DE102014215381A1 - Nitrogen containing compounds suitable for use in the production of polyurethanes - Google Patents

Abstract

The present invention is the use of nitrogen-containing compounds of the formula (I) and / or corresponding quaternized and / or protonated compounds for the preparation of polyurethanes, compositions containing these compounds and polyurethane systems, in particular polyurethane foams, which were obtained using the compounds.

Description

The present invention is in the field of nitrogen containing compounds, especially amines, and polyurethanes. It relates in particular to the use of nitrogen-containing compounds of the formula (I), corresponding to quaternized and / or protonated compounds, for the preparation of polyurethanes, in particular polyurethane foams, compositions containing these compounds and polyurethane systems obtained using the compounds.

The use of tertiary amines in the preparation of polyurethanes is known. A variety of structurally different amines is used as catalysts.

Polyurethanes are understood here to mean all reaction products starting from isocyanates, in particular from polyisocyanates, and correspondingly isocyanate-reactive molecules. This includes, inter alia, polyisocyanurates, polyureas and allophanate, biuret, uretdione, uretimine or carbodiimide-containing isocyanate or polyisocyanate reaction products. Preference is given to the use of tertiary amines in the preparation of polyisocyanate polyaddition products.

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

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

Polyurethane foams are cellular and / or microcellular polyurethane materials and can be broadly divided into closed cell or partially closed cell rigid polyurethane foams and open cell or partially open cell flexible polyurethane foams. Polyurethane rigid foams are predominantly used as insulating materials, for example in refrigerator systems or in the thermal insulation of buildings. Flexible polyurethane foams are used in a large number of industrial and private technical applications, for example for noise insulation, the manufacture of mattresses or the upholstery of 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, also referred to as cold foams (often referred to as "high resilience" (HR) foams), and rigid foams, and foams their properties Here, for example, hard foams can be used as a headliner, ester foams for 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 can also be distinguished between cold foams and hot foams, such. In EP 2042534 A1 which is fully incorporated herein by reference.

There is still a need for further alternative catalysts, preferably nitrogen-containing catalysts, particularly alternative amines useful for making polyurethanes and polyurethane foams, preferably suitable for producing low-odor, low-amine or other emissions-resistant polyurethane systems such as for example, formaldehyde and / or dimethylformamide (DMF).

A concrete object of the present invention was therefore to provide an alternative catalyst for the preparation of polyisocyanate reaction products, preferably polyurethanes, in particular polyurethane foams, which are preferably low odor, resistant to aging and / or free of emissions or possibly with low amine or other emissions, such as Formaldehyde and / or dimethylformamide (DMF), are afflicted.

Surprisingly, it has been found that compounds of the following formula (I), the corresponding quaternized and / or protonated compounds solve this problem, ie both the use of the compounds of formula (I), as well as the use of the corresponding protonated compounds as The use of the corresponding quaternized compounds as well as the use of corresponding mixtures in each case solves the task mentioned.

mit n = 1 bis 30, insbesondere 1 bis 12, vorzugsweise 2 bis 6, bevorzugt 2 oder 3, besonders bevorzugt 2,
a, b gleich oder ungleich voneinander 0 bis 3, mit der Maßgabe, dass a + b = 2 oder 3 ist, 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,

R₄, R₅ gleich oder ungleich voneinander H, 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 ist oder R₄ und R₅ zu einem Zyklus, bevorzugt zu einem Pyrrolidinrest, einem Morpholinrest, einem Imidazolrest oder einem Piperazinrest verbrückt sind, wobei

insbesondere gleich *-NH₂,

wobei R₇, R₈, R₉ 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 ist,
für Y = *-OR₆,
R₆ gleich 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 ist, wobei *-OR₆ bevorzugt gleich *-OH oder

