbesondere des Polyurethanschaumstoffs, zuerst eine Zusammensetzung hergestellt wird, beispielsweise im Sinne einer Vordosierung der Einzelkomponenten im Mischkopf oder als vorgemischte Katalysatorkombination, wie oben definiert, beinhaltend die vorgenannte Kombination. Insbesondere kann die genannte stickstoffhaltige Verbindung nach Formel (III) und/oder (IV) auch als technische Produktmischung eingesetzt werden. Geeignete technische Produktmischungen sind in der Beschreibung erläutert.It corresponds to a preferred embodiment of the invention if, in the context of the use according to the invention, at least one nitrogen-containing compound of the formula (III) and / or (IV) and / or a corresponding quaternized and / or protonated compound in combination with

1. a) one or more additional (ie not according to the invention) nitrogen-containing compounds as additional catalysts, preferably as defined above and described by way of example,
2. b) one or more additional metal-containing catalysts, in particular one or more tin, zinc, bismuth and / or potassium compounds, preferably as defined above and described by way of example,
3. c) one or more acids for blocking the amines present, preferably as described above,
4. d) water
5. e) one or more organic solvents, preferably as defined below and described by way of example,
6. f) one or more chemical or physical blowing agents, preferably as described below,
7. g) one or more stabilizers against oxidative degradation, for example antioxidants, preferably as described below,
8. h) one or more flame retardants, preferably as described below, and / or
9. i) one or more foam stabilizers based on siloxanes and / or polydialkylsiloxane-polyoxyalkylene copolymers, preferably as defined and described below, and / or
10. j) one or more further additives, for example selected from the group of the surfactants biocides, dyes, pigments, fillers, antistatic additives, crosslinking agents, chain extenders, cell openers, and / or fragrances

is used, advantageously before the production of the polyurethane, in particular the polyurethane foam, a composition is first produced, for example in the sense of a pre-metering of the individual components in the mixing head or as a premixed catalyst combination, as defined above, including the aforementioned combination. In particular, the nitrogenous compound according to formula (III) and / or (IV) mentioned can also be used as an industrial product mixture. Suitable technical product mixtures are explained in the description.

For the purposes of the aforementioned preferred embodiment, particularly preferred combinations in the context of the present invention are those compositions in which at least one nitrogen-containing compound of the formula (III) and / or (IV) and / or a corresponding quaternized and / or protonated compound is used in combination with a), with b), with c), with d), with e), with f), with a), b), c), d) e) and f), with a) and b), with a) and c), with a), b) and c), with a), b) and d), with a), b) and e), with a), b), d) and e), with a), b), d), e) and f), with a), b), e) and f), with a), c) and d), with a), c) and e), with a ), c), d) and e), with a), b) and e), with a), b), c) and e), with a), b), c), d) and e), with c) and d), with c) and e), with c), d) and e), with c), e) and f), with c), d), e) and f), with c) , d), e) and f), with b) and c), with b), c) and d), with b), c) and e), with b), c), d) and e), with b), c), e) and f), with b), c), d), e), f), with b) and d), with b) and e), with b), d) and e), with b), d) and f), with b), e) and f), or with b), d), e) and f).

The compounds of the formulas (III) and / or (IV) according to the invention, the corresponding protonated and / or quaternized compounds, can be used as pure substance or in a mixture, for example with suitable solvents and / or other additives, individually during foaming or as a premixed catalyst combination, such as defined above can be used.

All substances suitable according to the prior art are suitable as solvents. Depending on the application, aprotic-non-polar, aprotic-polar and protic solvents can be used. Suitable aprotic nonpolar solvents can be selected, for example, from the following substance classes or substance classes containing the following functional groups: aromatic hydrocarbons, aliphatic hydrocarbons (alkanes (paraffins) and olefins), carboxylic acid esters and polyesters, (poly) ethers and / or halogenated hydrocarbons lower Polarity. Suitable aprotic polar solvents can be selected, for example, from the following substance classes or substance classes containing the following functional groups: ketones, lactones, lactams, nitriles, carboxamides, sulfoxides and / or sulfones. Suitable protic solvents can be selected, for example, from the following substance classes, or substance classes containing the following functional groups: alcohols, polyols, (poly) alkylene glycols, amines, carboxylic acids, in particular fatty acids and / or primary and secondary amides.

Preferred solvents are, for example, mineral oils, hexane, pentane, heptane, decane or mixtures of saturated hydrocarbons, such as. B. Kaydol products from Sonneborn, glycol ethers such as ethylene glycol dimethyl ether (monoglyme), bis (2-methoxyethyl) ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), polyester and polyether polyols, polyols based on renewable raw materials NOPs), end-capped polyethers, preferably dialkyl polyethers which have butyl / methyl, methyl / methyl or butyl / butyl radicals as alkyl radicals, preferably those which are obtainable from diol-started polyethers, glycols, glycerol, Carboxylic acid esters, preferably fatty acid esters, for example ethyl acetate and isopropyl myristate, polycarbonates, phthalates, preferably dibutyl phthalate (DBP), dioctyl phthalate (DNOP), diethyl hexyl phthalate (DEHP), diisononyl phthalate (DINP), dimethyl phthalate (DMP), diethyl phthalate (DEP), cyclohexonyl cyclohexanoate, DINCH).

Solvents are particularly preferred are compounds which can be processed without difficulty in the foaming and do not adversely affect the properties of the foam. For example, isocyanate-reactive compounds are suitable because they react with the polymer matrix and do not generate any emissions in the foam. Examples are OH-functional compounds such as (poly) alkylene glycols, preferably monoethylene glycol (MEG or EG), diethylene glycol (DEG), triethylene glycol (TEG), 1-2-propylene glycol (PG), dipropylene glycol (DPG), trimethylene glycol (1.3 -Propanediol PDO), tetramethylene glycol (butanediol BDO), butyl diglycol (BDG), neopentyl glycol, 2-methyl-1,3-propanediol (Ortegol CXT) and higher homologues thereof such as polyethylene glycol (PEG) with average molecular weights between 200 and 3000. Further particularly preferred OH-functional compounds are polyethers with average molecular weights of 200 to 4500, in particular 400 to 2000, preferably water, allyl, butyl or nonyl-started polyethers, in particular those based on propylene oxide (PO) and / or ethylene oxide (EO) blocks.
If nitrogen-containing compounds according to the formula (III) and / or (IV) according to the invention or premixed catalyst combinations of the compounds according to the invention with additional catalysts, as defined above, are dissolved or used in combination with a solvent, the mass ratio of catalyst or catalyst combination to solvent is preferably from 100 to 1 to 1 to 4, preferably from 50 to 1 to 1 to 3 and particularly preferably from 25 to 1 to 1 to 2.

All substances known in the prior art which are used in the production of polyurethanes, in particular polyurethane foams, such as blowing agents, preferably water to form CO ₂ and, if necessary, further physical blowing agents, crosslinking agents, can be used as additives and chain extenders, stabilizers against oxidative degradation (so-called antioxidants), flame retardants, surfactants, biocides, cell-refining additives, cell openers, solid fillers, antistatic additives, nucleating agents, thickeners, dyes, pigments, color pastes, fragrances, emulsifiers, buffer substances and / or additional substances catalytically active substances, in particular as defined above.

If polyurethane foams are to be produced as polyurethane systems, it can be advantageous to use water as a blowing agent. Sufficient water is preferably used so that the amount of water is 0.10 to 25.0 pphp (pphp = parts by weight based on 100 parts by weight of polyol).

Suitable physical blowing agents can also be used. These are, for example, liquefied CO ₂ , and volatile liquids, for example hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclo-, iso- and n-pentane, fluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, chlorofluorocarbons, preferably HCFC 141b, hydrofluoroolefins (HFO) or hydrohaloolefins such as 1234ze, 1233zd (E) or 1336mzz, oxygen-containing compounds such as methyl formate, acetone and dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane and 1,2-dichloro.

In addition to water and the physical blowing agents, other chemical blowing agents that react with isocyanates under gas evolution, such as formic acid, can also be used.

Crosslinkers and chain extenders are low molecular weight, isocyanate-reactive, multi-functional compounds. For example, hydroxyl- or amine-terminated substances such as glycerol, neopentyl glycol, 2-methyl-1,3-propanediol, triethanolamine (TEOA), diethanolamine (DEOA) and trimethylolpropane are suitable. The use concentration is usually between 0.1 and 5 parts, based on 100 parts of polyol, but can also vary depending on the formulation. When crude MDI is used in the foaming process, this also has a cross-linking function. The content of low molecular weight crosslinkers can therefore be reduced accordingly with increasing amounts of crude MDI.

Suitable stabilizers against oxidative degradation, so-called antioxidants, are preferably all common radical scavengers, peroxide scavengers, UV absorbers, light stabilizers, complexing agents for metal ion impurities (metal deactivators). Compounds of the following substance classes, or substance classes containing the following functional groups, can preferably be used, preference being given in particular to substituents on the respective base bodies which have groups which are reactive toward isocyanate: 2- (2'-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, benzoic acids and Benzoates, phenols, in particular containing tert-butyl and or methyl substituents on aromatics, benzofuranones, diarylamines, triazines, 2,2,6,6-tetramethylpiperidines, hydroxylamines, alkyl and aryl phosphites, sulfides, zinc carboxylates, diketones. Examples of phenols which can be used are esters based on 3- (4-hydroxyphenyl) propionic acid, such as triethyleneglycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], octadecyl-3- (3,5- di-tert-butyl-4-hydroxyphenyl) propionate, or methylene diphenols such as 4,4'-butylidene-bis- (6-tert-butyl-3-methylphenol) can be used. As 2- (2'-hydroxyphenyl) benzotriazoles, for example 2- (2'Hydroxy-5'-methylphenyl) benzotriazole or 2- (2'Hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole are preferred. For example, 2-hydroxy-4-n-octoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone or 2,4-dihydroxybenzophenone are preferred as 2-hydroxybenzophenones. Examples of preferred benzoates are hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate or tannins.

Suitable flame retardants for the purposes of this invention are all substances which are considered suitable for this in the prior art. Preferred flame retardants are, for example, liquid organic phosphorus compounds, such as halogen-free organic phosphates, e.g. Triethyl phosphate (TEP), halogenated phosphates, e.g. Tris (1-chloro-2-propyl) phosphate (TCPP) and tris (2-chloroethyl) phosphate (TCEP) and organic phosphonates, e.g. Dimethyl methane phosphonate (DMMP), dimethyl propane phosphonate (DMPP), or solids such as ammonium polyphosphate (APP) and red phosphorus. Halogenated compounds, for example halogenated polyols, and solids such as expandable graphite and melamine are also suitable as flame retardants.

Surfactants which are used in particular in the production of polyurethane foams can, for example, be selected from the group comprising anionic surfactants, cationic surfactants, nonionic surfactants and / or amphoteric surfactants. According to the invention, polymeric emulsifiers such as polyalkylpolyoxyalkylpolyacrylates, polyvinylpyrrolidones or polyvinyl acetates can also be used as surfactants.

