DE102014215381B4 - Nitrogen containing compounds suitable for use in the manufacture of polyurethanes - Google Patents

Abstract

Use of at least one nitrogen-containing compound, a corresponding quaternized and / or protonated compound in the production of polyurethanes, characterized in that the nitrogen-containing compound of the formula (I) is sufficient with n = 1 to 30, a = 2 and b = 1, where the ethers - or amine building blocks, if present, can occur cumulatively, alternately, in blocks or in a disordered manner, R, R equals or unequal to one another, is a linear, branched or cyclic, aliphatic, saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, R = H or is a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted with one or more heteroatoms or interrupted by one or more heteroatoms hydrocarbon residue with 1 to 30 carbon atoms,

Description

The present invention is in the field of nitrogen-containing compounds, in particular amines, and polyurethanes. It relates in particular to the use of nitrogen-containing compounds of the formula (I), correspondingly quaternized and / or protonated compounds, for the production of polyurethanes, in particular polyurethane foams, and compositions which contain 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.

JP H08-259655 A describes amine catalysts for polyurethane production. There, however, only structures are disclosed which terminate on one side with an OH group.

DE841917 C describes a process for the preparation of bis-tert-aminoalkoxyalkanes. However, the structures disclosed there have no unit - (NR ₂ R ₃ ) _b -.

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 possibly with low amine or other emissions, such as formaldehyde and / or dimethylformamide (DMF).

Surprisingly, it was found that compounds of the formula (I) below, the corresponding quaternized and / or protonated compounds, achieve this task, i.e. Both the use of the compounds of the formula (I) and the use of the corresponding protonated compounds as well as the use of the corresponding quaternized compounds and the use of corresponding mixtures in each case achieve the stated object.

mit n = 1 bis 30, insbesondere 1 bis 12, vorzugsweise 2 bis 6, bevorzugt 2 oder 3, besonders bevorzugt 2, a = 2 und b = 1,
wobei die Ether- oder Amin-Bausteine, sofern vorhanden, kumulativ, alternierend, blockweise oder ungeordnet auftreten können,
R₁, R₂ gleich oder ungleich voneinander, ein linearer, verzweigter oder cyclischer, aliphatischer, gesättigter oder ungesättigter Kohlenwasserstoffrest mit 1 bis 30 Kohlenstoffatomen ist, insbesondere 2 bis 12, vorzugsweise 2 bis 6, bevorzugt 2 oder 3 Kohlenstoffatomen, besonders bevorzugt mit 2 Kohlenstoffatomen ist,
R₃ = H oder ein linearer, verzweigter oder cyclischer, aliphatischer oder aromatischer, gesättigter oder ungesättigter, gegebenenfalls mit einem oder mehreren Heteroatomen substituierter oder durch ein oder mehrere Heteroatome unterbrochener Kohlenwasserstoffrest mit 1 bis 30 Kohlenstoffatomen ist,
mit einem oder mehreren Heteroatomen substituierter oder durch ein oder mehrere Heteroatome unterbrochener Kohlenwasserstoffrest mit 1 bis 30 Kohlenstoffatomen ist,

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

with n = 1 to 30, in particular 1 to 12, preferably 2 to 6, preferably 2 or 3, particularly preferably 2, a = 2 and b = 1,
where the ether or amine building blocks, if present, can occur cumulatively, alternately, in blocks or in a disordered manner,
R ₁ , R _{2 are} identical or different from one another, is a linear, branched or cyclic, aliphatic, saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, in particular 2 to 12, preferably 2 to 6, preferably 2 or 3 carbon atoms, particularly preferably having 2 Carbon atoms is
R ₃ = H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted with one or more heteroatoms or interrupted by one or more heteroatoms, hydrocarbon residue with 1 to 30 carbon atoms,
is a hydrocarbon radical having 1 to 30 carbon atoms which is substituted by one or more heteroatoms or interrupted by one or more heteroatoms,

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 (I) used in accordance with the invention, and correspondingly quaternized and / or protonated compounds, and also mixtures of the abovementioned, are suitable as catalysts for the preparation of polyisocyanate reaction products, preferably polyurethanes, in particular polyurethane foams, and can be used both as gels and also catalyze 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 (I) 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, are advantageously low-emission with regard to emissions of nitrogen-containing compounds, hereinafter also called 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 preferably the flexible polyurethane foam, preferably for the production of polyurethanes for use in the automotive industry, in particular in automobile interiors, for example as a headliner, interior lining of doors, punched-out sun visors, steering wheels and / or seating systems, an amine emission, hereinafter also referred to as 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, has, according to the VDA 278 analysis method in the version from October 2011, "thermal desorption analysis of organic emissions to characterize non-metallic automotive materials" (30 minutes at 90 ° C), and / or that the polyurethane system, in particular the flexible polyurethane foam, particularly preferably the polyurethane cold white 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 seating systems, an amine emission, hereinafter also fog emission or fog value according to VDA 278 (Fog: low volatility substances that condense slightly at room temperature and contribute to fogging on the 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 of the formula (I), (II) and / or (III) and / or corresponding polyurethane systems, preferably polyurethane foams, in particular flexible polyurethane foams , particularly preferably flexible polyurethane hot foams, produced using the aforementioned compounds, have a DMF emission of 0 0 ppm and 5 5 ppm, preferably 1 1 ppm, particularly preferably 0,1 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 through 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 measuring method for determining the release of aldehyde, in particular formaldehyde the modified bottle method, whereby, in addition to the commonly used acetylacetone (via photometric detection), 2,4-dinitrophenylhydrazine (2,4-DNP) (detection via HPLC after external calibration) can also be used as the derivatization reagent of aldehydes in addition to formaldehyde and acetaldehyde and to better determine 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 (I) 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 are used conventional catalysts according to the prior art, in particular amines not according to the invention, can be prepared. 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, advantageously, a greater range of variation in the use concentration of the nitrogen-containing compounds according to the invention is possible without negatively influencing 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 according to the prior art for such applications Technology. This means an enormous amount of work for the user.

All reagents known as quaternizing reagents can be used for the possible quaternization of the compounds of the formula (I). 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.

If quaternized, the compounds of the formulas (I) can be quaternized once or more than once. The compounds of the formulas (I) are preferably only quaternized. In the case of simple quaternization, the compounds of the formulas (I) are preferably quaternized on a nitrogen atom which is part of a ring, preferably a pyrrolidine ring.

The compounds of formula (I) 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 (I) 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. Under polyurethane foam (PU foam) is within the scope of the present Invention understood foam that 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 polyurethane cold foams (often also referred to as “high resilience” (HR) foams), viscoelastic polyurethane foams, semi-rigid polyurethane foams and rigid polyurethane foams, as well as foams whose properties lie between these classifications and are used in the automotive industry, are particularly preferred will.

oder

oder

oder

mit m = 1 bis 12, insbesondere 1 bis 6, bevorzugt 2 oder 3, besonders bevorzugt 2, mit o, p, s, t gleich oder ungleich voneinander 1 bis 6, insbesondere 2 oder 3, bevorzugt 2, mit R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆ gleich oder ungleich voneinander H oder ein linearer, verzweigter oder cyclischer, aliphatischer oder aromatischer, gesättigter oder ungesättigter, gegebenenfalls mit einem oder mehreren Heteroatomen substituierter oder durch ein oder mehrere Heteroatome unterbrochener Kohlenwasserstoffrest mit 1 bis 30 Kohlenstoffatomen, wobei R₃ insbesondere ausgewählt ist aus:

According to a preferred embodiment of the invention, in the context of the use according to the invention, at least one nitrogen-containing compound of the formula (I) is used with
R ₃ selected from the following radicals:

or

or

or

with m = 1 to 12, in particular 1 to 6, preferably 2 or 3, particularly preferably 2, with o, p, s, t identical or different from one another 1 to 6, in particular 2 or 3, preferably 2, with R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R _16, identical or different from one another, H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more heteroatoms or by one or more heteroatoms Interrupted hydrocarbon radical with 1 to 30 carbon atoms, where R _{3 is} selected in particular from:

mit q gleich oder ungleich voneinander 2 oder 3 und R₁₇ gleich oder ungleich voneinander ∗-H oder ∗ -CH₃ ist,
und wobei R₃ insbesondere ausgewählt ist aus den folgenden Resten: ∗-H, ∗-CH₃,

mit m = 1 bis 12, insbesondere 1 bis 6, bevorzugt 2 oder 3, besonders bevorzugt 2 und o, p gleich oder ungleich voneinander 1 bis 6, insbesondere 2 oder 3, bevorzugt 2, und wobei

und wobei als stickstoffhaltige Verbindung der Formel (I) insbesondere eine Verbindung eingesetzt wird, die der Formel (II) genügt

Furthermore, it corresponds to a preferred embodiment of the invention if at least one nitrogen-containing compound of the formula (I) is used, where R ₁ , R _2, identical or different from one another, is a hydrocarbon radical having 1 to 30, preferably 2 or 3, carbon atoms, expressed by

where q is the same or different from each other 2 or 3 and R _{17 is the} same or different from each other ∗ -H or ∗ -CH ₃ ,
and wherein R _{3 is} selected in particular from the following radicals: ∗ -H, ∗ -CH ₃ ,

with m = 1 to 12, in particular 1 to 6, preferably 2 or 3, particularly preferably 2 and o, p identical or different from one another 1 to 6, in particular 2 or 3, preferably 2, and wherein

and wherein as the nitrogen-containing compound of formula (I) in particular a compound is used which satisfies formula (II)

mit n, a, b, R₃, Y wie bereits zuvor definiert, worin R₃ besonders bevorzugt

ist.Furthermore, it is particularly preferred in the sense of this invention if at least one nitrogen-containing compound of formula (I), preferably of formula (II), with
n, q and R ₁ , R ₂ , R ₃ as previously defined,
where q is particularly preferably 2, this compound being in particular of the formula (III)

with n, a, b, R ₃ , Y as previously defined, wherein R _{3 is} particularly preferred

is.