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

with n = 1 to 30, in particular 1 to 12, preferably 2 to 6, preferably 2 or 3, particularly preferably 2,
a, b are the same or different from each other 0 to 3, with the proviso that a + b = 2 or 3, whereby the ether or amine building blocks, if present, can occur cumulatively, alternately, blockwise or disorderly,
R ₁ , R _{2 is the} same or different, 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 2 Carbon atoms,
R ₃ = H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more hetero atoms or interrupted by one or more hetero atoms hydrocarbon radical having 1 to 30 carbon atoms,

R ₄ , R _{5 is the} same or different H, is a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more hetero atoms or interrupted by one or more hetero atoms hydrocarbon radical or R ₄ and R ₅ to a Cycle, preferably bridged to a pyrrolidine radical, a morpholine radical, an imidazole radical or a piperazine radical, wherein

in particular equal to * -NH ₂ ,

where R ₇ , R ₈ , R _{9 are} identical or different and denote H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more hetero atoms or interrupted by one or more hetero atoms hydrocarbon radical having 1 to 30 carbon atoms is
for Y = * -OR ₆ ,
R ₆ is H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more hetero atoms or interrupted by one or more hetero atoms hydrocarbon radical, wherein * -OR ₆ preferably equal to * -OH or

The term "use of at least one nitrogen-containing compound, a corresponding quaternized and / or protonated compound" in the context of this invention here and in the following includes the use of the relevant nitrogen-containing compound as well as the use of the corresponding protonated compounds as well as the use of the corresponding quaternized compounds also the use of appropriate mixtures.

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

Advantageously, the present invention also enables a reduction or avoidance of the catalysis-related emissions in the production of polyurethane systems, in particular of polyurethane foams.

In particular, an additional advantage of the invention is that the nitrogen-containing compounds according to the invention used according to the formula (I), corresponding quaternized and / or protonated compounds, and mixtures of the aforementioned, advantageously low emissions, preferably free with respect to typical undesirable emissions of the resulting polyurethane systems, especially polyurethane foams Particularly preferred polyurethane flexible foams are, namely advantageously low emissions with respect to emissions of nitrogen-containing compounds, hereinafter also referred to as amine emissions, advantageously low emissions with respect to emissions of dimethylformamide (DMF), and advantageously low emissions with respect to aldehyde emissions, especially in terms of formaldehyde emissions.

In the context of the present invention, "low emission" with respect to amines comprises in particular that the polyurethane system, preferably the polyurethane foam, more preferably the flexible polyurethane foam, particularly preferably the flexible polyurethane hot foam, preferably for the production of mattresses and / or upholstery, has an amine emission of .gtoreq.0 .mu.g / m ³ and ≤ 40 μg / m ³ , preferably ≤ 10 μg / m ³ , particularly preferably ≤ 5 μg / m ³ , determined according to the test chamber method based on the DIN standard DIN EN ISO 16000-9: 2008-04 , 24 hours after Prüfkammerbeladung, and / or that the polyurethane system, preferably the polyurethane foam, in particular the flexible polyurethane foam, particularly preferably the polyurethane foam, preferably for the production of polyurethanes for use in the automotive industry, in particular in automotive 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, more preferably ≤ 5 μg / g, according to VDA 278 analytical method in the version of October 2011, " Thermodesorption analysis of organic emissions for the characterization of non-metallic automotive materials " (30 minutes at 90 ° C), and / or the polyurethane system, in particular the flexible polyurethane foam, particularly preferably the polyurethane flexible foam, preferably for the production of polyurethanes for use in the automotive industry, especially in automotive interiors, for example as a headliner, interior lining of doors, punched out Sun visors, steering wheels and / or seating systems, an amine emission, hereinafter referred to as fog emission or fog value according to VDA 278 (Fog: low-volatility substances that condense slightly at room temperature and contribute to the fogging fitting on the windshield), of ≥ 0 μg / g and ≤ 40 μg / g, preferably ≤ 10 μg / g, more preferably ≤ 5 μg / g, according to the VDA 278 Analytical Procedure in the October 2011 version (60 minutes at 120 ° C). VDA is the Association of the Automotive Industry (www.vda.de). Depending on the field 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 _ges , and / or Fog _ges ), for example VOC _ges ≤ depending on the vehicle manufacturer specification 100 μg / g and / or fogges ≤ 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.