For example, commercially available products can be used as biocides, such as chlorophene, benzisothiazoline, hexahydro-1,3,5-tris (hydroxyethyl-s-triazine), chloromethylisothiazoline, methylisothiazoline or 1,6-dihydroxy-2,5-dioxohexane, which are listed below the trade names BIT 10, Nipacide BCP, Acticide MBS, Nipacide BK, Nipacide Cl, Nipacide FC are known.

To influence the foam properties of polyurethane foams, in particular siloxanes or organomodified siloxanes can be used in their production, it being possible to use the substances mentioned in the prior art. Those compounds are preferably used which are particularly suitable for the respective foam types (rigid foams, hot flexible foams, viscoelastic foams, ester foams, cold flexible foams (HR foams), semi-hard foams). Suitable (organomodified) siloxanes are described, for example, in the following documents: EP 0839852 , EP 1544235 , DE 102004001408 , EP 0839852 , WO 2005/118668 , US 20070072951 , DE 2533074 , EP 1537159 EP 533202 , US 3933695 , EP 0780414 , DE 4239054 , DE 4229402 , EP 867465 . The preparation of these connections can as described in the prior art. Suitable examples are e.g. B. in US 4147847 , EP 0493836 and US 4855379 described.

All stabilizers known from the prior art can be used as (foam) stabilizers. Foam stabilizers based on polydialkylsiloxane-polyoxyalkylene copolymers, as are generally used in the production of urethane foams, are preferably used. These compounds are preferably structured such that, for example, a long-chain copolymer of ethylene and propylene oxide is linked to a polydimethylsiloxane radical. The link between the polydialkylsiloxane and the polyether part can be made via an SiC link or an Si-OC bond. Structurally, the different polyether (s) can be bound terminally or laterally to the polydialkylsiloxane. The alkyl radical or the various alkyl radicals can be aliphatic, cycloaliphatic or aromatic. Methyl groups are particularly advantageous. The polydialkylsiloxane can be linear or contain branches. Suitable stabilizers, in particular foam stabilizers, are among others in US 2834748 , US2917480 as in US3629308 described. Suitable stabilizers can be obtained from Evonik Industries AG under the trade name TEGOSTAB ^® .

worin

a

unabhängig voneinander 0 bis 500 ist, vorzugsweise 1 bis 300 und insbesondere 2 bis 150,

b

unabhängig voneinander 0 bis 60 ist, vorzugsweise 1 bis 50 und insbesondere 1 bis 30,

c

unabhängig voneinander 0 bis 10, vorzugsweise 0 oder > 0 bis 5, ist,

d

unabhängig voneinander 0 bis 10, vorzugsweise 0 oder > 0 bis 5, ist,

mit der Maßgabe, dass pro Molekül der Formel (V) die mittlere Anzahl ∑d der T-Einheiten [SiR³R⁴O] und die mittlere Anzahl ∑c der Q-Einheiten [SiR³R³O] pro Molekül jeweils nicht größer als 50, die mittlere Anzahl ∑a der D-Einheiten [SiRRO] pro Molekül nicht größer als 2000 und die mittlere Anzahl ∑b der R¹ tragenden Siloxy-Einheiten pro Molekül nicht größer als 100 ist,

R

unabhängig voneinander mindestens ein Rest aus der Gruppe linearer, cyclischer oder verzweigter, aliphatischer oder aromatischer, gesättigter oder ungesättigter Kohlenwasserstoffreste mit 1 bis zu 20 C-Atomen, vorzugsweise jedoch ein Methylrest ist,

R²

unabhängig voneinander R¹ oder R ist,

R¹

ist ungleich R und unabhängig voneinander ein organischer Rest und/oder ein Polyetherrest, bevorzugt ist der R¹ ein Rest ausgewählt aus der Gruppe

-CH₂-CH₂-CH₂-O-(CH₂-CH₂O-)_x-(CH₂-CH(R')O-)_y-R" -CH₂-CH₂-O-(CH₂-CH₂O-)_x-(CH₂-CH(R')O-)_y-R" -O-(C₂H₄O-)_x-(C₃H₅O-)_y-R' -CH₂-R^IV -CH₂-CH₂-(O)_x'-R^IV -CH₂-CH₂-CH₂-O-CH₂-CH(OH)-CH₂OH

oder -CH₂-CH₂-CH₂-O-CH₂-C(CH₂OH)₂-CH₂-CH₃ ist, worin

x

0 bis 100, vorzugsweise > 0, insbesondere 1 bis 50,

x'

0 oder 1,

y

0 bis 100, vorzugsweise > 0, insbesondere 1 bis 50,

z

0 bis 100, vorzugsweise > 0, insbesondere 1 bis 10,

R'

unabhängig voneinander eine gegebenenfalls substituierte, beispielsweise mit Alkylresten, Arylresten oder Halogenalkyl- oder Halogenarylresten substituierte, Alkyl- oder Arylgruppe mit 1 bis 12 C-Atomen ist, wobei innerhalb eines Restes R¹ und/oder eines Moleküls der Formel (V) untereinander verschiedene Substituenten R' vorliegen können, und

R"

unabhängig voneinander ein Wasserstoffrest oder eine Alkylgruppe mit 1 bis 4 C-Atomen, eine Gruppe -C(O)-R"' mit R'" = Alkylrest, eine Gruppe -CH₂-O-R', eine Alkylarylgruppe, wie z. B. eine Benzylgruppe, die Gruppe -C(O)NH-R' bedeutet,

R^IV

ein linearer, cyclischer oder verzweigter, auch weiter substituierter, z. B. mit Halogenen substituierter, Kohlenwasserstoffrest mit 1 bis 50, vorzugsweise 9 bis 45, bevorzugt 13 bis 37 C-Atomen ist,

R⁴

unabhängig voneinander R, R¹ und/oder ein mit Heteroatomen substituierter, funktionalisierter, organischer, gesättigter oder ungesättigter Rest ausgewählt aus der Gruppe der Alkyl-, Aryl-, Chloralkyl-, Chloraryl-, Fluoralkyl-, Cyanoalkyl-, Acryloxyaryl-, Acryloxyalkyl-, Methacryloxyalkyl-, Methacryloxypropyl- oder Vinyl-Rest sein kann,

mit der Maßgabe, dass mindestens ein Substituent aus R¹, R² und R⁴ nicht gleich R ist. Die verschiedenen Monomereinheiten der in den Formeln angegebenen Bausteine (Siloxanketten bzw. Polyoxyalkylenkette) können untereinander blockweise aufgebaut sein mit einer beliebigen Anzahl an Blöcken und einer beliebigen Sequenz oder einer statistischen Verteilung unterliegen. Die in den Formeln verwendeten Indices sind als statistische Mittelwerte zu betrachten.Suitable siloxanes which can be used when using the nitrogen-containing compounds of the formula (III) and / or (IV) and / or the corresponding quaternized and / or protonated compounds according to the invention in the production of polyurethane foams have in particular the following structure:

wherein

a

is independently 0 to 500, preferably 1 to 300 and in particular 2 to 150,

b

is independently 0 to 60, preferably 1 to 50 and in particular 1 to 30,

c

is independently 0 to 10, preferably 0 or> 0 to 5,

d

is independently 0 to 10, preferably 0 or> 0 to 5,

with the proviso that the average number ∑d of the T units [SiR ³ R ⁴ O] and the average number ∑c of the Q units [SiR ³ R ³ O] per molecule are not greater per molecule of the formula (V) than 50, the average number ∑a of the D units [SiRRO] per molecule is not greater than 2000 and the average number ∑b of the R ¹ -bearing siloxy units per molecule is not greater than 100,

R

independently of one another at least one radical from the group consisting of linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having 1 to 20 C atoms, but preferably being a methyl radical,

R ²

is independently of one another R ¹ or R,

R ¹

is not equal to R and is independently an organic radical and / or a polyether radical, R ¹ is preferably a radical selected from the group

-CH ₂ -CH ₂ -CH ₂ -O- (CH ₂ -CH ₂ O-) _x - (CH ₂ -CH (R ') O-) _y -R " -CH ₂ -CH ₂ -O- (CH ₂ -CH ₂ O-) _x - (CH ₂ -CH (R ') O-) _y -R " -O- (C ₂ H ₄ O-) _x - (C ₃ H ₅ O-) _y -R ' -CH ₂ -R ^IV -CH ₂ -CH ₂ - (O) _{x '} -R ^IV -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH (OH) -CH ₂ OH

or -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -C (CH ₂ OH) ₂ -CH ₂ -CH ₃ , wherein

x

0 to 100, preferably> 0, in particular 1 to 50,

x '

0 or 1,

y

0 to 100, preferably> 0, in particular 1 to 50,

e.g.

0 to 100, preferably> 0, in particular 1 to 10,

R '

independently of one another is an optionally substituted, for example with alkyl, aryl or haloalkyl or haloaryl, substituted alkyl or aryl group having 1 to 12 carbon atoms, within a radical R ¹ and / or a molecule of formula (V) mutually different substituents R 'may be present, and

R "

independently of one another a hydrogen radical or an alkyl group having 1 to 4 carbon atoms, a group -C (O) -R "'with R'" = alkyl radical, a group -CH ₂ -O-R ', an alkylaryl group, such as, for. B. a benzyl group which means group -C (O) NH-R ',

R ^IV

a linear, cyclic or branched, also further substituted, e.g. B. is substituted with halogens, hydrocarbon radical having 1 to 50, preferably 9 to 45, preferably 13 to 37 carbon atoms,

R ⁴

independently of one another R, R ¹ and / or a functionalized, organic, saturated or unsaturated radical substituted with heteroatoms selected from the group consisting of alkyl, aryl, chloroalkyl, chloroaryl, fluoroalkyl, cyanoalkyl, acryloxyaryl, acryloxyalkyl , Methacryloxyalkyl, methacryloxypropyl or vinyl radical can be

with the proviso that at least one substituent from R ¹ , R ² and R ^{4 is} not equal to R. The various monomer units of the building blocks specified in the formulas (siloxane chains or polyoxyalkylene chain) can be built up in blocks with one another with any number of blocks and any sequence or a statistical distribution. The indices used in the formulas are to be regarded as statistical averages.

The siloxanes of the formula (V) can be prepared by known methods, such as, for example, the noble metal-catalyzed hydrosilylation reaction of compounds which contain a double bond with corresponding hydrogen siloxanes, for example in EP 1520870 , described. The font EP 1520870 is hereby introduced as a reference and is considered part of the disclosure content of the present invention.

As compounds which have at least one double bond per molecule, z. B. α-olefins, vinyl polyoxyalkylenes and / or allyl polyoxyalkylenes can be used. Vinylpolyoxyalkylenes and / or allylpolyoxyalkylenes are preferably used. Particularly preferred vinyl polyoxyalkylenes are e.g. B. vinyl polyoxyalkylenes with a molecular weight in the range of 100 g / mol to 8,000 g / mol, which can be constructed in blocks or randomly from the monomers propylene oxide, ethylene oxide, butylene oxide and / or styrene oxide and which are both hydroxy-functional and by a methyl ether function or a Acetoxy function may be end-capped. Particularly preferred allyl polyoxyalkylenes are e.g. B. allylpolyoxyalkylenes with a molecular weight in the range of 100 g / mol to 5,000 g / mol, which can be constructed in blocks or randomly from the monomers propylene oxide, ethylene oxide, butylene oxide and / or styrene oxide and which are both hydroxy-functional and also by a methyl ether function or one Acetoxy function can be end-capped. Particularly preferred compounds which have at least one double bond per molecule are the α-olefins, allyl alcohol, 1-hexenol, vinyl polyoxyalkylene and / or allyl polyoxyalkylene and allyl glycidyl ether and vinylcyclohexene oxide mentioned in the examples.