A further preferred embodiment of the invention corresponds when at least one nitrogen-containing compound of the formula (I), preferably of the formula (II), in particular of the formula (III) is used, where
a + b = 3 and
a = 2 and b = 1, where the ether and amine building blocks, if present, can occur cumulatively, alternately, in blocks or in a disordered manner.

und/oder

und/oder

eingesetzt wird, mit n, q, R₃, Y wie bereits zuvor definiert,
wobei wiederum

und/oder

bevorzugt eingesetzt werden.Furthermore, it corresponds to a preferred embodiment of the invention if, in the context of the present invention, at least one nitrogen-containing compound of the formula (I), preferably of the formula (II), in particular of the formula (III), is used, where a = 2 and b = 1 a connection in particular

and or

and or

is used, with n, q, R ₃ , Y as previously defined,
being again

and or

are preferably used.

With regard to all of its subjects and their preferred embodiments, the present invention in particular also includes the use of several different nitrogen-containing compounds of the formulas (I), (II) and / or (III) and the use of the corresponding protonated compounds and also the use of corresponding quaternized compounds and the use of corresponding mixtures of all of the aforementioned nitrogen-containing compounds of the formula (I), (II) and / or (III) corresponding protonated and / or quaternized compounds.

The nitrogen-containing compounds of the formula (I), (II) and / or (III) according to the invention described above are in principle accessible via customary processes for the preparation of amines. A good overview for the production and derivatization of amines, for example with ethylene oxide and propylene oxide (alkoxylation), in particular also for the synthesis of pyrrolidine, can be found 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 literature references contained therein.

Preferred synthesis building blocks in the sense of the present invention are, in particular, amines, polyamines, polyols, preferably diols, in particular glycols, amino alcohols, bischloroalkyl ethers and alkyl chlorides bearing amino groups. Polyamines used with preference are, for example, ethylenediamine (EDA) and higher homologs such as diethylenetriamine (DETA), triethylenetetramine (TETA) or tris (2-aminoethyl) amine (tren). Preferred amino alcohols or hydroxyl-bearing amines can be, for example, by reacting ammonia or amines with epoxides (alkoxylation), preferably with ethylene oxide (EO) and / or propylene oxide (PO) and / or by amination of alcohols or polyols, preferably diols , in particular of glycols such as monoethylene glycol (MEG), diethylene glycol (DEG), 1,2-propylene glycol (PG), dipropylene glycol (DPG), with ammonia or amines by known methods, such as, 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. Preferred amino alcohols for the purposes of this invention are, for example, monoethanolamine (MEA), 1- (2-hydroxyethyl) pyrrolidine, diethanolamine (DEOA), triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine. The amino alcohols described exactly here are all commercially available. An example of a bischloroalkylamine including the commercially available bis (2-chloroethyl) amine hydrochloride. Alkyl chlorides bearing amino groups can be obtained, for example, by reacting bischloro-alkyl compounds with an equivalent of an amine, in particular with pyrrolidine (nucleophilic substitution).

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 preferred to use pyrrolidine itself, for example when pyrrolidine is reacted with alkyl halides, in particular with alkyl chlorides (nucleophilic substitution), as described, for example, by Aitken et al. in Tetrahedron, 2002, Vol. 58, 29, pp. 5933-5940 or by Tijskens et al. in Journal of Organic Chemistry, 1995, Vol. 60, 26, pp. 8371-8374, and / or by reacting pyrrolidine with bischloroalkyl ethers, and / or by reacting pyrrolidine with epoxides (alkoxylation) or epoxy-bearing compounds, in particular with ethylene oxide (EO) and / or propylene oxide (PO), such as 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, p. 834 ff, and / or by reacting pyrrolidine with alcohols and / or polyols, preferably diols, in particular glycols, for example in a transition metal-catalyzed version such as Jenner et al. in Journal of Organometallic Chemistry, 373 (1989), 343-352 described. Furthermore, the pyrrolidine function can also be reacted with 1,4-butanediol with primary amines, 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 of polyols, in particular diols, preferably of glycols such as monoethylene glycol ( MEG) and / or amino alcohols, in particular containing a primary hydroxyl function, as described for example in DE 701825C. 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 (I) is described in detail in the example section.

Depending on the desired target structure, the amines thus obtained can also be further derivatized, for example in the sense of an alkoxylation, preferably with ethylene oxide (EO) and / or propylene oxide (PO), as already described above. Optionally, methyl groups can also be inserted into the molecular structure in the sense of N-methylation. Here, for example, the reductive methylation of primary and secondary amines using formaldehyde and formic acid in the sense of Eschweiler-Clarke methylation is known, which is a special case of the Leuckart-Wallach reaction ( R. Leuckart, Ber. 18, 2341 (1885) ., Wallach, Ann. 272, 99 (1892) ) represents. 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, for example 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.

Depending on the desired target compound, the N-methyl groups can also be introduced into the molecular structure, for example by using monomethylamine as the N-methyl building block, for example by transition-metal-catalyzed reaction, for example using Raney metals such as Raney Cobalt or Raney nickel, with compounds bearing hydroxyl groups, such as, for example, diols or amino alcohols. 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, a variety of by-products, 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 and / or amino alcohols.

Depending on the manufacturing process, a nitrogen-containing compound according to formula (I), preferably a nitrogen-containing compound according to formula (II) or (III), in particular a nitrogen-containing compound according to formula (III), depending on the quality of the selected process and the number of corresponding purification steps in technical quality, hereinafter also referred to as technical product mixture, that is to say, for example, intermediate and / or by-products as secondary components and / or further impurities.

This corresponds to the use, wherein at least one nitrogen-containing compound of the formula (I), preferably at least one nitrogen-containing compound of the formula (II) or (III), in particular a nitrogen-containing compound of the formula (III), is used as the technical product mixture, in particular containing impurities, intermediates and / or by-products as further ingredients, in particular comprising 1- (3-aminopropyl) pyrrolidine, 1- (2-aminoethyl) pyrrolidine, 1- (2-hydroxyethyl) pyrrolidine, 1- (3-hydroxypropyl) pyrrolidine, 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol, 1,1 '- (oxybis (ethane-2,1-diyl)) dipyrrolidine, ethylenediamine (EDA), 1,4-butanediol, monoethylene glycol ( MEG), diethylene glycol (DEG), 1,2-propylene glycol (PG), dipropylene glycol (DPG), diethanolamine, triethanolamine, and / or monoethanolamine (MEA), 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, before preferred embodiment of this invention.

1. (a) zumindest eine stickstoffhaltige Verbindung der Formel (I), insbesondere zumindest eine stickstoffhaltige Verbindung nach der Formel (II) oder (III), besonders bevorzugt zumindest eine stickstoffhaltige 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-(2-Hydroxyethyl)pyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20-95 Gew.-%, insbesondere 30-70 Gew.-%,
5. (e) optional 1-(3-Hydroxypropyl)pyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20-95 Gew.-%, insbesondere 30-70 Gew.-%,
6. (f) 2-(2-(Pyrrolidin-1-yl)ethoxy)ethanol, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20-95 Gew.-%, insbesondere 30-70 Gew.-%,
7. (g) 1,1'-(Oxybis(ethan-2,1-diyl))dipyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20-95 Gew.-%, insbesondere 30-70 Gew.-%,
8. (h) optional Ethylendiamin (EDA), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
9. (i) optional 1,4-Butandiol, vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
10. (j) optional Monoethylenglycol (MEG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
11. (k) optional Diethylenglycol (DEG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
12. (l) optional 1,2-Propylenglycol (PG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
13. (m) optional Dipropylenglycol (DPG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
14. (n) optional Diethanolamin, vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
15. (o) optional Triethanolamin, vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%, und/oder
16. (p) optional Monoethanolamin (MEA), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 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 (I), in particular at least one nitrogen-containing compound of the formula (II) or (III), particularly preferably at least one nitrogen-containing 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- (2-hydroxyethyl) pyrrolidine, advantageously in an amount ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
5. (e) optionally 1- (3-hydroxypropyl) pyrrolidine, advantageously in an amount ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
6. (f) 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol, advantageously in an amount ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
7. (g) 1,1 '- (oxybis (ethane-2,1-diyl)) dipyrrolidine, advantageously in an amount ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight ,
8. (h) optionally ethylenediamine (EDA), advantageously in an amount 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
9. (i) optionally 1,4-butanediol, advantageously in an amount of 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
10. (j) optionally monoethylene glycol (MEG), advantageously in an amount of 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
11. (k) optionally diethylene glycol (DEG), advantageously in an amount 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
12. (l) optionally 1,2-propylene glycol (PG), advantageously in an amount ≤ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
13. (m) optionally dipropylene glycol (DPG), advantageously in an amount of 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
14. (n) optionally diethanolamine, advantageously in an amount of 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
15. (o) optionally triethanolamine, advantageously in an amount of 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight, and / or
16. (p) optionally monoethanolamine (MEA), advantageously in an amount ≤ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,

corresponds to a preferred embodiment of this invention.