"Low emissions" with regard to emissions of dimethylformamide (DMF) in the context of the present invention means in particular that the nitrogen-containing compounds according to the invention of the formula (I), (II), (III) and / or (IV) and / or corresponding polyurethane systems are preferred Polyurethane foams, in particular flexible polyurethane foams, more preferably polyurethane hot foams produced using the aforementioned compounds, a DMF emission of ≥ 0 ppm and ≤ 5 ppm, preferably ≤ 1 ppm, more preferably ≤ 0.1 ppm. Advantageously, the present invention thus makes it possible, in particular, to provide flexible polyurethane foams, in particular polyurethane hot foams, which are particularly low in emissions with respect 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 emissions" with regard to emissions of aldehydes, in particular of formaldehyde, mean in particular that the polyurethane system, preferably the polyurethane foam, in particular the flexible polyurethane foam, by the foam manufacturers and the furniture industry in Europe and the USA within the framework of the voluntarily imposed program "CertiPUR" set limits for aldehyde emissions, in particular for formaldehyde emissions and / or that the replacement of conventional catalysts, in particular amines, especially tertiary amines containing one or more N-methyl or N, N-dimethyl groups, according to State of the art by inventively used nitrogen-containing compounds in the formulation of a corresponding polyurethane system to improve the aldehyde, in particular formaldehyde-related emissions leads. The limit for formaldehyde emissions according to "CertiPUR" for example for mattresses measured at 0.1 mg / m ³ according ASTM Method D5116-97 "Small Chamber Test" when conditioning for 16 hours. The person skilled in various analytical methods for the determination of aldehyde emissions are known. Examples are VDA 275, VDA 277 or also called VDA 278, as well as pointed to various chamber test methods. VDA is the Association of the Automotive Industry (www.vda.de). "VDA 275", after the version of July 1994 , provides a measuring method for determining the aldehyde, in particular the formaldehyde release by the modified bottle method, wherein as derivatization of aldehydes in addition to the acetylacetone commonly used (via photometric detection) and 2,4-dinitrophenylhydrazine (2,4-DNP) (detection via HPLC after external calibration) can be used in addition to formaldehyde to determine acetaldehyde and propionaldehyde better. In the context of this invention, both process interpretations of this VDA 275 are referred to as preferred methods for the determination of 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, with regard to emissions of nitrogen-containing compounds, also referred to below as amine emissions, are particularly low in emissions, preferably free from such emissions, even if different requirements are met.

Advantageously, the present invention thus makes it possible to provide polyurethane systems, preferably polyurethane foams, in particular flexible polyurethane foams prepared using the aforementioned nitrogen-containing compounds which are particularly low in emissions of dimethylformamide (DMF), preferably emission-free, preferably free of such emissions.

Advantageously, the present invention contributes to the provision of polyurethane systems, preferably polyurethane foams, in particular of flexible polyurethane foams, prepared using the aforementioned nitrogen-containing compounds which are lower in emissions of aldehydes, especially formaldehyde, even with different requirements, as corresponding nitrogen-containing catalysts or corresponding polyurethane systems, in which, instead of the nitrogen-containing compounds according to the invention, conventional catalysts, in particular tertiary amines, containing one or more N-methyl or N, N-dimethyl groups, according to the prior art, are used. For commercially available amines or PU systems containing commercially available amines, may otherwise contain, for example due to their industrial production formaldehyde as an impurity, for example, were used in the amine in the formaldehyde or methanol as the alkylating agent.

Advantageously, the present invention 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 using the nitrogen-containing compounds according to the invention as alternative catalysts to catalysts according to the prior art, which is verifiable in particular by olfactory review by a panel of people with an odor.