In the context of the present invention (in particular in the context of the use according to the invention), preference is given to using siloxanes of the formula (V) in which a is independently 1 to 300, b is independently 1 to 50, c is independently 0 to 4, d is independent of one another 0 to 4, with the proviso that the average number ∑ d of T units and the average number ∑ c of Q units per molecule are not greater than 20 per molecule of formula (V), the average number ∑ a of D units per molecule is not greater than 1500 and the average number ∑ b of the R ¹ -bearing siloxy units per molecule is not greater than 50.

In a particularly preferred embodiment of the present invention (especially in the context of the use according to the invention), siloxanes of the formula (V) are used in which R ^{1 is,} independently of one another, an organic radical -CH ₂ -CH ₂ -CH ₂ -O- (CH ₂ -CH ₂ O-) _x - (CH ₂ -CH (R ') O-) _y -R " -CH ₂ -CH ₂ -O- (CH ₂ -CH ₂ O-) _x - (CH ₂ -CH (R ') O-) _y -R " -CH ₂ -R ^IV in which x is 0 to 100, preferably> 0, in particular 1 to 50 and y is 0 to 100, preferably> 0, in particular 1 to 50, R 'can be different independently of one another and methyl, ethyl and / or phenyl Represent leftovers. R "independently of one another is a hydrogen radical or an alkyl group having 1 to 4 carbon atoms, a group -C (O) -R '" with R'"= alkyl radical, a group -CH ₂ -O-R ', an alkylaryl group, such as e.g. a benzyl group which means group -C (O) NH-R ', R ^{IV is} a linear, cyclic or branched, optionally substituted, for example substituted by halogens, hydrocarbon radical having 1 to 50, preferably 9 to 45 , is preferably 13 to 37 carbon atoms.

In a further preferred embodiment of the present invention (in particular in the context of the use according to the invention), preferably for the production of rigid foams, siloxanes of the formula (V) are used in which R ^{1 is,} independently of one another, an organic radical selected from the group comprising -CH ₂ -CH ₂ -CH ₂ -O- (CH ₂ -CH ₂ O-) _x - (CH ₂ -CH (R ') O-) _y -R "and / or -CH ₂ -CH ₂ -O- (CH ₂ - CH ₂ O-) _x - (CH ₂ -CH (R ') O-) _y -R "and / or -CH ₂ -R ^IV , wherein x is 0 to 100, preferably> 0, in particular 1 to 50, y 0 to 100, preferably> 0, in particular 1 to 50, R 'is methyl and R "independently of one another is a hydrogen radical or an alkyl group with 1 to 4 C atoms, a group C (O) -R'" with R '"= Alkyl radical, a group -CH2-O-R ', an alkylaryl group such as, for example, a benzyl group, the group C (O) NH-R', the molar proportion of oxyethylene units, based on the total amount of oxyalkylene units, makes up at least 70% of the oxalkylene units, ie x / (x + y)> 0.7. Under this condition, it is preferred that the polyoxyalkylene chain also carries hydrogen at the end. Under these conditions, according to a further preferred embodiment of the invention (in particular within the scope of the use according to the invention), siloxanes of the formula (V) are used in which the oxalkylene units contained in radical R ¹ are exclusively oxyethylene units and the radical R "is not hydrogen is.

In a further preferred embodiment of the present invention (in particular in the context of the use according to the invention), preferably for the production of flexible flexible foams, siloxanes of the formula (V) are used in which R1 is an organic radical selected independently of one another from the group comprising -CH ₂ -CH ₂ -CH ₂ -O- (CH ₂ -CH ₂ O-) _x - (CH ₂ -CH (R ') O-) _y -R "and / or -CH ₂ -CH ₂ -O- (CH ₂ -CH ₂ O-) _x - (CH ₂ -CH (R ') O-) _y -R "and / or -CH ₂ -R ^IV , where x is 0 to 100, preferably> 0, in particular 1 to 50, y 0 to 100, preferably> 0, in particular 1 to 50, R 'is methyl and R "independently of one another is a hydrogen radical or an alkyl group having 1 to 4 C atoms, a group C (O) -R'" with R '" =

Alkylrest, a group -CH2-O-R ', an alkylaryl group, such as. B. a benzyl group, the group C (O) NH-R ', the molar proportion of oxyethylene units based on the total amount of oxyalkylene units making up a maximum of 60% of the oxalkylene units, ie x / (x + y) <0, 6 is.

In a further preferred embodiment of the present invention (in particular in the context of the use according to the invention), siloxanes of the formula (V) are used in which, inter alia, olefins are used in the hydrosilylation, whereby R ^{1 is} at least 10 mol%, preferably at least 20 mol%, particularly preferably at least 40 mol% consists of CH ₂ -R ^IV , where R ^{IV is} a linear or branched hydrocarbon with 9 to 17 carbon atoms.

In a further preferred embodiment of the present invention (in particular in the context of the use according to the invention), siloxanes of the formula (V) are used in which the terminal positions, or else alpha- and omega-mentioned positions on the siloxane are at least partially functionalized with radicals R ¹ . At least 10 mol%, preferably at least 30 mol%, particularly preferably at least 50 mol% of the terminal positions are functionalized with radicals R ¹ .
In a particularly preferred embodiment of the invention (in particular in the context of the use according to the invention), siloxanes of the formula (V) are used in which, on average, a maximum of 50%, preferably a maximum of 45%, particularly preferably a maximum of 40% of the total average molecular weight of the siloxane is based on the the total molar mass of all, possibly different, radicals R ¹ in the siloxane is eliminated.

In a further preferred embodiment of the present invention (in particular in the context of the use according to the invention), siloxanes of the formula (V) are used in which the radical R is methyl and the number of structural elements with the index a is greater than the structural elements with the Index b, in such a way that the quotient a / b is at least seven, preferably greater than 10, particularly preferably greater than 12.

In a further preferred embodiment of the present invention (in particular in the context of the use according to the invention), siloxanes of the formula (V) are used in which the oxalkylene units contained in radical R ¹ are exclusively oxyethylene units and the radical R "is not hydrogen.

In the context of the present invention (in particular in the context of the use according to the invention), the siloxanes can also be used as part of compositions with different carrier media. Suitable carrier media are, for example, glycols, such as, for example, monoethylene glycol (MEG), diethylene glycol (DEG), propylene glycol (PG) or dipropylene glycol (DPG), alkoxylates or oils of synthetic and / or natural origin.

Preferably, the composition for the production of polyurethane systems, preferably polyurethane foams, is added with enough of the siloxanes of the formula (V) that the mass fraction of compounds of the formula (V) in the finished polyurethane system, preferably the polyurethane foam, is from 0.01 to 10% by weight. -%, preferably from 0.1 to 3 wt .-%.

The nitrogen-containing compounds of the formula (III) and / or (IV) according to the invention, corresponding quaternized and / or protonated compounds, are preferably used in the production of polyurethane systems, in particular polyurethane foams.

It can be advantageous if a composition is produced and / or used in the production of the polyurethane system which contains at least one nitrogen-containing compound according to the invention of the formula (III) and / or (IV), as previously defined, and / or a corresponding quaternized and / or protonated compound, at least one polyol component, optionally at least one isocyanate component and optionally one or more blowing agents, and this composition is reacted. Compositions which have the substances or components described above for use in the production of polyurethanes, in particular polyurethane foams, are particularly preferably used.

Another object of the invention is the use of the previously described nitrogen-containing compound of the formula (III) and / or (IV), and / or a corresponding quaternized and / or protonated compound, for the production of low-emission polyurethanes, in particular low-emission polyurethane foams, namely advantageously low-emission with regard to emissions of nitrogen-containing compounds, as previously also called amine emissions, advantageously low-emission with regard to emissions of dimethylformamide (DMF), and / or advantageously low-emission with regard to aldehyde emissions, in particular formaldehyde emissions. With regard to the term “low emissions”, reference is made to the preceding description and the explanations there, in particular test methods. With regard to preferred configurations of this subject, reference is also made to the preceding description, in particular to the preferred embodiments mentioned.

Another object of the invention is the use of the previously described nitrogen-containing compound of the formula (III) and / or (IV), and / or a corresponding quaternized and / or protonated compound, for the production of low-odor polyurethanes, preferably low-odor polyurethane foams, in particular of low-odor flexible polyurethane foams. With regard to the term “low odor”, reference is made to the preceding description and the explanations there. With regard to preferred configurations of this subject, reference is also made to the preceding description, in particular to the preferred embodiments mentioned.

Another object of the invention is the use of the previously described nitrogen-containing compound of the formula (III) and / or (IV), and / or a corresponding quaternized and / or protonated compound, for the production of aging-resistant polyurethane systems, in particular polyurethane foams. With regard to the term “resistant to aging”, reference is made to the preceding description and the explanations and test methods there. With regard to preferred configurations of this subject, reference is also made to the preceding description, in particular to the preferred embodiments mentioned.

Another object of the invention is the use of the previously described nitrogen-containing compound of the formula (III) and / or (IV), and / or a corresponding quaternized and / or protonated compound, for the production of discoloration-minimized polyurethane systems, in particular polyurethane foams, preferably of Polyurethanes for use in the automotive industry, especially in automobile interiors, for example as headliners, interior linings of doors, punched-out sun visors, steering wheels and / or seating systems. Discoloration minimized means that the polyurethane systems provided using nitrogen-containing catalysts according to the invention in particular lead to less discoloration of plastics, in particular plastic covers, in automobile interiors than those polyurethane systems which are produced using conventional catalysts according to the prior art, in particular amines not according to the invention, as can be shown, for example, by means of a PVC discoloration test. Here too, reference is made to the preceding description and the explanations and test methods there. With regard to preferred configurations of this subject, reference is also made to the preceding description, in particular to the preferred embodiments mentioned.

Another object of the invention is the use of the previously described nitrogen-containing compound of formula (III) and / or (IV), and / or a corresponding quaternized and / or protonated compound, for the production of polyurethane systems with a wide range of processing, in particular of semi-hard polyurethane foams (open-cell rigid foams, especially for use as headliners in automobile interiors). “Broad processing game” means that advantageously a greater range of variation in the use concentration of the nitrogen-containing compounds according to the invention is possible without negative influence on the desired material properties, for example the open-cell nature of the foam or the density distribution over the foam block, compared to comparable or customarily used amine catalysts for such applications the state of the art. Here too, reference is made to the preceding description and the explanations and test methods there. With regard to preferred configurations of this subject, reference is also made to the preceding description, in particular to the preferred embodiments mentioned.

The invention further relates to a composition comprising at least one polyol component, the composition comprising at least one nitrogen-containing compound of the formula (III) and / or (IV) as previously defined and described, and / or the corresponding quaternized and / or protonated compounds, where the composition preferably has at least one isocyanate component, and the nitrogen-containing compound of the formula (III) and / or (IV) is preferably present as an industrial product mixture, as described above,
and wherein the composition preferably comprises additional amine catalysts different from formula (III) and / or (IV).