• mit b), mit c), mit d), mit e), mit f), mit g), mit h), mit i), mit j), mit k), mit l), mit m), mit n), mit o), mit p), mit b) und c), mit b), c) und d), mit b), c), d) und e), mit c) und d), mit c), d) und e), mit d) und b), mit d) und e), mit d), b) und e), mit e) und b), mit e) und c), mit e) und b), mit f) und g), mit b), c), d), e), f) und g), mit b), c), d), e) und f), mit b), c), d), e) und g),
• mit b) und j), mit c) und j), mit d) und j), mit e) und j), mit f) und j), mit g) und j), mit b), c) und j), mit b), c), d) und j), mit b), c), d), e) und j), mit c), d) und j), mit c), d), e) und j), mit d), b) und j), mit d), e) und j), mit d), b), e) und j), mit e), b) und j), mit e), c) und j), mit e), b) und j), mit f) und j), mit g) und j), mit f), g) und j), mit f), g) und j), mit b), c), d), e), f), g) und j), mit b), c), d), e), f) und j), mit b), c), d), e), g) und j),
• mit b) und k), mit c) und k), mit d) und k), mit e) und k), mit f) und k), mit g) und k), mit b), c) und k), mit b), c), d) und k), mit b), c), d), e) und k), mit c), d) und k), mit c), d), e) und k), mit d), b) und k), mit d), e) und k), mit d), b), e) und k), mit e), b) und k), mit e), c) und k), mit e), b) und k), mit f) und k), mit g) und k), mit f), g) und k), mit f), g) und k), mit b), c), d), e), f), g) und k), mit b), c), d), e), f) und k), mit b), c), d), e), g) und k),
• mit b) und m), mit c) und m), mit d) und m), mit e) und m), mit f) und m), mit g) und m), mit b), c) und m), mit b), c), d) und m), mit b), c), d), e) und m), mit c), d) und m), mit c), d), e) und m), mit d), b) und m), mit d), e) und m), mit d), b), e) und m), mit e), b) und m), mit e), c) und m), mit e), b) und m), mit f) und m), mit g) und m), mit f), g) und m), mit f), g) und m), mit b), c), d), e), f), g) und m), mit b), c), d), e), f) und m), mit b), c), d), e), g) und m),
• mit b) und l), mit c) und l), mit d) und l), mit e) und l), mit f) und l), mit g) und l), mit b), c) und l), mit b), c), d) und l), mit b), c), d), e) und l), mit c), d) und l), mit c), d), e) und l), mit d), b) und l), mit d), e) und l), mit d), b), e) und l), mit e), b) und l), mit e), c) und l), mit e), b) und l), mit f) und l), mit g) und l), mit f), g) und l), mit f), g) und l), mit b), c), d), e), f), g) und l), mit b), c), d), e), f) und l) oder in Kombination mit b), c), d), e), g) und l). Hierbei sind besonders bevorzugt Kombinationen mit b), mit c) mit j), mit k), mit l) und mit m).

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 (I), in particular of the formula (II) or (III), preferably of the formula (III) , and / or a corresponding quaternized and / or protonated compound is used in combination:

• with b), with c), with d), with e), with f), with g), with h), with i), with j), with k), with l), with m), with n ), with o), with p), with b) and c), with b), c) and d), with b), c), d) and e), with c) and d), with c) , d) and e), with d) and b), with d) and e), with d), b) and e), with e) and b), with e) and c), with e) and b ), with f) and g), with b), c), d), e), f) and g), with b), c), d), e) and f), with b), c) , d), e) and g),
• with b) and j), with c) and j), with d) and j), with e) and j), with f) and j), with g) and j), with b), c) and j ), with b), c), d) and j), with b), c), d), e) and j), with c), d) and j), with c), d), e) and j), with d), b) and j), with d), e) and j), with d), b), e) and j), with e), b) and j), with e) , c) and j), with e), b) and j), with f) and j), with g) and j), with f), g) and j), with f), g) and j) , with b), c), d), e), f), g) and j), with b), c), d), e), f) and j), with b), c), d ), e), g) and j),
• with b) and k), with c) and k), with d) and k), with e) and k), with f) and k), with g) and k), with b), c) and k ), with b), c), d) and k), with b), c), d), e) and k), with c), d) and k), with c), d), e) and k), with d), b) and k), with d), e) and k), with d), b), e) and k), with e), b) and k), with e) , c) and k), with e), b) and k), with f) and k), with g) and k), with f), g) and k), with f), g) and k) , with b), c), d), e), f), g) and k), with b), c), d), e), f) and k), with b), c), d ), e), g) and k),
• with b) and m), with c) and m), with d) and m), with e) and m), with f) and m), with g) and m), with b), c) and m ), with b), c), d) and m), with b), c), d), e) and m), with c), d) and m), with c), d), e) and m), with d), b) and m), with d), e) and m), with d), b), e) and m), with e), b) and m), with e) , c) and m), with e), b) and m), with f) and m), with g) and m), with f), g) and m), with f), g) and m) , with b), c), d), e), f), g) and m), with b), c), d), e), f) and m), with b), c), d ), e), g) and m),
• with b) and l), with c) and l), with d) and l), with e) and l), with f) and l), with g) and l), with b), c) and l ), with b), c), d) and l), with b), c), d), e) and l), with c), d) and l), with c), d), e) and l), with d), b) and l), with d), e) and l), with d), b), e) and l), with e), b) and l), with e) , c) and l), with e), b) and l), with f) and l), with g) and l), with f), g) and l), with f), g) and l) , with b), c), d), e), f), g) and l), with b), c), d), e), f) and l) or in combination with b), c) , d), e), g) and l). Combinations with b), with c) with j), with k), with l) and with m) are particularly preferred.

The compounds of the formula (I), (II) or (III) 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 Manufacture of polyurethane foams used as catalysts. The compounds of the formula (I) and / or the corresponding quaternized and / or protonated compounds can be used in addition to conventional catalysts or as a replacement for conventional 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 (I), preferably at least one nitrogen-containing compound of the formula (II) or (III), in particular at least one nitrogen-containing compound of the formula (III), has one quaternized and / or protonated compound, or mixtures of the nitrogen-containing compound of formula (I), (II) or (III) with corresponding 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 foam, for example hot, cold, Ester-flexible polyurethane foams or rigid polyurethane foams which select the substances required for this, such as isocyanates, polyols, stabilizers, surfactants, etc., 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 nitrogen-containing compound of the formula (I), preferably at least one nitrogen-containing compound of the formula (II) or (III), in particular at least one nitrogen-containing compound of the formula (III) , and / or a corresponding quaternized and / or protonated compound, at least one polyol component and at least one isocyanate component, optionally in the 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 (I), (II) or (III) to be used according to the invention and / or a correspondingly quaternized and / or protonated compound, in total amount, are preferably in a mass fraction of 0.01 to 20.0 parts (pphp) , preferably 0.01 to 5.00 parts and particularly preferably 0.02 to 3.00 parts based on 100 parts (pphp) of polyol component.

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 (I), preferably at least one nitrogen-containing compound of the formula (II) or (III) in particular at least one nitrogen-containing compound of the formula (III) and / or a corresponding quaternized and / or protonated compound, and furthermore 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 the 4,4'- as well as the 2,4'- and 2,2'-isomers of MDI and higher core products) as well as the binuclear product called "pure MDI" 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 be determined in particular according to the DIN standard DIN 53240: 1971-12.

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 as DMC Called catalysts, represents ( 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 that 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. 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 are preferably used which carry primary hydroxyl groups and are predominantly based on ethylene oxide, in particular with an ethylene oxide block content of> 70%, 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, 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 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. Usually, the polyol combinations used here consist of a low molecular weight “crosslinker” polyol, for example a rigid foam polyol, with high functionality (> 3) and / or a conventional one 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 can be preferred according to the invention that, in addition to the nitrogen-containing compounds according to the invention of the formula (I), (II) and / or (III) and / or corresponding protonated and / or quaternized compounds, additional catalysts are used, individually while the foaming or as a catalyst combination premixed with the nitrogen-containing compounds according to the invention of the formula (I), (II) and / or (III) and / or corresponding protonated and / or quaternized compounds.

For the purposes of this invention, the term “additional catalysts” includes in particular the use of compounds which are not the same as the nitrogen-containing compounds according to the invention of the formula (I), (II) and / or (III) and / or corresponding protonated and / or quaternized compounds , and at the same time are able to catalyze isocyanate reactions, in particular the reactions mentioned below, and / or in the production of polyisocyanate reaction products, in particular in the production of polyurethane systems, particularly preferably in the production of polyurethane foams as catalysts, Catalysts or activators are used.

For the purposes of this invention, the term “premixed catalyst combination”, hereinafter also referred to as catalyst combination, encompasses, in particular, finished mixtures of nitrogen-containing compounds of the formula (I), (II) and / or (III) of corresponding protonated and / or quaternized compounds, Additional catalysts, as well as 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 used as foams before such are present 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 formulas (I) to (III) which catalyze and / or to one of the abovementioned isocyanate reactions Production of polyurethanes, in particular polyurethane foams, can be used.