Advantageously, the present invention further contributes to the improvement of the aging behavior, in particular to the heat resistance and / or aging resistance during 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 preparing the polyurethane systems and usually lead to material fatigue. With the nitrogen-containing compounds according to the invention, the heat resistance and / or durability of the corresponding polyurethane systems over polyurethane systems which have been prepared with conventional catalysts according to the prior art can be advantageously improved here. Advantageously, this effect, in particular in polyurethane foams, preferably soft block foams, in particular in the sense of a dry heat aging after DIN standard DIN EN ISO 2440 / A1: 2009-01 especially 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 nitrogen-containing compounds according to formula (I) according to the invention which are used in the foaming are used as alternatives to structurally related catalysts according to the prior art.

Advantageously, the present invention also provides the provision of preferably discoloration minimized polyurethane systems, in particular polyurethane foams, preferably of polyurethanes for use in the automotive industry, especially in automotive interiors, such as headliners, door panels, punched sun visors, steering wheels and / or seating systems, the polyurethane systems prepared by using nitrogen-containing catalysts according to the invention in particular to lower discoloration of plastics, in particular plastic covers, in automotive interiors as such polyurethane systems that can be prepared using conventional catalysts according to the prior art, in particular non-inventive amines. This can be demonstrated in particular by means of a PVC discoloration test according to the Volkswagen test specification VW PV 3937, amine emissions according to the indicator method.

Advantageously, the present invention allows a broader processing play in the production of polyurethane systems, in particular semi-rigid polyurethane foams (open-cell rigid foams, for example for use as a headliner in automotive interiors). This means that advantageously a greater range of variation of the use concentration of the nitrogen-containing compounds of the invention without adversely affecting the desired material properties, such as the open-cell foam or the space weight distribution over the foam block, is possible over comparable or customarily used for such applications amine catalysts according to the prior Technology. This means a huge amount of work for the user.

For possible quaternization of the compounds of the formula (I), all reagents known as quaternizing reagents can be used. Preferably used as quaternizing alkylating agents, such as. For example, dimethyl sulfate, methyl chloride or benzyl chloride, preferably methylating agent used in particular dimethyl sulfate. Likewise, it is possible to quaternize with alkylene oxides, for example ethylene oxide, propylene oxide or butylene oxide, preferably with subsequent neutralization with inorganic or organic acids.

The compounds of formula (I), if quaternized, may be quaternized one or more times. Preferably, the compounds of formulas (I) are only quaternized. In simple quaternization, the compounds of formula (I) are preferably quaternized on a nitrogen atom which is part of a ring, preferably a pyrrolidine ring.

The compounds of the formula (I) can be converted by reaction with organic or inorganic acids into the corresponding protonated compounds. These protonated compounds may, for. B. be preferred if z. B. a slowed polyurethane reaction is to be achieved or when the reaction mixture should have an improved flow behavior in the application.

As organic acids, for example, all of the following organic acids, for example carboxylic acids having 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 polymeric acids such. As polyacrylic or polymethacrylic acids are used. As inorganic acids, for. As phosphorus-based acids, sulfur-based acids or boron-based acids.

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. Given below, ranges, general formulas, or classes of compounds are intended to encompass not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by removing individual values (ranges) or compounds can be. If documents are cited in the context of the present description, their content, in particular with regard to the facts in connection with which the document was cited, should be included in full in the disclosure of the present invention. Percentages are by weight unless otherwise indicated. If mean values are given below, the weight average is, unless stated otherwise. If subsequently parameters are specified 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 reaction of polyisocyanates and polyols or compounds with isocyanate-reactive groups. It can be formed in addition to the polyurethane and other functional groups, such as. As uretdiones, carbodiimides, isocyanurates, allophanates, biurets, ureas and / or uretimines. Therefore, for the purposes of the present invention, PU is understood as meaning polyisocyanate reaction products containing polyurethane as well as polyisocyanurate, polyureas and uretdione, carbodiimide, allophanate, biuret and uretimine groups. In the context of the present invention, polyurethane foam (PU foam) is understood as meaning foam which is obtained as a reaction product based on polyisocyanates and polyols or compounds with isocyanate-reactive groups. In addition to the name-giving polyurethane, it is also possible to form further functional groups, such as, for example, As allophanates, biurets, ureas, carbodiimides, uretdiones, isocyanurates or uretimines. Therefore, PU foams in the sense of the present invention are understood as meaning both polyurethane foams (PUR foams) and polyisocyanurate foams (PIR foams). Preferred polyurethane foams are flexible polyurethane foams, rigid polyurethane foams and integral polyurethane foams. Particularly preferred herein are conventional flexible polyurethane foams based on ether or ester polyol, high-elastic polyurethane 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 become.