The molar ratio of the total amount of nitrogen-containing catalysts, comprising the nitrogen-containing compounds of the formula (III) and / or (IV), to the total amount of the isocyanate-reactive groups of the polyol component is preferably from 4 × 10 ^-4 to 1 to 0.2 to 1.

It is preferred that the nitrogen-containing compounds of the formula (III) and / or (IV), corresponding quaternized and / or protonated compounds, in total in a mass fraction of 0.01 to 20.0 parts (pphp), preferably 0.01 up to 5.00 parts and particularly preferably 0.02 to 3.00 parts based on 100 parts (pphp) of polyol component.

The composition according to the invention can additionally have one or more blowing agents, as described above. In addition to or instead of blowing agents, the composition according to the invention can have further additives / auxiliaries or additives which are used in the production of polyurethane systems, preferably polyurethane foams. A selection of suitable auxiliaries / additives / additives, such as. B. foam stabilizers or flame retardants, has already been described above in the manufacture of the polyurethane systems, especially the polyurethane foams.

The compositions according to the invention can be processed into polyurethane systems, in particular polyurethane foams, by all processes known to the person skilled in the art, for example by hand mixing or preferably by means of foaming machines, in particular low-pressure or high-pressure foaming machines. Discontinuous processes, for example for the production of molded foams, refrigerators, automobile seats, and panels, or continuous processes, for example for insulation boards, metal composite elements, block foams or for spray processes, can be used.

All processes known to the person skilled in the art can be used for the production of polyurethane foams. For example, the foaming process can take place in both horizontal and vertical directions, in discontinuous or continuous systems. The compositions used according to the invention can also be used for CO ₂ technology. The use in low-pressure and high-pressure machines is possible, the compositions being able to be metered directly into the mixing chamber, or one of the components subsequently entering the mixing chamber can also be mixed in before the mixing chamber. The addition can also take place in the raw material tank.

The inventive polyurethane systems described below can be obtained by using nitrogen-containing compounds of the formula (III) and / or (IV) and / or the corresponding quaternized and / or protonated compounds according to the invention.

1. (a) zumindest eine stickstoffhaltige Verbindung der Formel (III) und/oder (IV), insbesondere eine Verbindung nach der Formel (III) und/oder (IV), besonders bevorzugt eine Verbindung nach der Formel (III), vorteilhafterweise in einer Gesamtmenge von ≥ 5 Gew.-%, bevorzugt 20-95 Gew.-%, insbesondere 30-70 Gew.-%,
2. (b) optional 1-(3-Aminopropyl)pyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20-95 Gew.-%, insbesondere 30-70 Gew.-%,
3. (c) optional 1-(2-Aminoethyl)pyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20-95 Gew.-%, insbesondere 30-70 Gew.-%,
4. (d) optional 1,4-Butandiol, vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
5. (e) optional Monoethylenglycol (MEG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
6. (f) optional Diethylenglycol (DEG) vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
7. (g) optional Propylenglycol (PG) vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
8. (h) optional Dipropylenglycol (DPG) vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
9. (i) optional weitere Piperazin- und/oder Morpholin-Gruppen enthaltende Nebenprodukte, insbesondere 4-(3-(pyrrolidin-1-yl)propyl)morpholin, 4-(2-(pyrrolidin-1-yl)ethyl)morpholin, 1-(3-(pyrrolidin-1-yl)propyl)piperazin, 1-(2-(pyrrolidin-1-yl)ethyl)piperazin, 2-(4-(3-(pyrrolidin-1-yl)propyl)piperazin-1-yl)ethanol, 2-(4-(2-(pyrrolidin-1-yl)ethyl)piperazin-1-yl)ethanol, 2-(4-(3-(pyrrolidin-1-yl)propyl)piperazin-1-yl)ethanamin, 2-(4-(2-(pyrrolidin-1-yl)ethyl)piperazin-1-yl)ethanamin, 1-(4-(3-(pyrrolidin-1-yl)propyl)piperazin-1-yl)propan-2-ol und/ode5r 1-(4-(2-(pyrrolidin-1-yl)ethyl)piperazin-1-yl)propan-2-ol, in einer Menge ≤ 95 Gew.-%, vorzugsweise ≤ 70 Gew.-%, insbesondere ≤ 30 Gew.-%, bevorzugt ≤ 10 Gew.-%, besonders bevorzugt ≤ 5 Gew.-%, und/oder
10. (j) optional Trimethylenglycol, Butyldiglycol, Neopentylglycol, 2-Methyl-1,3-propandiol, N,N-Dimethylcyclohexylamin, N,N-Dimethylaminopropylamin, Triethylendiamin, 2,2,4-Trimethyl-2-silamorpholin, N-Ethyl-2,2-dimethyl-2-silamorpholin, N-(2-Aminoethyl)morpholin, N-(2-Hydroxyethyl)morpholin, N,N-Dimethylaminoethanol, N,N-Diethylaminoethanol, Bis(2-Dimethylaminoethylether), 1-(2-Hydroxyethyl)pyrrolidin, 1-(3-Hydroxyethyl)pyrrolidin, N,N-Dimethylaminoethoxyethanol, N,N,N'-Trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl)ether, Tris(dimethylaminopropyl)hexahydro-1,3,5-triazin, 1,8-Diazabicyclo[5.4.0]undec-7-en, 1,5-Diazabicyclo[4.3.0]non-5-en, 1,5,7-triazabicyclo[4.4.0]dec-5-en, N-Methyl-1,5,7-triazabicyclo-[4.4.0]dec-5-en, 1,4,6-triazabicyclo[3.3.0]oct-4-en, 1,1,3,3-Tetramethylguanidin und/oder 2,4,6-Tris(dimethylaminomethyl)phenol, vorteilhafterweise in einer Gesamtmenge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%.

Another object of the present invention is a composition suitable for use in the production of polyurethanes, in particular containing polyurethane foams

1. (a) at least one nitrogen-containing compound of the formula (III) and / or (IV), in particular a compound of the formula (III) and / or (IV), particularly preferably a compound of the formula (III), advantageously in a total amount of ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
2. (b) optionally 1- (3-aminopropyl) pyrrolidine, advantageously in an amount ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
3. (c) optionally 1- (2-aminoethyl) pyrrolidine, advantageously in an amount ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
4. (d) optionally 1,4-butanediol, advantageously in an amount 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
5. (e) optionally monoethylene glycol (MEG), advantageously in an amount ≤ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
6. (f) optionally diethylene glycol (DEG) advantageously in an amount of 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
7. (g) optionally propylene glycol (PG) advantageously in an amount of 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
8. (h) optionally dipropylene glycol (DPG) advantageously in an amount of 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
9. (i) optionally by-products containing further piperazine and / or morpholine groups, in particular 4- (3- (pyrrolidin-1-yl) propyl) morpholine, 4- (2- (pyrrolidin-1-yl) ethyl) morpholine, 1 - (3- (pyrrolidin-1-yl) propyl) piperazine, 1- (2- (pyrrolidin-1-yl) ethyl) piperazine, 2- (4- (3- (pyrrolidin-1-yl) propyl) piperazin- 1-yl) ethanol, 2- (4- (2- (pyrrolidin-1-yl) ethyl) piperazin-1-yl) ethanol, 2- (4- (3- (pyrrolidin-1-yl) propyl) piperazin- 1-yl) ethanamine, 2- (4- (2- (pyrrolidin-1-yl) ethyl) piperazin-1-yl) ethanamine, 1- (4- (3- (pyrrolidin-1-yl) propyl) piperazin- 1-yl) propan-2-ol and / or 5r 1- (4- (2- (pyrrolidin-1-yl) ethyl) piperazin-1-yl) propan-2-ol, in an amount ≤ 95% by weight , preferably ≤ 70% by weight, in particular ≤ 30% by weight, preferably ≤ 10% by weight, particularly preferably ≤ 5% by weight, and / or
10. (j) optionally trimethylene glycol, butyl diglycol, neopentyl glycol, 2-methyl-1,3-propanediol, N, N-dimethylcyclohexylamine, N, N-dimethylaminopropylamine, triethylene diamine, 2,2,4-trimethyl-2-silamorpholine, N-ethyl 2,2-dimethyl-2-silamorpholine, N- (2-aminoethyl) morpholine, N- (2-hydroxyethyl) morpholine, N, N-dimethylaminoethanol, N, N-diethylaminoethanol, bis (2-dimethylaminoethyl ether), 1- ( 2-hydroxyethyl) pyrrolidine, 1- (3-hydroxyethyl) pyrrolidine, N, N-dimethylaminoethoxyethanol, N, N, N'-trimethyl-N '- (2-hydroxyethyl) bis (2-aminoethyl) ether, tris (dimethylaminopropyl) hexahydro-1,3,5-triazine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,5,7-triazabicyclo [ 4.4.0] dec-5-ene, N-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1,4,6-triazabicyclo [3.3.0] oct-4-ene , 1,1,3,3-tetramethylguanidine and / or 2,4,6-tris (dimethylaminomethyl) phenol, advantageously in a total amount of Gew 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight .-%.

For the purposes of the aforementioned subject matter of the present invention, particularly preferred compositions are those compositions in which at least one nitrogen-containing compound of the formula (III) and / or (IV) and / or a corresponding quaternized and / or protonated compound is used in combination with a) , with b), with c), with d), with e), with f), with g), with h), with i), with j), with b) and e), with b) and f) , with b) and g), with b) and h), with c) and e), with c) and f), with c) and g), with c) and h), with i) and e), with i) and f), with i) and g), with i) and h), with j) and e), with j) and f), with j) and g), with j) and h), with b) and c), with b), c) and i), with b), c) and j), with b), c), i) and j), with b) and j), with c) and j), with i) and j), with b), c) and e), with b), c), i) and e), with b), c) and f), with b), c), i) and f), with b), c) and g), with b), c), i) and g), with b), c) and h), with b), c), i) and h ), with b), c), j) and h), with b), c), i), j) and h), with b), j) and h), with c), j) and h), with i), j) and h), with b), c), j) and g), with b), c), i), j) and g ), with b), j) and g), with c), j) and g), with i), j) and g), with b), c), j) and f), with b), c ), i), j) and f), with b), j) and f), with c), j) and f), with i), j) and f), with b), c), j) and e), with b), c), i), j) and e), with b), j) and e), with c), j) and e) or with i), j) and e).

A polyurethane system which is obtainable through use as previously described is described.

These polyurethane systems according to the invention are preferably polyurethane foams, preferably rigid polyurethane foams, flexible polyurethane foams, viscoelastic foams, highly elastic foams, so-called “high resilience foams” (HR), semi-rigid polyurethane foams, thermoformable polyurethane foams or integral foams. The term polyurethane is again a generic term for a species consisting of di- or polyisocyanates and polyols or other isocyanate-reactive species, e.g. Amines, polymer to be understood, wherein the urethane bond need not be the exclusive or predominant bond type. Polyisocyanurates and polyureas are also expressly included.