For the purposes of this invention, the term “nitrogen-containing compounds of the formula (I)” 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 (I), (II) and / or (III) in each case includes the corresponding protonated and / or quaternized compounds and mixtures of these compounds. The expression “at least one nitrogen-containing compound of the formula (I), preferably at least one nitrogen-containing compound of the formula (II) or (III), in particular at least one nitrogen-containing compound of the formula (III)” also includes the use of such compounds in the context of this invention nitrogenous compounds.

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-dimethylaminopropylurea, 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 ( I) to (III) 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 (for example tin organyls) or organometallic or organometallic compounds (for example organotin compounds) ) designated. For the purposes of this invention, the term “organometallic or organometallic salts” includes in particular the use of organometallic or organometallic compounds with a salt character, ie ionic compounds in which either the anion or cation is organometallic in 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” includes in particular the use of metal-containing compounds or metal salts in which neither anion nor cation is an organic compound, e.g. Metal chlorides (e.g. tin (II) chloride), pure or mixed, i.e. containing several metals, metal oxides (e.g. 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 organochemical, that is to say carbon-containing, compounds which have a functional group which can enter into an equilibrium reaction in the sense of an acid-base reaction with water and other protonatable solvents.

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, if appropriate with one or more heteroatoms, preferably with hydroxy groups (* -OH), primary, secondary or tertiary amino groups (* -NH ₂ , * -NHR, * -NR ₂ ) or mercapto groups (* -SH), substituted, or by one or more heteroatoms interrupted 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 interrupted by one or more heteroatoms, monohydric alcohols, 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-bis-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 (II) ricinoleate, zinc (II) acetate, zinc (II) - 2-ethylhexanoate (zinc (II) octoate), 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 can 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 (I) according to the invention, ( II) and / or (III) 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. For the purposes of this invention, catalyst combinations are preferably free of dimethylamine-bearing nitrogen-containing compounds if 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 contain dimethylamine-bearing nitrogen-containing compounds in the catalyst mixture. 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 (I), (II) and / or (III) and / or additional nitrogen-containing catalysts with additional metal-containing catalysts, in particular potassium, zinc and / or or tin catalysts, it may be preferred to store these components separately from one another 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 z.B als vorgemischte Katalysatorkombination, insbesondere wie oben definiert, beinhaltend die vorgenannte Kombination. Insbesondere kann die genannte stickstoffhaltige Verbindung nach Formel (I), (II) oder (III) 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 (I), preferably of the formula (II) or (III), in particular of the formula (III), 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, for example, as a premixed catalyst combination, in particular as defined above, including the aforementioned combination. In particular, the nitrogenous compound of formula (I), (II) or (III) 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 within the scope of the present invention are those compositions in which at least one nitrogen-containing compound of the formula (I), (II) and / or (III) 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) un d e), with b), d) and f), with b), e) and f), or with b), d), e) and f).

The compounds of the formulas (I), (II) and / or (III) 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 premixed catalyst combination 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), diethylhexyl phthalate (DEHP), diisononyl phthalate (DINP), dimethyl phthalate (DMP), diethyl phthalate (DEP), cyclohexanoate (preferably dianoonyl) cyclo.

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), 3-methyl-1,5-pentanediol 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 from 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 (I), (II) and / or (III) 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 is to solvents 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-dichloroethane.

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, 3-methyl-1,5-pentanediol, 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 CI, 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 . These compounds can be prepared 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 Σd der T-Einheiten [SiR³R⁴O] und die mittlere Anzahl Σc der Q-Einheiten [SiR³R³O] pro Molekül jeweils nicht größer als 50, die mittlere Anzahl Σa der D-Einheiten [SiRRO] pro Molekül nicht größer als 2000 und die mittlere Anzahl Σb 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 in the use according to the invention of the nitrogen-containing compounds of the formula (I), (II) and / or (III) and / or the corresponding quaternized and / or protonated compounds in the production of polyurethane foams have in particular 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 Σd of the T units [SiR ³ R ⁴ O] and the average number Σc of the Q units [SiR ³ R ³ O] per molecule of each formula (V) are not greater than 50 , the average number Σa of the D units [SiRRO] per molecule is not greater than 2000 and the average number Σb 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 1 520 870 , described. The font EP 1 520 870 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 Σd of T units and the average number Σc of Q units per molecule are not greater than 20 per molecule of formula (V), the average number Σa of D units per molecule is not greater than 1500 and the average number Σb 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"'withR'"= 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 "is independently a hydrogen radical or an alkyl group with 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 a benzyl group, the group C (O) NH-R 'means, the molar fraction of oxyethylene units, based on the total amount of oxyalkylene units, making up at least 70% of the oxalkylene units, ie x / (x + y)> 0.7 This prerequisite 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 those in the radical R ¹ contained oxalkylene units are exclusively oxyethylene units and the radical R "is not hydrogen.

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 , 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 "is independently 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 a benzyl group, the Group C (O) NH-R 'means that the molar proportion of oxyethylene units, based on the total amount of oxyalkylene units, makes up a maximum of 60% of the oxalkylene units, ie x / (x + y) <0.6.

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 Hydrosilylation inter alia olefins are used whereby R ¹ consists of at least 10 mol%, preferably at least 20 mol%, particularly preferably at least 40 mol% 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 according to the formula (I), (II) and / or (III) corresponding quaternized and / or protonated compounds are preferably used in the production of polyurethane systems, in particular polyurethane foams.

It may 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 (I), (II) and / or (III) as previously defined, and / or one 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 nitrogen-containing compound of the formula (I, (II) and / or (III) and / or a corresponding quaternized and / or protonated compound described above 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-emission”, reference is made to the preceding description and the explanations there, in particular test methods, are referred to With regard to preferred configurations of this subject, reference is also made to the preceding description, in particular to the preferred embodiments mentioned n.

Another object of the invention is the use of the previously described nitrogen-containing compound of the formula (I), (II) and / or (III) and / or a corresponding quaternized and / or protonated compound for the production of low-odor polyurethanes, preferably low-odor Polyurethane foams, especially 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 according to formula (I), (II) and / or (III) 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 nitrogen-containing compound according to formula (I), (II) and / or (III) and / or a corresponding quaternized and / or protonated compound described above for the production of discoloration-minimized polyurethane systems, in particular polyurethane foams , preferably of polyurethanes for use in the automotive industry, in particular in automobile interiors, for example as a headlining, 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 nitrogen-containing compound of formula (I), (II) and or (III) and / or a corresponding quaternized and / or protonated compound described above for the production of polyurethane systems with a wide range of processing, in particular from semi-rigid 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 (I), (II) and / or (III) as previously defined and described, and / or the corresponding quaternized and / or protonated compounds, the composition preferably having at least one isocyanate component, and wherein the nitrogen-containing compound of the formula (I), (II) and / or (III) is preferably present as a technical product mixture, as described above,
and wherein the composition preferably comprises additional amine catalysts different from formula (I), (II) and / or (III).

The molar ratio of the total amount of nitrogen-containing catalysts comprising the nitrogen-containing compounds of the formula (I), (II) and / or (III) 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 (I), (II) and / or (III) corresponding quaternized and / or protonated compounds, in total in a mass fraction of 0.01 to 20.0 parts (pphp), preferred 0.01 to 5.00 parts and particularly preferably 0.02 to 3.00 parts based on 100 parts (pphp) of polyol component can be used.

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 being 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 (I), (II) and / or (III) and / or the corresponding quaternized and / or protonated compounds according to the invention.

1. (a) zumindest eine stickstoffhaltige Verbindung der Formel (I), insbesondere zumindest eine stickstoffhaltige Verbindung nach der Formel (II) oder (III), besonders bevorzugt zumindest eine stickstoffhaltige 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-(2-Hydroxyethyl)pyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20-95 Gew.-%, insbesondere 30-70 Gew.-%,
5. (e) optional 1-(3-Hydroxypropyl)pyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20-95 Gew.-%, insbesondere 30-70 Gew.-%,
6. (f) 2-(2-(Pyrrolidin-1-yl)ethoxy)ethanol, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20-95 Gew.-%, insbesondere 30-70 Gew.-%,
7. (g) 1,1'-(Oxybis(ethan-2,1-diyl))dipyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20-95 Gew.-%, insbesondere 30-70 Gew.-%,
8. (h) optional Ethylendiamin (EDA), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
9. (i) optional 1,4-Butandiol, vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
10. (j) optional Monoethylenglycol (MEG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
11. (k) optional Diethylenglycol (DEG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
12. (l) optional 1,2-Propylenglycol (PG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
13. (m) optional Dipropylenglycol (DPG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
14. (n) optional Diethanolamin, vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
15. (o) optional Triethanolamin, vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
16. (p) optional Monoethanolamin (MEA), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%, und/oder
17. (q) 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), 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 (I), in particular at least one nitrogen-containing compound of the formula (II) or (III), particularly preferably at least one nitrogen-containing 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- (2-hydroxyethyl) pyrrolidine, advantageously in an amount ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
5. (e) optionally 1- (3-hydroxypropyl) pyrrolidine, advantageously in an amount ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
6. (f) 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol, advantageously in an amount ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
7. (g) 1,1 '- (oxybis (ethane-2,1-diyl)) dipyrrolidine, advantageously in an amount ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight ,
8. (h) optionally ethylenediamine (EDA), advantageously in an amount 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
9. (i) optionally 1,4-butanediol, advantageously in an amount of 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
10. (j) optionally monoethylene glycol (MEG), advantageously in an amount of 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
11. (k) optionally diethylene glycol (DEG), advantageously in an amount 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
12. (l) optionally 1,2-propylene glycol (PG), advantageously in an amount ≤ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
13. (m) optionally dipropylene glycol (DPG), advantageously in an amount of 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
14. (n) optionally diethanolamine, advantageously in an amount of 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
15. (o) optionally triethanolamine, advantageously in an amount of 95 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
16. (p) optionally monoethanolamine (MEA), advantageously in an amount ≤ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight, and / or
17. (q) 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), 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 ≤ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight.