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: *-H, *-CH₃,

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

with m = 1 to 12, in particular 1 to 6, preferably 2 or 3, particularly preferably 2,
with o, p, s, t equal to 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 equal or different from each other H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted with one or more hetero atoms or hydrocarbon radical interrupted by one or more heteroatoms and having 1 to 30 carbon atoms,
wherein R _{3 is} in particular selected from: * -H, * -CH ₃ ,

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 Y insbesondere ausgewählt ist aus folgenden Resten: *-OH, *-NH₂,

oder

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
wherein R ₁ , R ₂ equal to or different from each other, a hydrocarbon radical having 1 to 30, preferably 2 or 3 carbon atoms, expressed by

with q equal to or different from each other 2 or 3 and R _{17 are the} same or different from each other * -H or * -CH ₃ , and wherein R _{3 is} in particular selected 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 are equal to or different from one another, from 1 to 6, in particular 2 or 3, preferably 2,
and Y is in particular selected from the following radicals: * -OH, * -NH ₂ ,

or

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

mit n, a, b, R₃, Y wie bereits zuvor definiert,
worin R₃ besonders bevorzugt *-H, *-CH₃,

Y besonders bevorzugt *-OH oder

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

with n, a, b, R ₃ , Y as already defined above,
in which R ₃ particularly preferably * -H, * -CH ₃ ,

Y particularly preferably * -OH or

is.

It also corresponds to a preferred embodiment of the present invention, when at least one nitrogen-containing compound of the formula (I), preferably of the formula (II), in particular of the formula (III) is used, wherein
a + b = 2 and
a, b are the same or different from each other 0, 1 or 2,
wherein the ether and amine building blocks, if present, can occur cumulatively, alternately, blockwise or disorderly.

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

bevorzugt eingesetzt werden, so liegt ebenfalls eine bevorzugten Ausführungsform dieser Erfindung vor.Is used in the context of this invention, at least one nitrogen-containing compound of formula (I), preferably of the formula (II), in particular of the formula (III), wherein
a = 2 and b = 0,
in particular a compound

is used, with n, q, Y as previously defined,
again

are preferably used, there is also a preferred embodiment of this invention.

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

bevorzugt eingesetzt werden.In addition, it corresponds to a preferred embodiment of this invention, if at least one nitrogen-containing compound of formula (I), preferably of formula (II), in particular of formula (III) is used, wherein
a = 0 and b = 2,
in particular a connection

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

are preferably used.

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

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

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

are preferably used.

A further preferred embodiment of the invention corresponds to when at least one nitrogen-containing compound of the formula (I), preferably of the formula (II), in particular of the formula (III) is used, wherein
a + b = 3 and
a, b are the same or different 0, 1, 2 or 3,
wherein the ether and amine building blocks, if present, can occur cumulatively, alternately, blockwise or disorderly.

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

besonders bevorzugt sind.Yet another preferred embodiment of the invention corresponds to when at least one nitrogen-containing compound of the formula (I), preferably of the formula (II), in particular of the formula (III) is used, wherein
a = 3 and b = 0 is used,
in particular a connection

is used, with n, q, Y as previously defined,
again

are particularly preferred.

und/oder

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

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

and or

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

are preferably used.