The polyurethane system according to the invention, in particular polyurethane foam, is preferably distinguished by the fact that it is a rigid polyurethane foam, a flexible polyurethane foam, a viscoelastic foam, a high resilience (HR) foam, a semi-rigid polyurethane foam, a thermoformable polyurethane foam or an integral foam, it preferably being a mass fraction nitrogenous Compounds of the formula (III) and / or (IV), and / or the corresponding quaternized and / or protonated compounds or the residues obtained by reacting these on the finished polyurethane foam from 0.005 to 10% by weight, preferably from 0.05 to 3% by weight, particularly preferably 0.1 to 1% by weight.

In a preferred embodiment, the polyurethane foams according to the invention or produced according to the invention are open-celled polyurethane foams, in particular flexible foams, particularly preferably flexible soft foams. In the context of the present invention, open-cell means that a foam has good air permeability (= porosity). The air permeability of the foam can be determined by measuring the dynamic pressure on the foam. The dynamic pressure measurement can be based on EN 29053. If the measured dynamic pressure is given in mm water column, then open-cell polyurethane foams, in particular flexible polyurethane foams, have a dynamic pressure of less than 100 mm, preferably 50 50 mm water column, determined according to the measurement method described in the examples.

A preferred composition for the production of polyurethane or polyisocyanurate foam in the sense of the present invention has a density (RG) of preferably 5 to 800, in particular 5 to 300, preferably 5 to 150, particularly preferably 10 to 90 kg / m ³ and in particular has the following composition: component Weight percentage Polyol 100 (Amine) catalyst 0.05 to 5 Potassium trimerization catalyst 0 to 10 Siloxane 0.1 to 15, preferably 0.2 to 7 water 0 to <25, preferably 0.1 to 15 Propellant 0 to 130 Flame retardant 0 to 70 Fillers 0 to 150 other additives 0 to 20 Isocyanate index: bigger than 15

It is possible to use polyurethane systems, in particular polyurethane foams, as described above, as refrigerator insulation, insulation board, sandwich element, pipe insulation, spray foam, 1- & 1.5-component can foam, imitation wood, model foam, floral foam, packaging foam, mattress, furniture upholstery, molded furniture foam , Pillows, rebonded foam, sponge foam, automobile seat cushion, headrest, instrument panel, automobile interior lining, automobile headlining, sound absorption material, steering wheel, shoe sole, carpet back foam, filter foam, sealing foam, sealant and adhesive or for the manufacture of corresponding products.

In the examples listed below, the present invention is described by way of example, without the invention, the scope of which results from the entire description and the claims, being restricted to the embodiments mentioned in the examples.

Examples:

Production of nitrogen-containing compounds according to the invention

The 1- (3-aminopropyl) pyrrolidine (CAS 23159-07-1) required for the synthesis of the compounds of the formula (III) and (IV) was, as is known in the prior art, via the Michael addition of Acrylonitrile on pyrrolidine and subsequent hydrogenation of the resulting nitrile and final fine distillation.

Synthesis example 1: Preparation of 1-pyrrolidine propanenitrile

chemical CAS supplier Acrylonitrile,> 99% 107-13-1 Sigma-Aldrich Chemie GmbH Pyrrolidine, 99% 123-75-1 ABCR Dichloromethane 75-09-2 Sigma-Aldrich Chemie GmbH Sodium hydroxide, ≥99%, p.a. 1310-73-2 Karl Roth GmbH Sodium chloride, ≥99.8%, 7647-14-5 Karl Roth extra fine GmbH Methanol, ≥99.8% 67-56-1 Sigma-Aldrich Chemie GmbH

2224 ml of water are placed in a 6 L five-necked flask equipped with a dropping funnel, thermometer, KPG stirrer and nitrogen feed and the reaction vessel is rendered inert. Then 861.2 ml (737.18 g, 10.37 mol) of pyrrolidine were slowly added, the temperature rising to 35 ° C. The reaction apparatus was again rendered inert via the dropping funnel and this was filled with 625 ml (500 g, 9.42 mol) of acrylonitrile. The amine solution was cooled to -5 ° C. by means of a cooling bath and the addition of the acrylonitrile was then started. The dropping rate was regulated over 5 hours in such a way that the reaction temperature did not exceed 5 ° C. The reaction mixture was allowed to warm to room temperature and stirred for an hour. Then 2.1 L of a 33% by weight aqueous sodium hydroxide solution were added, whereupon a milky suspension formed. After decanting into a separating funnel, phase separation occurred and the cloudy, upper organic phase still containing water was separated. For better phase separation, 200 ml of dichloromethane and 50 ml of a cold saturated saline solution were added. The upper, slightly opaque organic phase was dried over magnesium sulfate and the solvent was concentrated on a rotary evaporator. The following fine distillation gave 1.25 kg of a clear, slightly yellow oil, the NMR spectroscopic analysis was in line with the expectation. A GC measurement confirmed a purity of> 95%.

Synthesis example 2: Preparation of 1- (3-aminopropyl) pyrrolidine

The subsequent hydrogenation of the previously prepared 1-pyrrolidine propanenitrile was carried out using Pd / Al ₂ O ₃ (5% by weight) as described by Krupka and Jiri et al. in - "Hydrogenation of 3- (dimethylamino) propionitrile over palladium catalysts" (Czechoslovak Chemical Communications, 65 (11), 1805-1819; 2000). The crude reaction mixture obtained was mixed with Celite ^® filter aid, filtered off and washed with methanol. The solvent was concentrated and the crude product was subjected to fine distillation, the main fraction being transferred in a membrane pump vacuum at 24 mbar at a top temperature of 90.degree. An alternative electrochemical method is described in SU1421738 (A1).

Synthesis example 3: Preparation of the compound according to formula (III), technical product mixture

chemical CAS supplier 1- (3-aminopropyl) pyrrolidine according to synthesis example 2 23159-07-1 Propylene oxide,> 99% 75-56-9 Sigma-Aldrich Chemie GmbH

An amount of 64.07 g (0.5 mol) of 1- (3-aminopropyl) pyrrolidine was added to a 250 ml laboratory autoclave equipped with a stirrer, a heatable jacket, pressure transducer and temperature probe as well as an inert gas supply while cooling with an ice bath Synthesis example 2 was prepared, and 58.08 g (1 mol) of propylene oxide were introduced. The autoclave was closed, rendered inert with nitrogen and the jacket was heated to 100 ° C. with a thermal oil. The reaction temperature was then kept under stirring for 4 hours. When the reaction time had ended, the mixture was allowed to cool to room temperature, the pressure vessel was let down and flushed with nitrogen. The crude reaction mixture was examined by gas chromatography, in addition to 24.8% unreacted starting material and 44.1% monopropoxylated product, 25.2% of the desired di-propoxylated product according to formula (III) and a total of 5.9% higher propoxylates and others By-products found. A fine distillation was then carried out to isolate the products. At a pressure of 3.1 mbar and a head temperature of 120-125 ° C., the mono-propoxylated product was obtained in a GC purity of 95.8% as a clear fraction. The distillation residue freed from the educt and the mono-propoxylated product was then distilled using a short-path evaporator in order to obtain the di-propoxylated product. At 0.3-0.5 mbar and ~ 135 ° C jacket temperature, the di-propoxylated product according to formula (III) passed as a slightly viscous oil at room temperature in a GC purity of 96.9%. The NMR spectroscopic as well as the GC or GC / MS analyzes of the respective fractions confirmed the formation of the two products.

Synthesis example 4: Preparation of the compound according to formula (IV), technical product mixtures

chemical CAS supplier 1- (2-aminoethyl) pyrrolidine 7154-73-6 ABCR Propylene oxide,> 99% 75-56-9 Sigma-Aldrich Chemie GmbH

A quantity of 57.10 g (0.5 mol) of 1- (2-aminoethyl) pyrrolidine and 58, in a 250 ml laboratory autoclave equipped with a stirring device, a heatable jacket, pressure transducer and temperature probe and an inert gas supply, were cooled with an ice bath. 08 g (1 mol) of propylene oxide submitted. The autoclave was closed, rendered inert with nitrogen and the jacket was heated to 100 ° C. with a thermal oil. The reaction temperature was then kept under stirring for 4 hours. When the reaction time had ended, the mixture was allowed to cool to room temperature, the pressure vessel was let down and flushed with nitrogen. The crude reaction mixture was examined by gas chromatography, in addition to 21.3% of unreacted starting material and 44% of mono-propoxylated product, 30.1% of the desired di-propoxylated product of the formula (IV), and a total of 4.5% of higher propoxylates and other by-products were found. A fine distillation was then carried out to isolate the product.
It was thus possible to obtain the mono-propoxylated product in a GC purity of 97.1% as a clear fraction at a pressure of 1 mbar and a head temperature of 95-110 ° C. As the distillation proceeded, the di-propoxylated product according to formula (IV) was able to be obtained in the subsequent fraction at a pressure of 1 mbar and a head temperature of 115-125 ° C as a clear, slightly viscous oil at room temperature in a GC purity of 97 , 5% can be won. The NMR spectroscopic as well as the GC or GC / MS analyzes of the respective fractions confirmed the product formation of the two products.

Hard foam - examples of foaming

Example 1: Production of rigid polyurethane foams, for example for use in the insulation of refrigerated cabinets

The foam formulation given in Table 1 was used for the application-related testing of the nitrogen-containing compounds according to the invention. Table 1: Formulation 1 for rigid foam applications. Formulation 1 Parts by mass (pphp) Polyol 1 ¹ ) 100 parts water 2.60 parts Cyclopentane 13.1 parts Amine 1.50 parts TEGOSTAB ^® B 8460 ²⁾ 1.50 parts Desmodur ^® 44V20L ³⁾ 198.5 parts ¹⁾ Polyol 1: Sorbitol / glycerol-based polyether polyol with an OH number of 471 mgKOH / g. ²⁾ Polyether modified polysiloxane. ³⁾ polymeric MDI from Bayer, 200 mPas, 31.5% NCO, functionality 2.7.

The foaming was carried out by hand mixing. The formulations, as indicated in Table 1, were used with various nitrogen-containing catalysts (amines). For this purpose, polyol 1, conventional or nitrogen-containing catalyst (amine) according to the invention, water, foam stabilizer and blowing agent were weighed into a beaker and mixed with a 6 cm diameter stirrer at 1000 rpm for 30 seconds. By weighing again, the amount of blowing agent evaporated during the mixing process was determined and supplemented again. Now the isocyanate (MDI) was added, the reaction mixture was stirred with the described stirrer for 5 s at 3000 rpm and immediately transferred to a box lined with paper (27 cm × 14 cm base area and 14 cm height). The following characteristic parameters were determined in order to assess the catalytic properties: cream time, gel time (thread-pulling time), rise time and tack-free time.

The results of the assessment of the catalytic properties of the nitrogen-containing compounds of the formula (III) and (IV) according to the invention are summarized in Table 2. N, N-dimethylcyclohexylamine (DMCHA), dimethylaminoethoxyethanol (DMEE) and N '- (3-dimethylaminopropyl) -N, N-diisopropylamine (TEGOAMIN ^® ZE 1, available from Evonik Industries) were used as comparative catalysts according to the prior art . Table 2: Results of the foaming according to formulation 1 (Table 1). Amine Cream time [s] ¹⁾ Gel time [s] ¹⁾ Rise time [s] ¹⁾ Tack free time [s] ¹⁾ DMCHA 38 148 293 315 DMEE 31 154 272 303 TEGOAMIN ^® ZE 1 40 243 325 415 FORMULA (III) 57 235 340 423 FORMULA (IV) 64 236 356 429 ¹⁾ Time information in seconds [s].