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• mit b) und l), mit c) und l), mit d) und l), mit e) und l), mit f) und l), mit g) und l), mit b), c) und l), mit b), c), d) und l), mit b), c), d), e) und l), mit c), d) und l), mit c), d), e) und l), mit d), b) und l), mit d), e) und l), mit d), b), e) und l), mit e), b) und l), mit e), c) und l), mit e), b) und l), mit f) und l), mit g) und l), mit f), g) und l), mit f), g) und l), mit b), c), d), e), f), g) und l), mit b), c), d), e), f) und l), mit b), c), d), e), g) und l),
• mit q) und j), mit a), b), c), d), e), f), g), q) und j), mit a), q) und j), mit b), q) und j), mit c), q) und j), mit d), q) und j), mit e), q) und j), mit f), q) und j), mit g), q) und j), mit f), g) q), und j), mit b), d), q) und j), mit c), d), q) und j), mit c), f), g), q) und j), mit b), f), g), q) und j), mit c), g), q) und j), mit b), g), q) und j)
• mit q) und k), mit a), b), c), d), e), f), g), q) und k), mit a), q) und k), mit b), q) und k), mit c), q) und k), mit d), q) und k), mit e), q) und k), mit f), q) und k), mit g), q) und k), mit f), g) q), und k), mit b), d), q) und k), mit c), d), q) und k), mit c), f), g), q) und k), mit b), f), g), q) und k), mit c), g), q) und k), mit b), g), q) und k)
• mit q) und l), mit a), b), c), d), e), f), g), q) und l), mit a), q) und l), mit b), q) und l), mit c), q) und l), mit d), q) und l), mit e), q) und l), mit f), q) und l), mit g), q) und l), mit f), g) q), und l), mit b), d), q) und l), mit c), d), q) und l), mit c), f), g), q) und l), mit b), f), g), q) und l), mit c), g), q) und l), mit b), g), q) und l)
• mit q) und m), mit a), b), c), d), e), f), g), q) und m), mit a), q) und m), mit b), q) und m), mit c), q) und m), mit d), q) und m), mit e), q) und m), mit f), q) und m), mit g), q) und m), mit f), g) q), und m), mit b), d), q) und m), mit c), d), q) und m), mit c), f), g), q) und m), mit b), f), g), q) und m), mit c), g), q) und m) oder in Kombination mit b), g), q) und m).

For the purposes of the aforementioned subject of the present invention, particularly preferred compositions are those compositions in which at least one nitrogen-containing compound of the formula (I), preferably at least one nitrogen-containing compound of the formula (II) or (III), in particular at least one nitrogen-containing compound of the formula (III) and / or a corresponding quaternized and / or protonated compound is used in combination:

• with b), with c), with d), with e), with f), with g), with h), with i), with j), with k), with l), with m), with n ), with o), with p), with b) and c), with b), c) and d), with b), c), d) and e), with c) and d), with c) , d) and e), with d) and b), with d) and e), with d), b) and e), with e) and b), with e) and c), with e) and b ), with f) and g), with b), c), d), e), f) and g), with b), c), d), e) and f), with b), c) , d), e) and g),
• with q), with a), b), c), d), e), f), g) and q), with a) and q), with b) and q), with c) and q), with d) and q), with e) and q), with f) and q), with g) and q), with f), g) and q), with b), d) and q), with c ), d) and q), with c), f), g) and q), with b), f), g) and q), with c), g) and q), with b), g) and q)
• with b) and j), with c) and j), with d) and j), with e) and j), with f) and j), with g) and j), with b), c) and j ), with b), c), d) and j), with b), c), d), e) and j), with c), d) and j), with c), d), e) and j), with d), b) and j), with d), e) and j), with d), b), e) and j), with e), b) and j), with e) , c) and j), with e), b) and j), with f) and j), with g) and j), with f), g) and j), with f), g) and j) , with b), c), d), e), f), g) and j), with b), c), d), e), f) and j), with b), c), d ), e), g) and j),
• with b) and k), with c) and k), with d) and k), with e) and k), with f) and k), with g) and k), with b), c) and k ), with b), c), d) and k), with b), c), d), e) and k), with c), d) and k), with c), d), e) and k), with d), b) and k), with d), e) and k), with d), b), e) and k), with e), b) and k), with e) , c) and k), with e), b) and k), with f) and k), with g) and k), with f), g) and k), with f), g) and k) , with b), c), d), e), f), g) and k), with b), c), d), e), f) and k), with b), c), d ), e), g) and k),
• with b) and m), with c) and m), with d) and m), with e) and m), with f) and m), with g) and m), with b), c) and m ), with b), c), d) and m), with b), c), d), e) and m), with c), d) and m), with c), d), e) and m), with d), b) and m), with d), e) and m), with d), b), e) and m), with e), b) and m), with e) , c) and m), with e), b) and m), with f) and m), with g) and m), with f), g) and m), with f), g) and m) , with b), c), d), e), f), g) and m), with b), c), d), e), f) and m), with b), c), d ), e), g) and m),
• with b) and l), with c) and l), with d) and l), with e) and l), with f) and l), with g) and l), with b), c) and l ), with b), c), d) and l), with b), c), d), e) and l), with c), d) and l), with c), d), e) and l), with d), b) and l), with d), e) and l), with d), b), e) and l), with e), b) and l), with e) , c) and l), with e), b) and l), with f) and l), with g) and l), with f), g) and l), with f), g) and l) , with b), c), d), e), f), g) and l), with b), c), d), e), f) and l), with b), c), d ), e), g) and l),
• with q) and j), with a), b), c), d), e), f), g), q) and j), with a), q) and j), with b), q ) and j), with c), q) and j), with d), q) and j), with e), q) and j), with f), q) and j), with g), q ) and j), with f), g) q), and j), with b), d), q) and j), with c), d), q) and j), with c), f) , g), q) and j), with b), f), g), q) and j), with c), g), q) and j), with b), g), q) and j )
• with q) and k), with a), b), c), d), e), f), g), q) and k), with a), q) and k), with b), q ) and k), with c), q) and k), with d), q) and k), with e), q) and k), with f), q) and k), with g), q ) and k), with f), g) q), and k), with b), d), q) and k), with c), d), q) and k), with c), f) , g), q) and k), with b), f), g), q) and k), with c), g), q) and k), with b), g), q) and k )
• with q) and l), with a), b), c), d), e), f), g), q) and l), with a), q) and l), with b), q ) and l), with c), q) and l), with d), q) and l), with e), q) and l), with f), q) and l), with g), q ) and l), with f), g) q), and l), with b), d), q) and l), with c), d), q) and l), with c), f) , g), q) and l), with b), f), g), q) and l), with c), g), q) and l), with b), g), q) and l )
• with q) and m), with a), b), c), d), e), f), g), q) and m), with a), q) and m), with b), q ) and m), with c), q) and m), with d), q) and m), with e), q) and m), with f), q) and m), with g), q ) and m), with f), g) q), and m), with b), d), q) and m), with c), d), q) and m), with c), f) , g), q) and m), with b), f), g), q) and m), with c), g), q) and m) or in combination with b), g), q) and m).

A polyurethane system is made possible, which is obtainable through use as described above.

These polyurethane systems 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, in particular polyurethane foam, is preferably characterized 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 of nitrogenous ones Compounds of the formula (I), (II) and / or (III) 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 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

The use of polyurethane systems, in particular polyurethane foams, as described above, is made possible 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 nitrogenous compounds

Chemikalie CAS Lieferant 1,2-Bis(2-chloroethoxy)-ethan, >97% 112-26-5 Sigma-Aldrich Chemie GmbH Pyrrolidin, > 99% 123-75-1 Sigma-Aldrich Chemie GmbH Synthesis example 1: Preparation of a compound according to formula (III), using the example of the compound according to formula (Illa)

chemical CAS supplier 1,2-bis (2-chloroethoxy) ethane,> 97% 112-26-5 Sigma-Aldrich Chemie GmbH Pyrrolidine,> 99% 123-75-1 Sigma-Aldrich Chemie GmbH

35.0 g (0.187 mol) of 1,2-bis (2-chloroethoxy) ethane were placed in a 250 ml four-necked flask equipped with a KPG stirrer, reflux condenser, temperature measuring probe and inert gas feed. After the reaction apparatus had been rendered inert by means of nitrogen, the mixture was heated to 50 ° C. At a reaction temperature of 50 ° C, the addition of 60.0 g (0.84 mol) of pyrrolidine was started using a dropping funnel. The metering was carried out within 30 minutes, the exothermic nature of the reaction causing the temperature to rise to 73 ° C. After the metering had ended, the mixture was heated to 90 ° C. and the reaction temperature was kept for 5 hours. After the reaction time was complete, the reaction mixture was allowed to cool to room temperature. The next day, it was found that by-products formed by quaternization had crystallized out in the reaction mixture. In order to separate them, the mixture was heated to 60 ° C. and 150 ml of heptane were added. It was then filtered off through a folded filter and the solvent and volatile constituents were distilled off on a rotary evaporator at 105 ° C. and <1 mbar. In this way, 42.11 g of a clear, slightly yellowish product according to formula (IIIa) could be obtained. The 13 C-NMR analysis met expectations and confirmed product formation.