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

mit m, n, q gleich oder ungleich voneinander 2 bis 6, insbesondere 2 oder 3, vorzugsweise 2, bevorzugt eingesetzt werden.It therefore corresponds to a further preferred embodiment of the invention, if at least one nitrogen-containing compound of formula (I), preferably of formula (II), in particular of formula (III) is used, wherein
a = 1 and b = 2 is used,
in particular a connection

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

with m, n, q equal or different from each other 2 to 6, in particular 2 or 3, preferably 2, are preferably used.

eingesetzt wird mit n, q, R₃, Y wie bereits zuvor definiert,
wobei besonders bevorzugte Verbindungen ausgewählt sind aus der Gruppe umfassen

mit m, n, q gleich oder ungleich voneinander 2 bis 6, insbesondere 2 oder 3, vorzugsweise 2.Likewise, it corresponds to a further preferred embodiment of the invention, if at least one nitrogen-containing compound of the formula (I), preferably of the formula (II), in particular of the formula (III) is used, wherein
a = 0 and b = 3,
in particular a connection

is used with n, q, R ₃ , Y as previously defined,
particularly preferred compounds being selected from the group comprising

with m, n, q equal or different from each other 2 to 6, in particular 2 or 3, preferably 2.

so dass die stickstoffhaltig Verbindung der Formel (I) der Formel (IV) genügt

mit a, b, n, R₁, R₂, R₃ wie bereits zuvor definiert,
c, d gleich oder ungleich voneinander 0 bis 6, insbesondere 0 bis 3, bevorzugt 1 oder 2, mit der Maßgabe, dass die Ether- oder Amin-Bausteine a, b, c und d, sofern vorhanden, kumulativ, alternierend, blockweise oder ungeordnet auftreten können,
mit R₁₈, R₁₉ gleich oder ungleich voneinander, ein linearer, verzweigter oder cyclischer, aliphatischer, gesättigter oder ungesättigter Kohlenwasserstoffrest mit 1 bis 30 Kohlenstoffatomen, insbesondere 2 bis 12, vorzugsweise 2 bis 6, bevorzugt 2 oder 3 Kohlenstoffatomen, besonders bevorzugt mit 2 Kohlenstoffatomen,
mit R₂₀ = 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, bevorzugt ein Rest ausgewählt aus

darin m = 2–6, vorzugsweise 2 oder 3,

mit o, p gleich oder ungleich voneinander 2 oder 3,

mit s, t gleich oder ungleich voneinander 2 oder 3 und R₁₆ wie bereits zuvor definiert, bevorzugt *-H, *-CH₃,

Moreover, it corresponds to a preferred embodiment of the invention, if in the present invention, a nitrogen-containing compound of formula (I) is used with

such that the nitrogen-containing compound of the formula (I) of the formula (IV) satisfies

with a, b, n, R ₁ , R ₂ , R ₃ as already defined above,
c, d are identical or different from each other 0 to 6, in particular 0 to 3, preferably 1 or 2, with the proviso that the ether or amine building blocks a, b, c and d, if present, cumulative, alternating, blockwise or can occur disorderly
R ₁₈ , R _{19 are} identical or different, 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 2 carbon atoms,
with R ₂₀ = H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more hetero atoms or interrupted by one or more hetero atoms hydrocarbon radical having 1 to 30 carbon atoms, preferably a radical selected from

where m = 2-6, preferably 2 or 3,

with o, p equal or different from each other 2 or 3,

with s, t equal or different from each other 2 or 3 and R ₁₆ as previously defined, preferably * -H, * -CH ₃ ,

With a view to all its subjects and their preferred embodiments, the present invention also includes, in particular, the use of a plurality of different nitrogen-containing compounds of the formulas (I), (II), (III) and / or (IV), eg. As the joint use of nitrogen-containing compounds of the formulas (III) and (IV), and the use of the corresponding protonated compounds and the use of the corresponding quaternized compounds and the use of appropriate Mixtures of all of the abovementioned nitrogen-containing compounds of the formula (I), (II), (III) and / or (IV), corresponding protonated and / or quaternized compounds.