As can be seen from Table 2, the nitrogen-containing compounds of the formula (III) and (IV) according to the invention show a moderate catalytic activity in the selected rigid polyurethane foam application. Both compounds have a somewhat lower activity towards DMCHA and also towards the reactive DMEE. However, they show a catalytic profile comparable to that TEGOAMIN ^® ZE 1, but a stronger selectivity of the catalysis towards the gel reaction, which can be seen from the lower gel time.

Soft foam - application tests

Physical properties of flexible polyurethane foams:

1. a) Rücksacken des Schaumstoffes nach dem Ende der Steigphase (=Rückfall): Der Rückfall, bzw. das Nachsteigen ergibt sich aus der Differenz der Schaumhöhe nach direktem Abblasen und nach 3 Minuten. nach Abblasen des Schaums. Die Schaumhöhe wird dabei durch eine an einem Zentimetermaß befestigte Nadel auf dem Maximum in der Mitte der Schaumkuppe gemessen. Ein negativer Wert beschreibt hierbei das Rücksacken des Schaumes nach dem Abblasen, ein positiver Wert beschreibt entsprechend das Nachsteigen des Schaumes.
2. b) Schaumhöhe: Die Endhöhe des Schaums wird dadurch bestimmt, dass der Rückfall bzw. das Nachsteigen von bzw. zu der Schaumhöhe nach dem Abblasen subtrahiert bzw. addiert wird. Die Schaumhöhe wird in Zentimeter (cm) angegeben.
3. c) Raumgewicht (RG): Die Bestimmung erfolgt, wie in ASTM D 3574 - 11 unter Test A beschrieben, durch Messung der Core Density. Das Raumgewicht wird in kg/m³ angegeben.
4. d) Porosität: Die Luftdurchlässigkeit des Schaums wurde durch eine Staudruckmessung am Schaumstoff ermittelt. Der gemessene Staudruck wird in mm Wassersäule angegeben, wobei niedrigere Staudruckwerte einen offeneren Schaum charakterisieren. Die Werte wurden im Bereich von 0 bis 300 mm gemessen. Die Messung des Staudrucks erfolgte mittels einer Apparatur umfassend eine Stickstoffquelle, Reduzierventil mit Manometer, Durchflussregelschraube, Waschflasche, Durchflussmessgerät, T-Stück, Auflagedüse und einem skaliertem Glasrohr, in welches Wasser gefüllt ist. Die Auflagedüse weist eine Kantenlänge von 100 × 100 mm, ein Gewicht von 800 g, eine lichte Weite der Austrittsöffnung von 5 mm, eine lichte Weite des unteren Auflageringes von 20 mm und einen Außendurchmesser des unteren Auflageringes von 30 mm auf. Die Messung erfolgt durch Einstellung des Stickstoffvordrucks per Reduzierventil auf 1 bar und Einregeln der Durchflussmenge auf 480 l/h. Die Wassermenge wird im skalierten Glasrohr so eingestellt, dass keine Druckdifferenz aufgebaut und ablesbar ist. Für die Vermessung des Prüfkörpers mit einer Dimension von 250 × 250 × 50 mm wird die Auflagedüse an den Ecken des Prüfkörpers kantenkongruent aufgelegt sowie einmal an der (geschätzten) Mitte des Prüfkörpers (jeweils auf der Seite mit der größten Oberfläche) aufgelegt. Abgelesen wird, wenn sich ein konstanter Staudruck eingestellt hat. Die Auswertung erfolgt durch Mittelwertbildung über die fünf erhaltenen Messwerte.
5. e) Stauchhärte CLD, 40 % nach DIN EN ISO 3386 . Die Angabe der Messwerte erfolgt in Kilopascal (kPa).

The flexible polyurethane foams produced were assessed on the basis of the following physical properties:

1. a) Bagging back of the foam after the end of the climbing phase (= relapse): The relapse or the climb back results from the difference in foam height after direct blowing off and after 3 minutes. after blowing off the foam. The foam height is measured by a needle attached to a centimeter at the maximum in the middle of the foam tip. A negative value describes the sagging of the foam after blowing off, a positive value describes the rising of the foam.
2. b) Foam height: The final height of the foam is determined by subtracting or adding the relapse or rising from or to the foam height after blowing off. The foam height is given in centimeters (cm).
3. c) Bulk density (RG): The determination is carried out, as described in ASTM D 3574-11 under test A, by measuring the core density. The density is given in kg / m ³ .
4. d) Porosity: The air permeability of the foam was determined by a dynamic pressure measurement on the foam. The measured dynamic pressure is given in mm water column, whereby lower dynamic pressure values characterize a more open foam. The values were measured in the range from 0 to 300 mm. The back pressure was measured using an apparatus comprising a nitrogen source, reducing valve with manometer, flow regulating screw, wash bottle, flow meter, T-piece, support nozzle and a scaled glass tube into which water is filled. The support nozzle has an edge length of 100 × 100 mm, a weight of 800 g, a clear width of the outlet opening of 5 mm, a clear width of the lower support ring of 20 mm and an outer diameter of the lower support ring of 30 mm. The measurement is carried out by setting the nitrogen inlet pressure to 1 bar using a reducing valve and adjusting the flow rate to 480 l / h. The amount of water is set in the scaled glass tube so that no pressure difference can be built up and read. For the measurement of the test specimen with a dimension of 250 × 250 × 50 mm, the support nozzle is placed at the corners of the test specimen with a congruent edge and once placed on the (estimated) center of the test specimen (each on the side with the largest surface). Readings are made when a constant dynamic pressure has set in. The evaluation is carried out by averaging the five measured values obtained.
5. e) CLD compression hardness, 40% after DIN EN ISO 3386 . The measured values are stated in kilopascals (kPa).

• Das Verfahren dient zur Ermittlung von Emissionen aus nichtmetallischen Materialein, die für Formteile in Kraftfahrzeugen zum Einsatz kommen. Die Emission von leichtflüchtigen organischen Verbindungen (VOC-Wert, 30 Minuten bei 90 °C) sowie dem Anteil kondensierbarer Substanzen (Fog-Wert, 60 Minuten bei 120 °C), insbesondere der Katalyse-bedingten Emissionen, die Emissionen der einzelnen Bestandteile erfindungsgemäßer Katalysatorkombinationen oder ihrer Zer- oder Umsetzungsprodukte, wurde in Anlehnung an die Prüfvorschrift VDA 278 in der Version vom Oktober 2011 bestimmt. Im Folgenden wird die Durchführung der entsprechenden Thermodesorption mit anschließender Gaschromatographie/Massenspektrometrie-Kopplung (GC/MS) beschrieben.
  1. a) Messtechnik: Die Thermodesorption wurde mit einem Thermodesorber „TDS2“ mit Probenwechsler der Fa. Gerstel, Mülheim, in Verbindung mit einem Agilent 7890/5975 GC/MSD-System durchgeführt.
  2. b) Die Messbedingungen für VOC-Messungen sind in Tabellen 3 und 4 angegeben.

Tabelle 3: Messparameter Thermodesorption für den VOC-Analysenlauf. Thermodesorption Gerstel TDS2 Desorptionstemperatur 90 °C Desorptionsdauer 30 min Fluss 65 ml/min Transferline 280°C Kryofokussierung KAS 4 Liner Glasverdampferrohr mit silanisierter Glaswolle Temperatur -150°C Tabelle 4: Messparameter Gaschromatographie/Massenspektrometrie für den VOC-Analysenlauf. GC Kapillar-GC Agilent 7890 Injektor PTV Split 1:50 Temperaturprogramm -150°C; 1 min; ⇗10°C/s; 280°C Säule Agilent 19091B-115, Ultra 2, 50 m * 0,32 mm dF 0,5µm Fluss 1,3 ml/min const. Flow Temperaturprogramm 50°C; 2 min; ⇗3°C/min; 92°C; ⇗5°C/min; 160°C; ⇗10°C/min; 280°C, 20 min Detektor Agilent MSD 5975 Modus Scan 29-350 amu 2,3 scans/sec Auswertung Auswertung des Totalionenstrom-Chromatrogramms durch Berechnung als Toluoläquivalent

• c) Kalibrierung: Zur Kalibrierung wurde 2 µl eines Gemisches aus Toluol und Hexadekan in Methanol (je 0,125 mg/ml) auf ein gereinigtes, mit Tenax^® TA (mesh 35/60) gefülltes Adsorptionsröhrchen gegeben und vermessen (Desorption 5 min; 280 °C).
• d) Bei Tenax^® TA handelt es sich um ein poröses Polymerharz basierend auf 2.6-Diphenylen¬oxid, erhältlich beispielsweise bei der Firma Scientific Instrument Services, 1027 Old York Rd., Ringoes, NJ 08551.
• e) Probenvorbereitung für die VOC-Messung: 15 mg Schaumstoff wurden in drei Teilproben in einem Thermodesorptionsröhrchen platziert. Dabei wurde darauf geachtet, dass der Schaum nicht komprimiert wird.
• f) Probenvorbereitung für die Fog-Messung: Es wurde die gleiche Schaumprobe verwendet, wie für die VOC-Messung. Hinsichtlich der Messanordnung wurde immer zuerst die VOC-Messung und im Anschluss die Fog-Messung durchgeführt, wobei mittels eines Autosampler-Systems ein jeweils konstanter Abstand zwischen den entsprechenden VOC- und Fog-Messungen gewährleistet wurde.
• g) Die Messbedingungen für Fog-Messungen sind in Tabelle 5 und 6 wiedergegeben.

Tabelle 5: Messparameter Thermodesorption für den Fog-Analysenlauf. Thermodesorption Gerstel TDS2 Desorptionstemperatur 120 °C Desorptionsdauer 60 min Fluss 65 ml/min Transferline 280°C Kryofokussierung KAS 4 Liner Glasverdampferrohr mit silanisierter Glaswolle Temperatur -150°C Tabelle 6: Messparameter Gaschromatographie/Massenspektrometrie für den Fog-Analysenlauf. GC Kapillar-GC Agilent 7890 Injektor PTV Split 1:50 Temperaturprogramm -150°C; 1 min; ⇗10°C/s; 280°C Säule Agilent 19091B-115, Ultra 2, 50 m * 0,32 mm dF 0,5µm Fluss 1,3 ml/min const. Flow Temperaturprogramm 50°C; 2 min; ⇗25°C/min; 160°C; ⇗10°C/min; 280°C; 20 min Detektor Agilent MSD 5975 Modus Scan 29-450 amu 2,3 scans/sec Auswertung Auswertung des Totalionenstrom-Chromatrogramms durch Berechnung als Hexadekanäquivalent

• h) Kalibrierung: Zur Kalibrierung wurde 2 µl eines Gemisches aus Toluol und Hexadekan in Methanol (je 0,125 mg/ml) auf ein gereinigtes, mit Tenax^®TA (mesh 35/60) gefülltes Adsorptionsröhrchen gegeben und vermessen (Desorption 5 min; 280 °C).