Chemikalie CAS Lieferant 2-[2-(2-Chloroethoxy)ethoxy]ethanol, 96% 5197 -62-6 Sigma-Aldrich Chemie GmbH Pyrrolidin, > 99% 123-75-1 Sigma-Aldrich Chemie GmbH Kaliumcarbonat, wasserfrei 584-08-7 Sigma-Aldrich Chemie GmbH Acetonitril, wasserfrei 99,8 % 75-05-8 Sigma-Aldrich Chemie GmbH Ethylacetat, wasserfrei 99 % 141-78-6 Sigma-Aldrich Chemie GmbH Diethylether, wasserfrei 99 % 60-29-7 Sigma-Aldrich Chemie GmbH Synthesis example 2: Preparation of a compound according to formula (III), using the example of the compound according to formula (IIIb)

chemical CAS supplier 2- [2- (2-chloroethoxy) ethoxy] ethanol, 96% 5197 -62-6 Sigma-Aldrich Chemie GmbH Pyrrolidine,> 99% 123-75-1 Sigma-Aldrich Chemie GmbH Potassium carbonate, anhydrous 584-08-7 Sigma-Aldrich Chemie GmbH Acetonitrile, anhydrous 99.8% 75-05-8 Sigma-Aldrich Chemie GmbH Ethyl acetate, anhydrous 99% 141-78-6 Sigma-Aldrich Chemie GmbH Diethyl ether, anhydrous 99% 60-29-7 Sigma-Aldrich Chemie GmbH

The technical teaching of EP 1945222 B1 (Intermediate 11) following, an amount of 18.67 g (263 mmol) pyrrolidine and 375 ml acetonitrile were placed in an apparatus consisting of a 1 L multi-necked flask equipped with KPG stirrer, reflux condenser, dropping funnel and temperature sensor with inert gas feed. The mixture was heated to reflux of the solvent and a solution of 42.16 g (250 mmol) of 2- [2- (2-chloroethoxy) ethoxy] ethanol in 125 ml of acetonitrile was added dropwise. After a reaction time of 24 hours, the reaction mixture was allowed to cool to room temperature and filtered through a pleated filter, washing with only a little ethyl acetate. The filtrate was then sharply concentrated on a rotary evaporator, the residue was taken up in a little diethyl ether, provided with filter aid (Celite ^© ) and filtered again. The filtrate was again sharply concentrated on a rotary evaporator so that 41.16 g (81% of theory) of a slightly yellow oil could be obtained as a product according to the formula (Illb). Analysis by 1H and 13C NMR spectroscopy was in line with expectations and confirmed product formation.

CAS Lieferant Chemikalie 1-(2-Aminoethyl)pyrrolidin 7154-73-6 ABCR Ethylenglykol, 99,8 % (wasserfrei) 107-21-1 Sigma-Aldrich Chemie GmbH Ruthenium(III)chlorid-Trihydrat, techn. 13815-94-6 Sigma-Aldrich Chemie GmbH Triphenylphosphin, 99% 603-35-0 Sigma-Aldrich Chemie GmbH Synthesis example 3: Preparation of a compound according to formula (III), using the example of the compound according to formula (IIIc)

CAS supplier chemical 1- (2-aminoethyl) pyrrolidine 7154-73-6 ABCR Ethylene glycol, 99.8% (anhydrous) 107-21-1 Sigma-Aldrich Chemie GmbH Ruthenium (III) chloride trihydrate, techn. 13815-94-6 Sigma-Aldrich Chemie GmbH Triphenylphosphine, 99% 603-35-0 Sigma-Aldrich Chemie GmbH

The technical teaching of G. Jenner et all. (Journal of Organometallic Chemistry, 373, 1989, 343-352 ) a quantity of 159.57 g (1.4 mol) of 1- (2-aminoethyl) pyrrolidine, 37.24 g (in a 500 ml laboratory autoclave equipped with a stirrer, a heatable jacket, pressure transducer and temperature probe and inert gas feed) 600 mmol) of ethylene glycol, 1.17 g (4.5 mmol) of ruthenium (III) chloride trihydrate (0.75 mol% based on diol) and 3.54 g (13.5 mmol) of triphenylphosphine. The autoclave was sealed, rendered inert with nitrogen and the jacket was heated to 190 ° C. with a thermal oil, an increase in pressure being observed. The reaction temperature was then kept under stirring for 9 hours. When the reaction time had ended, the mixture was allowed to cool to room temperature and the reaction mixture was examined by gas chromatography. In addition to unreacted 1- (2-aminoethyl) pyrrolidine, the analysis showed a small proportion of the mono-attached product and the product according to formula (IIIc). The crude reaction mixture was provided with a little filter aid (Celite ^© ), filtered through a pleated filter and then subjected to fine distillation. In a clear fraction (1 mbar / 85 - 90 ° C), 23.2 g of the mono-deposited product could be obtained in a purity of 97.2% and in a likewise clear, slightly yellowish and oil-like viscous fraction at room temperature (0.5 - 0.8 mbar / 128 - 138 ° C) 61.3 g of the di-deposited product according to formula (IIIc) can be obtained. The NMR spectroscopic as well as the GC or GC / MS analyzes confirmed the product formation.

Chemikalie CAS Lieferant 1-(2-Aminoethyl)pyrrolidin 7154-73-6 ABCR N-Methyldiethanolamin ≥99%, 105-59-9 Sigma-Aldrich Chemie GmbH Ruthenium(III)chlorid-Trihydrat, techn. 13815-94-6 Sigma-Aldrich Chemie GmbH Triphenylphosphin, 99% 603-35-0 Sigma-Aldrich Chemie GmbH Synthesis example 4: Preparation of a compound according to formula (III), using the example of the compound according to formula (IIId) and (IIIe)

chemical CAS supplier 1- (2-aminoethyl) pyrrolidine 7154-73-6 ABCR N-methyldiethanolamine ≥99%, 105-59-9 Sigma-Aldrich Chemie GmbH Ruthenium (III) chloride trihydrate, techn. 13815-94-6 Sigma-Aldrich Chemie GmbH Triphenylphosphine, 99% 603-35-0 Sigma-Aldrich Chemie GmbH

The technical teaching of G. Jenner et all. (Journal of Organometallic Chemistry, 373, 1989, 343-352 ) In a 500 ml laboratory autoclave equipped with a stirrer, a heated jacket, pressure transducer and temperature probe and an inert gas feed, an amount of 113.98 g (1 mol) of 1- (2-aminoethyl) pyrrolidine, 71.5 g (600 mmol ) N-methyldiethanolamine, 1.17 g (4.5 mmol) of ruthenium (III) chloride trihydrate (0.75 mol% based on diol) and 3.54 g (13.5 mmol) of triphenylphosphine. The autoclave was sealed, rendered inert with nitrogen and the jacket was heated to 190 ° C. with a thermal oil, an increase in pressure being observed. The reaction temperature was then kept under stirring for 9 hours. When the reaction time had ended, the mixture was allowed to cool to room temperature and the reaction mixture was examined by gas chromatography. In addition to unreacted 1- (2-aminoethyl) pyrrolidine, the analysis showed both a mono-attached product and the diane-attached product. The crude reaction mixture was provided with a little filter aid (Celite ^© ), filtered through a pleated filter and then subjected to fine distillation using a short-path evaporator. In a slightly yellowish, but clear fraction at 0.8-1 mbar and a jacket temperature of 100 ° C., a quantity of 44.2 g of the mono-deposited product according to the formula (Illd) could be obtained in a purity of 95.5 % be won. Furthermore, in a likewise clear, but clearly orange-colored and viscous fraction at room temperature, at a pressure of 0.05 - 0.09 mbar and a jacket temperature of 160 ° C., a quantity of 51.3 g of the di-deposited product according to the formula could (IIIe) can be obtained. The NMR spectroscopic as well as the GC or GC / MS analyzes confirmed the product formation.

Chemikalie CAS Lieferant Pyrrolidin, 99 % 123-75-1 ABCR Ethylenoxid, 3 M in THF 75-21-8 Sigma-Aldrich Chemie GmbH Synthesis example 5: Preparation of 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol

chemical CAS supplier Pyrrolidine, 99% 123-75-1 ABCR Ethylene oxide, 3 M in THF 75-21-8 Sigma-Aldrich Chemie GmbH

In a 1000 ml laboratory autoclave equipped with a stirrer, a heatable jacket, pressure transducer and temperature probe as well as an inert gas supply, 333.4 ml of a 3 molar solution of ethylene oxide in THF (equivalent to 1 mol Ethylene oxide) and another 35.56 g (0.5 mol) of pyrrolidine were added. The autoclave which had previously been flushed with nitrogen was then heated to 100 ° C. over the jacket with a thermal oil, an increase in pressure being observed. The reaction temperature was then kept under stirring for 6 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 solvent was removed on a rotary evaporator at a bath temperature of 50 ° C in a membrane pump vacuum for several hours. The crude reaction mixture was then examined by gas chromatography, in addition to 15.1% of unreacted pyrrolidine, 42.9% of the desired mono-ethoxylated pyrrolidine and 26.7% of the di-ethoxylated pyrrolidine and 10.7% of tri-ethoxylated pyrrolidine and a total of 4 , 6% of other by-products or solvent residues were found. A fine distillation was then carried out to isolate the desired mono- and di-ethoxylated pyrrolidine. At a pressure of 16 mbar and a head temperature of 75 - 78 ° C in a clear fraction, the mono-ethoxylated product in a GC purity of 96.9% and at a pressure of 3 mbar and a head temperature of 90 - 95 ° C in a likewise clear fraction, the diethoxylated target product 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol can be obtained in a GC purity of 94.2%. The NMR spectroscopic as well as the GC or GC / MS analyzes confirmed the product formation.

Chemikalie CAS Lieferant 2-(2-(pyrrolidin-1-yl)ethoxy)ethanol 4076-32-8 2-Methylamino-ethanol, >98% 109-83-1 Sigma-Aldrich Chemie GmbH Ruthenium(III)chlorid-Trihydrat, techn. 13815-94-6 Sigma-Aldrich Chemie GmbH Triphenylphosphin, 99% 603-35-0 Sigma-Aldrich Chemie GmbH Synthesis example 6: Preparation of a compound according to formula (III), using the example of the compound according to formula (IIIf)

chemical CAS supplier 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol 4076-32-8 2-methylaminoethanol,> 98% 109-83-1 Sigma-Aldrich Chemie GmbH Ruthenium (III) chloride trihydrate, techn. 13815-94-6 Sigma-Aldrich Chemie GmbH Triphenylphosphine, 99% 603-35-0 Sigma-Aldrich Chemie GmbH

The technical teaching of G. Jenner et al. (Journal of Organometallic Chemistry, 373, 1989, 343-352 ) a quantity of 159.23 g (1 mol) of 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol was added to a 500 ml laboratory autoclave equipped with a stirring device, a heated jacket, pressure transducer and temperature probe as well as an inert gas feed, 75.11 g (1 mol) of 2-methylaminoethanol, 981 mg (3.75 mmol) of ruthenium (III) chloride trihydrate (0.375 mol% based on 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol) and 2.95 g (11.25 mmol) triphenylphosphine. The autoclave was sealed, rendered inert with nitrogen and the jacket was heated to 190 ° C. with a thermal oil, an increase in pressure being observed. The reaction temperature was then kept under stirring for 9 hours. When the reaction time had ended, the mixture was allowed to cool to room temperature and the reaction mixture was examined by gas chromatography. In addition to unreacted 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol, the GC and GC / MS analysis showed 38% of the desired product, but also significant amounts of by-products from the intermolecular reaction of the 2nd -Methylaminoethanols. The crude reaction mixture was therefore provided with ethanol and a little filter aid (Celite ^© ), filtered through a pleated filter and the solvent was then removed on a rotary evaporator. A fractional fine distillation was then carried out so that the desired product according to formula (IIIf) could be obtained in a yield of 23%. The NMR spectroscopic as well as the GC or GC / MS analyzes confirmed the desired product formation.

Chemikalie CAS Lieferant 2-(2-(pyrrolidin-1-yl)ethoxy)ethanol 4076-32-8 Methylamin, 2 M in THF 74-89-5 Sigma-Aldrich Chemie GmbH Ruthenium(III)chlorid-Trihydrat, techn. 13815-94-6 Sigma-Aldrich Chemie GmbH Triphenylphosphin, 99% 603-35-0 Sigma-Aldrich Chemie GmbH Synthesis example 7: Preparation of a compound according to formula (III), using the example of the compound according to formula (IIIg), according to the invention

chemical CAS supplier 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol 4076-32-8 Methylamine, 2 M in THF 74-89-5 Sigma-Aldrich Chemie GmbH Ruthenium (III) chloride trihydrate, techn. 13815-94-6 Sigma-Aldrich Chemie GmbH Triphenylphosphine, 99% 603-35-0 Sigma-Aldrich Chemie GmbH

The technical teaching of G. Jenner et al. (Journal of Organometallic Chemistry, 373, 1989, 343-352 ) a quantity of 79.62 g (0.5 mol) of 2- (2- (pyrrolidin-1-yl) ethoxy) was subsequently placed in a 500 ml laboratory autoclave equipped with a stirring device, a heatable jacket, pressure transducer and temperature probe as well as an inert gas feed line. ethanol, 250 ml (corresponding to 0.5 mol) of a solution of methylamine (2 M in THF), 491 mg (1.875 mmol) ruthenium (III) chloride trihydrate (0.375 mol% based on 2- (2- (pyrrolidine -1-yl) ethoxy) ethanol) and 1.48 g (5.7 mmol) triphenylphosphine. The autoclave was closed, rendered inert with nitrogen and the jacket was heated to 130 ° C. with a thermal oil, an increase in pressure being observed. The reaction temperature was then kept under stirring for 12 hours. When the reaction time had ended, the mixture was allowed to cool to room temperature and the reaction mixture was examined by gas chromatography. The GC and GC / MS analysis showed significant proportions of unreacted 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol, but also proportions of the desired product of 23%, in addition to various other by-products. The crude reaction mixture was therefore provided with ethanol and a little filter aid (Celite ^© ), filtered through a pleated filter and the solvent was then removed on a rotary evaporator. The residue was then subjected to a fractional fine distillation, the desired product according to the formula (IIIg) being able to be obtained in one fraction with a yield of 12%. The GC purity of this fraction was 94.3% and the NMR spectroscopic as well as the GC / MS analyzes confirmed the desired product formation.

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 0.80 or 1.50 parts (see table 2) 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 compound of the formula (III) according to the invention are summarized in Table 2. N, N-dimethylcyclohexylamine (DMCHA), dimethylaminoethoxyethanol (DMEE), pentamethyldiethylene triamine (PMDETA) and bis (2-dimethylaminoethyl ether) (BDE) 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 Gel time Rise time Tack free time [s] ³⁾ [s] ³⁾ [s] ³⁾ [s] ³⁾ DMCHA ¹⁾ 40 143 305 329 DMEE ¹⁾ 31 158 274 308 PMDETA ²⁾ 15 129 205 234 BDE ²⁾ 8th 121 179 196 FORMULA (IIIa *) ¹⁾ 20th 160 235 325 FORMULA (IIIb *) ¹⁾ 39 176 277 290 FORMULA (IIIc *) ¹⁾ 62 282 435 510 FORMULA (IId *) ¹⁾ 53 214 378 432 FORMULA (IIIe *) ¹⁾ 55 219 390 420 FORMULA (IIIf *) ¹⁾ 20th 136 203 218 FORMULA (IIIg *) ^{1) **} 17th 128 227 278 ¹⁾ 1.50 parts of catalyst used. ²⁾ 0.80 parts of catalyst used. ³⁾ Time information in seconds [s]. * each obtained according to the aforementioned synthesis examples ** according to the invention

As can be seen from Table 2, the nitrogen-containing compounds of the formula (III) show moderate to very good catalytic activity in the rigid foam. In particular, the nitrogen-containing compounds of the formula (IIIa), (IIId) and (IIIg), according to the invention, have a high activity precisely at the beginning of the foaming, which can be seen from the values for the cream time. The further reaction profile suggests that, similar to PMDETA and BDE, these are catalysts that preferentially catalyze the blowing reaction. The remaining nitrogen-containing compounds of the formula (III) are in the DMEE range in terms of their catalytic profile, the nitrogen-containing compound of the formula (IIIb) in particular here showing a slight improvement in terms of the final curing.

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 rising 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 19091 B-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 19091 B-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 the isocyanate (TDI) had been added, the reaction mixture was stirred at 2500 rpm for 7 s and immediately transferred to a paper-lined box (27 cm × 27 cm base area and 27 cm high) 2. 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 compound of the formula (III) according to the invention and the physical properties of the resulting flexible block foams are summarized in Table 10. As comparative catalysts of the prior art were triethylenediamine, 33% solution in dipropylene glycol Gew.ige (TEGOAMIN ^® 33, available from Evonik Industries), N, N-dimethylethanolamine (DMEA TEGOAMIN ^®, available from Evonik Industries), bis (2-dimethylaminoethyl ether), 70% by weight solution in dipropylene glycol (TEGOAMIN ^® BDE, available from Evonik Industries) and N, N, N'-trimethyl-N '- (2-hydroxyethyl) bis (2-aminoethyl ) ether (Jeffcat ^® ZF-10, available from Huntsman). 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 ^® 33 120 0.1 28.6 31.6 24th 4.4 TEGOAMIN ^® DMEA 137 0.1 28.0 31.2 17th 3.8 TEGOAMIN ^® BDE 93 0.6 29.0 30.9 12 3.5 Jeffcat ^® ZF-10 108 0.6 29.0 30.7 10th 3.5 FORMULA (IIIa *) 120 0.3 28.7 31.2 18th 3.7 FORMULA (IIIb *) 150 0.0 27.5 31.6 36 4.2 FORMULA (IIIc *) 133 0.2 28.0 31.3 20th 4.0 FORMULA (IIId *) 119 0.4 28.6 31.0 16 3.9 FORMULA (IIIe *) 128 0.2 28.4 31.4 21st 3.9 FORMULA (IIIf *) 112 0.4 28.8 31.0 15 3.7 FORMULA (IIIg *) ** 115 0.3 28.7 31.2 18th 3.9 ¹⁾ = (dynamic pressure in mm water column). * each obtained according to the aforementioned synthesis examples ** according to the invention

As can be seen from Table 10, some of the compounds of the formula (III) have high catalytic activity in the flexible flexible foam. In the formulation chosen, it was possible to produce sufficiently open-cell soft foams with all compounds of the formula (III). With respect to the activity and selectivity of the highly active nitrogen-containing compounds according to formula (III) are similarly classified as Jeffcat ZF-10 ^®, as a catalyst that favors the blowing reaction catalyze. The nitrogen-containing compounds of the formula (IIIb), (IIIc) and (IIIe) have a similar performance to TEGOAMIN ^® DMEA. The compounds of the formulas (IIIa) and (IIId) are comparable to TEGOAMIN ^® 33 with regard to the rise time. However, the physical measurement values obtained indicate that these are catalysts which have balanced selectivity, but the driving forces Prefer reaction slightly.