Measurement of foam emissions (VOC and fog value) based on the test specification VDA 278 in the version from October 2011:

• The method is used to determine emissions from non-metallic materials that are used for molded parts in motor vehicles. The emission of volatile organic compounds (VOC value, 30 minutes at 90 ° C) and the proportion of condensable substances (fog value, 60 minutes at 120 ° C), in particular the emissions caused by catalysis, the emissions of the individual components of catalyst combinations according to the invention or their decomposition or implementation products was determined based on the test specification VDA 278 in the version from October 2011. In the following, the implementation of the corresponding thermal desorption with subsequent gas chromatography / mass spectrometry coupling (GC / MS) is described.
  1. a) Measurement technology: The thermal desorption was carried out with a thermal desorber "TDS2" with sample changer from Gerstel, Mülheim, in connection with an Agilent 7890/5975 GC / MSD system.
  2. b) The measurement conditions for VOC measurements are given in Tables 3 and 4.

Table 3: Thermal desorption measurement parameters for the VOC analysis run. Thermal desorption Gerstel TDS2 Desorption temperature 90 ° C Desorption time 30 min flow 65 ml / min Transferline 280 ° C Cryofocusing KAS 4 Liner Glass evaporator tube with silanized glass wool temperature -150 ° C Table 4: Measurement parameters gas chromatography / mass spectrometry for the VOC analysis run. GC Capillary GC Agilent 7890 Injector PTV split 1:50 Temperature program -150 ° C; 1 min; ⇗10 ° C / s; 280 ° C pillar Agilent 19091B-115, Ultra 2, 50 m * 0.32 mm dF 0.5 µm flow 1.3 ml / min const. Flow Temperature program 50 ° C; 2 min; ⇗3 ° C / min; 92 ° C; ⇗5 ° C / min; 160 ° C; ⇗10 ° C / min; 280 ° C, 20 min detector Agilent MSD 5975 mode Scan 29-350 amu 2.3 scans / sec evaluation Evaluation of the total ion current chromatogram by calculation as toluene equivalent

• c) Calibration: For the calibration, 2 μl of a mixture of toluene and hexadecane in methanol (0.125 mg / ml each) were placed on a cleaned adsorption tube filled with Tenax ^® TA (mesh 35/60) and measured (desorption 5 min; 280 ° C).
• d) Tenax ^® TA is a porous polymer resin based on 2,6-diphenylene oxide, available for example from Scientific Instrument Services, 1027 Old York Rd., Ringoes, NJ 08551.
• e) Sample preparation for VOC measurement: 15 mg foam was placed in three partial samples in a thermodesorption tube. Care was taken to ensure that the foam is not compressed.
• f) Sample preparation for the fog measurement: The same foam sample was used as for the VOC measurement. With regard to the measurement arrangement, the VOC measurement was always carried out first and then the fog measurement, with an autosampler system ensuring a constant distance between the corresponding VOC and fog measurements.
• g) The measurement conditions for fog measurements are shown in Tables 5 and 6.

Table 5: Measurement parameters thermal desorption for the Fog analysis run. Thermal desorption Gerstel TDS2 Desorption temperature 120 ° C Desorption time 60 min flow 65 ml / min Transferline 280 ° C Cryofocusing KAS 4 Liner Glass evaporator tube with silanized glass wool temperature -150 ° C Table 6: Measurement parameters gas chromatography / mass spectrometry for the Fog analysis run. GC Capillary GC Agilent 7890 Injector PTV split 1:50 Temperature program -150 ° C; 1 min; ⇗10 ° C / s; 280 ° C pillar Agilent 19091B-115, Ultra 2, 50 m * 0.32 mm dF 0.5 µm flow 1.3 ml / min const. Flow Temperature program 50 ° C; 2 min; ⇗25 ° C / min; 160 ° C; ⇗10 ° C / min; 280 ° C; 20 min detector Agilent MSD 5975 mode Scan 29-450 amu 2.3 scans / sec evaluation Evaluation of the total ion current chromatogram by calculation as hexadecane equivalent

• h) Calibration: For the calibration, 2 μl of a mixture of toluene and hexadecane in methanol (0.125 mg / ml each) were added to a cleaned adsorption tube filled with Tenax ^® TA (mesh 35/60) and measured (desorption 5 min; 280 ° C).

1. a) Messtechnik: Die Thermodesorption wurde mit einem Thermodesorber „TDS2“ mit Probenwechsler der Fa. Gerstel, Mülheim, in Verbindung mit einem Agilent 7890/5975 GC/MSD-System durchgeführt.
2. b) Die Messbedingungen sind in Tabelle 7 und 8 angegeben.

Tabelle 7: Messparameter Thermodesorption für PK-Messung. Thermodesorption Gerstel TDS2 Desorptionstemperatur 280°C Desorptionsdauer 5 min Fluss 65 ml/min Transferline 280°C Kryofokussierung KAS 4 Liner Glasverdampferrohr mit silanisierter Glaswolle Temperatur -150°C Tabelle 8: Messparameter Gaschromatographie/Massenspektrometrie für PK-Messung. GC Kapillar-GC Agilent 7890 Temperaturprogramm -150°C; 1 min; ⇗10°C/s; 280°C Säule Agilent 19091B-115, Ultra 2, 50 m * 0,32 mm dF 0,5µm Fluss 1,3 ml/min const. Flow Temperaturprogramm 50°C; 2 min; ⇗3°C/min; 92°C; ⇗5°C/min; 160°C; ⇗10°C/min; 280°C, 20 min Detektor Agilent MSD 5975 Auswertung Auswertung des Totalionenstrom-Chromatrogramms durch Berechnung als Toluoläquivalent

• c) Zur Kalibrierung wurde 2 µl eines Gemisches aus Toluol und Hexadekan in Methanol (je 0,125 mg/ml) auf ein gereinigtes, mit Tenax^® TA (mesh35/60) gefülltes Adsorptionsröhrchen gegeben und vermessen (Desorption 5 min; 280°C).

Determination of the room temperature emission according to the so-called test chamber test (PK): The emission from the foams obtained, in particular the emissions caused by catalysis, the emissions of the individual components of catalyst combinations according to the invention or their decomposition or conversion products, at room temperature in accordance with DIN Regulation DIN EN ISO 16000-9: 2008-04 certainly. Samples were taken after 24 hours. For this purpose, 2 liters of the test chamber atmosphere were passed at a flow rate of 100 ml / min through an adsorption tube filled with Tenax ^® TA (mesh 35/60). The implementation of thermal desorption with subsequent gas chromatography / mass spectrometry coupling (GC / MS) is described below.

1. a) Measurement technology: The thermal desorption was carried out with a thermal desorber "TDS2" with sample changer from Gerstel, Mülheim, in connection with an Agilent 7890/5975 GC / MSD system.
2. b) The measurement conditions are given in Tables 7 and 8.

Table 7: Measurement parameters thermal desorption for PK measurement. Thermal desorption Gerstel TDS2 Desorption temperature 280 ° C Desorption time 5 min flow 65 ml / min Transferline 280 ° C Cryofocusing KAS 4 Liner Glass evaporator tube with silanized glass wool temperature -150 ° C Table 8: Measurement parameters gas chromatography / mass spectrometry for PK measurement. GC Capillary GC Agilent 7890 Temperature program -150 ° C; 1 min; ⇗10 ° C / s; 280 ° C pillar Agilent 19091B-115, Ultra 2, 50 m * 0.32 mm dF 0.5 µm flow 1.3 ml / min const. Flow Temperature program 50 ° C; 2 min; ⇗3 ° C / min; 92 ° C; ⇗5 ° C / min; 160 ° C; ⇗10 ° C / min; 280 ° C, 20 min detector Agilent MSD 5975 evaluation Evaluation of the total ion current chromatogram by calculation as toluene equivalent

• c) For the calibration, 2 μl of a mixture of toluene and hexadecane in methanol (0.125 mg / ml each) were placed on a cleaned adsorption tube filled with Tenax ^® TA (mesh 35/60) and measured (desorption 5 min; 280 ° C.).

Soft foam - examples of foaming

Example 2: Production of flexible polyurethane foams (soft block foam)

The foam formulation given in Table 9 was used to test the application of the nitrogen-containing compounds according to the invention. Table 9: Formulation 2 for soft block foam applications. Formulation 2 Parts by mass (pphp) Polyol 1 ¹⁾ 100 parts water 3.00 parts Tin catalyst ²⁾ 0.20 parts Amine 0.20 parts TEGOSTAB ^® BF 2370 ³⁾ 0.80 parts Desmodur ^® T 80 ⁴⁾ 38.1 parts ¹⁾ Polyol 1: glycerol-based polyether polyol with an OH number of 48 mgKOH / g. ²⁾ KOSMOS ^® 29, available from Evonik Industries: tin (II) salt of 2-ethylhexanoic acid. ³⁾ Polyether modified polysiloxane. ⁴⁾ Toluene diisocyanate T 80 (80% 2,4-isomer, 20% 2,6-isomer) from Bayer, 3 mPas, 48% NCO, functionality 2.

500 g of polyol were used in the foaming; the other formulation components were converted accordingly. For example, 1.00 part of a component meant 1.00 g of a substance per 100 g of polyol.

The foaming was carried out by hand mixing. The formulations, as indicated in Table 9, were used with various nitrogen-containing catalysts (amines). For this purpose, polyol, conventional or inventive nitrogen-containing catalyst (amine), tin catalyst, water and foam stabilizer were weighed into a beaker and mixed for 60 seconds at 1000 rpm. After addition of the isocyanate (TDI), the reaction mixture was stirred for 7 s at 2500 rpm and immediately transferred to a box lined with paper (27 cm × 27 cm base area and 27 cm height). To assess the catalytic properties, the following characteristic parameters were determined: cream time, rise time, rise height, strength of the blow-off (= blow off) and sagging of the foam after the end of the rise phase (= relapse).

Defined foam bodies were cut out of the resulting foam blocks, which were further analyzed. The following physical properties were determined using the test specimens: density (RG), porosity (= air permeability) and compressive strength CLD (40%).

The results of the assessment of the catalytic properties of the nitrogen-containing compounds of the formula (III) and (IV) according to the invention and of the physical properties of the resulting flexible block foams are summarized in Table 10.

As comparative catalysts of the prior art were triethylenediamine, 33 wt% -. Solution in dipropylene glycol (TEGOAMIN ^® 33, available from Evonik Industries) and N '- (3- dimethylaminopropyl) -N, N-diisopropylamine (TEGOAMIN ^® ZE 1, available from Evonik Industries). 0.20 pphp (= parts by weight based on 100 parts by weight of polyol) amine were used in each case. Table 10: Results of the foaming according to formulation 2 (Table 9). Amine Rise time [s] Relapse [cm] Height [cm] RG [kg / m ³ ] Porosity [mm] ¹⁾ CLD 40% [kPa] TEGOAMIN ^® 33 122 0.1 28.7 31.2 19th 4.2 TEGOAMIN ^® ZE 1 142 0.2 28.3 31.9 24th 3.9 FORMULA (III) 141 0.0 27.9 32.0 35 4.2 FORMULA (IV) 140 0.1 28.3 31.9 30th 4.1 ¹⁾ = (dynamic pressure in mm water column).