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, a defined foam cube (7 cm × 7 cm × 7 cm) was cut out of the resulting foam block, 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 Amine PK _total ¹⁾ [µg / m ³ ] PK _amine ¹⁾ [µg / m ³ ] TEGOAMIN ^® 33 96 68 TEGOAMIN ^® DMEA 28 <10 TEGOAMIN ^® BDE 316 289 Jeffcat ZF-10 <20 <10 FORMULA (IIIa *) <20 <10 FORMULA (IIIb *) <20 <10 FORMULA (IIIc *) <20 <10 FORMULA (IIId *) <20 <10 FORMULA (IIIe *) <20 <10 FORMULA (IIIf *) <20 <10 FORMULA (IIIg *) ** <20 <10 ¹⁾ PK _tot = total emission; PK _amine = amine emissions of all volatile organic compounds in the test chamber test. * each obtained according to the aforementioned synthesis examples ** according to the invention

Table 12 shows that the flexible block foams obtained using the nitrogen-containing compounds of the formula (III) have lower amine emissions after the test chamber test, as described above, than using conventional catalysts such as TEGOAMIN ^® BDE or TEGOAMIN ^® 33 In the formulation used here, as for TEGOAMIN ^® DMEA and Jeffcat ^® ZF-10, it was even possible to obtain low amine emissions <10 µg / m ³ , in most cases the foams obtained were even free of such emissions. With regard to the amine emissions according to VDA 278, as described above, a partial reduction of the amine emissions was observed with a corresponding catalyst exchange of TEGOAMIN ^® BDE or TEGOAMIN ^® 33.

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⁾ Polyol 2: 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 compound according to the formula (III) 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, N-dimethylethanolamine (TEGOAMIN ^® DMEA, available from Evonik Industries), were used as comparative catalysts according to the prior art. Bis (2-dimethylaminoethyl ether), 70% by weight solution in dipropylene glycol (TEGOAMIN ^® BDE, available from Evonik Industries) and N, N, N'-trimethyl-N '- (2-hydroxyethyl) to (2- aminoethyl) ether (Jeffcat ZF-10 ^®, are used obtainable from 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 97 189 31.3 0.3 10.5 TEGOAMIN ^® BDE 55 78 33.5 1.8 10.0 Jeffcat ZF-10 80 119 32.8 0.8 10.0 TEGOAMIN ^® DMEA 154 263 26.3 collapse collapse FORMULA (IIIa *) 97 206 30.6 0.0 10.0-10.5 FORMULA (IIIb *) 170 298 25.8 collapse collapse FORMULA (IIIc *) 156 256 26.8 -0.1 9.0 FORMULA (IIId *) 138 231 27.8 0.2 9.5 FORMULA (IIIe *) 147 248 27.6 0.2 9.0 FORMULA (IIIf *) 75 125 32.8 0.7 10.0 FORMULA (IIIg *) ** 71 98 33.0 1.1 10.0 ¹⁾ Number of cells = number of cells per cm [cm ^-1 ]. * each obtained according to the aforementioned synthesis examples ** according to the invention

Table 14 again shows that the compounds of the formula (III) partly have high catalytic activity in cold foam. In terms of selectivity, the catalysts are partly balanced catalysts, i.e. compounds which catalyze the gel reaction and the blowing reaction (for example the nitrogen-containing compound of the formula (IIIc)), partly balanced catalysts with a slight preference for the blowing reaction (for example the nitrogen-containing compounds) Compounds according to the formula (IIIa) and (IIIb)), partly as balanced catalysts with a slight preference for the gel reaction (for example the nitrogen-containing compounds according to the formula (IIId) and (IIIe)) or as catalysts which prefer the blowing reaction catalyze (for example, the nitrogen-containing compounds of the formula (IIIf) and (IIIg) according to the invention), to divide. In this very critical formulation, the amount of nitrogen-containing compound of the formula (IIIb) used is insufficient to obtain a stable foam. Similar to the TEGOAMIN ^® DMEA, a larger amount of catalyst is required here. The nitrogen-containing compounds of the formula (IIIf) and (IIIg), according to the invention are in terms of selectivity and activity comparable to ^® Jeffcat ZF-tenth

Claims (14)

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

with n = 1 to 30, a = 2 and b = 1, where the ether or amine building blocks, if present, can occur cumulatively, alternately, in blocks or in a disordered manner, R ₁ , R _{2 are} identical or different from one another, a linear, branched or cyclic, aliphatic, saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, R ₃ = H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more heteroatoms or by one or more heteroatoms interrupted hydrocarbon radical with 1 to 30 carbon atoms,

Use after Claim 1 , characterized in that at least one nitrogen-containing compound of the formula (I) is used where R ₁ , R _2, identical or different from one another, is a hydrocarbon radical with 1 to 30, expressed by

where q is the same or different from each other 2 or 3 and R _{17 is the} same or different from each other * -H or * -CH ₃ . Use according to one of the Claims 1 or 2nd , characterized in that at least one nitrogen-containing compound of the formula (III),

with n, a, b, R ₃ , Y as defined in the preceding claims is used. Use according to one of the Claims 1 to 3rd , characterized in that a nitrogenous compound

and or

and or

is used, with n, q, R ₃ , Y as under Claim 1 - 3rd Are defined. Use according to one of the Claims 1 to 4th , characterized in that a nitrogenous compound

and or

is used. Use after Claim 1 to 5 , characterized in that at least one nitrogen-containing compound of the formula (I) is used as an industrial product mixture, containing impurities, intermediates and / or by-products as further ingredients, comprising 1- (3-aminopropyl) pyrrolidine, 1- (2-aminoethyl ) pyrrolidine, 1- (2-hydroxyethyl) pyrrolidine, 1- (3-hydroxypropyl) pyrrolidine, 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol, 1,1 '- (oxybis (ethane-2,1 -diyl)) dipyrrolidine, ethylenediamine (EDA), 1,4-butanediol, monoethylene glycol (MEG), diethylene glycol (DEG), 1,2-propylene glycol (PG), dipropylene glycol (DPG), diethanolamine, triethanolamine, and / or monoethanolamine ( MEA), in a total amount of up to 95% by weight. Use after Claim 6 , wherein the technical product mixture used contains (a) at least one nitrogen-containing compound of the formula (I) in a total amount of 20-95% by weight. Use according to one of the preceding claims, characterized in that the at least one nitrogen-containing compound of the formula (I), 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 preparation of the polyurethane a composition is produced which contains at least one nitrogen-containing compound of the formula (I), a corresponding quaternized and / or protonated compound, and furthermore at least one polyol component, at least one isocyanate component has, 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 (I) and / or a corresponding quaternized and / or protonated compound in combination with a) one or more additional (ie not according to the invention) nitrogen-containing compounds as additional Catalysts, b) one or more additional metal-containing catalysts, c) one or more acids for blocking the amines present, d) water e) one or more organic solvents, f) one or more chemical or physical blowing agents, g) one or more stabilizers against oxidative degradation, h) one or more flame retardants, and / or i) one or more foam stabilizers based on siloxanes and / or polydialkylsiloxane-polyoxyalkylene copolymers, and / or j) one or more further additives. Use according to one of the preceding claims, characterized in that the at least one nitrogen-containing compound of the formula (I) is used in combination with at least one solvent, the mass ratio of the total catalyst used comprising all catalytically active compounds being the same and not the same as the formula ( I) to solvent is from 100 to 1 to 1 to 4. Composition containing at least one polyol component, characterized in that the composition has at least one nitrogen-containing compound of the formula (I), as defined in the preceding claims, and / or the corresponding quaternized and / or protonated compounds. Composition according to Claim 12 , characterized in that the molar ratio of the total amount of nitrogen-containing catalysts comprising the nitrogen-containing compounds of formula (I) to the total amount of isocyanate-reactive groups of the polyol component is from 4 × 10 ^-4 to 1 to 0.2 to 1. Compositions according to Claim 12 or 13 , characterized in that the nitrogen-containing compounds of formula (I), corresponding quaternized and / or protonated compounds, are used in a mass fraction of 0.01 to 20.0 parts (pphp) based on 100 parts (pphp) polyol component.