As can be seen in Table 10, the nitrogen-containing compounds of the formulas (III) and (IV) according to the invention show a comparable catalytic activity and selectivity to TEGOAMIN ^® ZE 1 in flexible foam. However, because of the reactive hydroxyl groups, a larger amount is required to achieve the performance of TEGOAMIN ^® 33. This applies to most reactive amine catalysts according to the prior art.

Example 3: Emissions of flexible polyurethane block foams

In order to investigate the influence of the nitrogen-containing compounds according to the invention on the foam emissions, the foam formulation given in Table 11, which contains a low-emission polyol and a low-emission tin catalyst, was used for the application-related testing of flexible flexible foams. Table 11: Formulation 3, foam emissions in soft block foam applications. Formulation 3 Parts by mass (pphp) Polyol 1 ¹⁾ 100 parts water 3.00 parts Tin catalyst ²⁾ 0.60 parts Amine 0.15 parts TEGOSTAB ^® BF 2370 ³⁾ 0.80 parts Desmodur ^® T 80 ⁴⁾ 41.6 parts ¹⁾ Polyol 1: Low-emission glycerin-based polyether polyol with an OH number of 56 mgKOH / g. ²⁾ KOSMOS ^® EF, available from Evonik Industries: tin (II) salt of ricinoleic acid. ³⁾ Polyether modified polysiloxane. ⁴⁾ Toluene diisocyanate T 80 (80% 2,4-isomer, 20% 2,6-isomer) from Bayer, 3 mPas, 48% NCO, functionality 2.

500 g of polyol were used in the foaming; the other formulation components were converted accordingly. For example, 1.00 part of a component meant 1.00 g of a substance per 100 g of polyol.

The foaming was carried out by hand mixing. The formulations, as indicated in Table 11, were used with various nitrogen-containing catalysts (amines). For this purpose, low-emission polyol, conventional or inventive nitrogen-containing catalyst (amine), low-emission tin catalyst, water and foam stabilizer were weighed into a beaker and mixed for 60 seconds at 1000 rpm. After the addition of the isocyanate (TDI), the reaction mixture was stirred for 7 s at 2500 rpm and immediately transferred to a box lined with paper (27 cm × 27 cm base area and 27 cm height) and the resulting foam after blowing off with polyethylene film hermetically sealed. After a curing phase of 24 hours, the resulting foam block cut out a defined foam cube (7 cm × 7 cm × 7 cm), which was completely enclosed with aluminum foil and further sealed with polyethylene foil.

The emission behavior of the foams described above was then determined at room temperature after the test chamber test based on the DIN regulation DIN EN ISO 16000-9: 2008-04 as described above. The results are shown in Table 12. Table 12: Emissions of flexible slabstock foams according to formulation 3 (Table 11). Volatile organic compounds content according to the test chamber test (PK) Amine PK _tot ¹⁾ PK _Amine ¹⁾ [µg / m ³ ] [µg / m ³ ] TEGOAMIN ^® 33 90 61 TEGOAMIN ^® ZE 1 <20 <10 FORMULA (III) <20 <10 FORMULA (IV) <20 <10 ¹⁾ PK _tot = total emission; PK _amine = amine emissions of all volatile organic compounds in the test chamber test.

Table 12 shows that the amine emissions when using a nitrogen-containing compound according to formula (III) or (IV) according to the invention can not only be reduced in comparison to unreactive amines such as TEGOAMIN ^® 33, but also comparable values can be obtained as with the built-in, VOC-optimized TEGOAMIN ^® ZE 1. In particular, compared to the use of TEGOAMIN ^® 33, alternative use of the catalysts according to formula (III) and (IV) means that flexible polyurethane foams with significantly reduced amine emissions, in this case even foams, are almost free of amine emissions can be obtained. With regard to the amine emissions according to VDA 278, as described above, a considerable reduction in the amine emissions was observed with a corresponding catalyst exchange, in particular when using compounds of the formulas (III) and (IV).

Example 4: Production of HR foams (Block / Molded)

The foam formulation given in Table 13 was used for the application-related testing of the nitrogen-containing compounds according to the invention. Table 13: Formulation 4 for cold flexible foam applications (HR block / molded). Formulation 4 Parts by mass (pphp) Polyol 1 ¹⁾ 70.0 parts Polyol 2 ²⁾ 30.0 parts water 3.70 parts Glycerin 0.50 parts Diethanolamine (DEOA) 1.00 parts Amine 0.25 parts TEGOSTAB ^® B 8716 LF2 ³⁾ 1.00 parts Desmodur ^® T 80 ⁴⁾ 44.0 parts ¹⁾ Polyol 1: Sorbitol / glycerin-based polyether polyol, with an OH number of 32 mgKOH / g. ²⁾ Polyol2: glycerol-based polyether polyol, containing 43% solids (SAN), with an OH number of 20 mgKOH / g. ³⁾ Preparation of organomodified polysiloxanes. ⁴⁾ Toluene diisocyanate T 80 (80% 2,4-isomer, 20% 2,6-isomer) from Bayer, 3 mPas, 48% NCO, functionality 2.

The same foaming methods were used here as for the classic flexible polyurethane foam in Examples 2 and 3.

500 g of polyol were used in the foaming; the other formulation components were converted accordingly. For example, 1.00 part of a component meant 1.00 g of a substance per 100 g of polyol.

For foaming, the polyol, water, amine and silicone stabilizer were mixed well with stirring. After the isocyanate had been added, the mixture was stirred at 3000 rpm for 4 s. stirred and the mixture poured into a paper lined wooden box (27 cm × 27 cm base and 27 cm high). The result was a foam that was subjected to the application tests described below.

The results of the assessment of the catalytic properties of the nitrogen-containing compounds of the formula (III) and (IV) according to the invention and the physical properties of the resulting foams are summarized in Table 14. Triethylenediamine, 33% by weight solution in dipropylene glycol (TEGOAMIN ^® 33, available from Evonik Industries), N '- (3-dimethylaminopropyl) -N, N-diisopropylamine (TEGOAMIN ^® ZE 1, available from Evonik Industries), ZR-50 available inserted 1- [bis [3- (dimethylamino) propyl] amino] -2-propanol (Jeffcat ^® from Evonik Huntsman). 0.25 pphp (= parts by weight based on 100 parts by weight of polyol) amine were used in each case. Table 14: Results of the foaming according to formulation 4 (Table 13). Amine Gel time Rise time height Relapse Cell count ¹⁾ [s] [s] [cm] [cm] [cm ^-1 ] TEGOAMIN ^® 33 94 147 31.6 0.8 10.5 TEGOAMIN ^® ZE 1 132 214 30.5 0.0 9.5 Jeffcat ZR-50 90 161 31.6 0.5 10.5 FORMULA (IIII) 111 189 31.9 0.3 10.0 FORMULA (IV) 131 214 30.5 0.1 9.5 ¹⁾ Number of cells = number of cells per cm [cm ^-1 ].

As can be seen from Table 14, the nitrogen-containing compounds of the formulas (III) and (IV) according to the invention show good catalytic activity in flexible cold foam. With regard to the catalytic profile, the catalysts (III) and (IV) can be classified as balanced catalysts which catalyze both the gel and the blowing reaction, the compounds of the formula (III) in particular being higher than TEGOAMIN ^® ZE 1 Activity and also has a noticeable increase in gel selectivity. The compound of the formula (IV) is similarly active and selective as TEGOAMIN ^® ZE 1.

The emission behavior of the foams described above was then examined in accordance with the test specification VDA 278 in the version from October 2011, as described above. The results are shown in Table 15. Table 15: Emissions of flexible cold foams according to VDA 278. Volatile Organic Compound (VOC) content Amine VOC _total ¹⁾ [µg / g] VOC _amine ¹⁾ [µg / g] Fog _total ²⁾ [µg / g] Fog _Amine ²⁾ [µg / g] TEGOAMIN ^® 33 508 186 280 <10 TEGOAMIN ^® ZE 1 313 <10 325 <10 Jeffcat ZR-50 332 <10 418 103 FORMULA (IIII) 320 <10 330 <10 FORMULA (IV) 350 <10 380 <10 ¹⁾ VOC _total = total emission; VOC _amine = amine emissions of all volatile organic compounds at 90 ° C (30 minutes). ²⁾ Fog _total = total emission; Fog _amine = amine emissions of all volatile organic compounds at 120 ° C (60 minutes).

As the table 15 can be removed, nitrogen-containing compounds of the invention exhibit the formula (III) and (IV) no emission according to VDA 278. With regard to the VOC emissions meet example Jeffcat ^® ZR-50 and TEGOAMIN ^® ZE 1 these requirements too. However, TEGOAMIN ^® ZE 1 has a better fog test than Jeffcat ^® ZR-50, but is significantly weaker in terms of its catalytic activity. The compound according to formula (III) has a slightly better catalytic activity than TEGOAMIN ^® ZE 1, but also improved values compared to Jeffcat ^® ZR-50 in terms of fog emissions. For automotive applications, this means a reduction in potential deposits of easily condensable substances in the interior of the automobile, for example on the windshield, also referred to as “windshield fogging”.

Claims (8)

Use of at least one nitrogen-containing compound and / or a corresponding quaternized and / or protonated compound in the production of polyurethanes, characterized in that a compound of the formula (III) and / or (IV)

is used. Use after Claim 1 , characterized in that at least one nitrogen-containing compound of the formula (III) and / or (IV) is used as the technical product mixture, containing impurities, intermediate and / or by-products as further ingredients in a total amount of Gew 10% by weight. Use according to one of the previous ones Claims 1 or 2nd , characterized in that the nitrogen-containing compound of formula (III) or (IV), a correspondingly quaternized and / or protonated compound, is used as a catalyst in the production of polyurethanes. Use according to one of the preceding claims, characterized in that in the production of the polyurethane a composition is produced which contains at least one nitrogen-containing compound of the formula (III) and / or (IV), a corresponding quaternized and / or protonated compound, and furthermore at least has a polyol component, at least one isocyanate component and one or more blowing agents, and this composition is reacted. Use according to one of the preceding claims, characterized in that the at least one nitrogen-containing compound of the formula (III) and / or (IV) is used in combination with at least one solvent, the mass ratio of the total catalyst used comprising all catalytically active compounds the same and different from the formula (III) and / or (IV), is from 100 to 1 to 1 to 4 to solvent. Composition containing at least one polyol component, characterized in that the composition has at least one nitrogen-containing compound of the formula (III) and / or (IV), as defined in the preceding claims, and / or the corresponding quaternized and / or protonated compounds. Composition according to Claim 6 , characterized in that the molar ratio of the total amount of nitrogen-containing catalysts, comprising the nitrogen-containing compounds of the formula (III) and / or (IV), to the total amount of the isocyanate-reactive groups of the polyol component from 4 × 10 ^-4 to 1 to 0 , Is 2 to 1. Compositions according to Claim 6 or 7 , characterized in that the nitrogen-containing compounds of formula (III) and / or (IV), corresponding quaternized and / or protonated compounds, in total in a mass fraction of 0.01 to 20.0 parts (pphp), preferably 0.01 up to 5.00 parts and particularly preferably 0.02 to 3.00 parts based on 100 parts (pphp) of polyol component.