The nitrogen-containing compounds of the formula (I), (II), (III) and / or (IV) according to the invention described above are in principle accessible via customary processes for amine preparation. A good overview of the preparation and derivatization of amines, for example with ethylene oxide and propylene oxide (alkoxylation), in particular for the synthesis of pyrrolidine, is in the article "Amines, Aliphatic" in Ullmann's Encylopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2012, Vol. 2, pp. 647-698 (DOI: 10.1002 / 14356007.a02_001) and the references contained therein.

Preferred synthesis components, for the purposes of the present invention, are in particular amines, polyamines, polyols, preferably diols, in particular glycols, amino alcohols, bischloroalkyl ethers and amino-containing alkyl chlorides. Polyamines which are preferably used are, for example, ethylenediamine (EDA) and higher homologs, such as diethylenetriamine (DETA), triethylenetetramine (TETA) or tris (2-aminoethyl) amine (trene). Amines which are preferably used for amino alcohols or hydroxyl groups can be synthesized, for example, by reaction of 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 according to known methods, such as Beller et al. in Chem. Asian J. 2007, 2, 403-410 , from Milstein et al. in Angew. Chem. 2008, 120, 8789-8792 , from Watson and Williams in Science 2010, Vol. 329, pp. 635-636 or from Börner et al. in ChemCatChem 2010, 2, 640-643 described, can be obtained. 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 in detail herein are all commercially available. An example of a bischloroalkylamine, inter alia, the commercially available bis (2-chloroethyl) amine hydrochloride. Amino group-bearing alkyl chlorides can be obtained, for example, by reacting bischloro-alkyl compounds with one 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 preferable to use pyrrolidine itself, for example in the reaction of pyrrolidine with alkyl halides, especially with alkyl chlorides (nucleophilic substitution), such as from Aitken et al. in Tetrahedron, 2002, Vol. 58, 29, pp. 5933-5940 or from Tijskens et al. in Journal of Organic Chemistry, 1995, Vol. 60, 26, pp. 8371-8374 described, and / or by reacting pyrrolidine with Bischloroalkylethern, and / or by reacting pyrrolidine with epoxides (alkoxylation) or epoxide-bearing compounds, in particular with ethylene oxide (EO) and / or propylene oxide (PO), such as Reppe et al. in Justus Liebigs Annalen der Chemie, 1955, Vol. 596, p. 1149 or from Moffett et al. in Journal of Organic Chemistry, 1949, Vol. 14, pp. 862-866 and in Org. Synth. Coll., 1963, Vol. IV, pp. 834ff , and / or by reacting pyrrolidine with alcohols and / or polyols, preferably diols, in particular glycols, for example in a transition-metal-catalyzed embodiment such as Jenner et al. in Journal of Organometallic Chemistry, 373 (1989), 343-352 described. Furthermore, the pyrrolidine function can also be achieved by reacting 1,4-butanediol with primary amines, such as, for example, from Jenner et al. in Journal of Organometallic Chemistry, 373 (1989), 343-352 described, and / or by reacting 1,4-butanediol with organic compounds carrying ammonia and hydroxyl groups, 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 , such as in DE 701825C described, are introduced. Depending on the process conditions and the selected reaction regime, it is also possible to use a variety of by-products, for example by incomplete or only partial reaction of the starting materials, and by side reactions, for example between the selected starting materials, for example between polyamines, polyols, in particular 1,4-butanediol, and / or Amino alcohols, occur.

By way of illustration, the preparation and performance testing of selected compounds according to formula (I) according to the invention are 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 added to the molecular structure in the sense of an N-methylation. Here, for example, the reductive methylation of primary and secondary amines with the use of formaldehyde and formic acid in the sense of an Eschweiler-Clarke Methylation, which is a special case of the Leuckart-Wallach reaction ( R. Leuckart, Ber. 18, 2341 (1885) ., O. Wallach, Ann. 272, 99 (1892) ). Descriptions of Eschweiler-Clarke methylation can be found, inter alia, in W. Eschweiler, Ber. 38, 880 (1905) and Clarke, et al., J. Am. Chem. Soc. 55, 4571 (1933) as well as other synthetic applications z. B. also in E. Farkas, CJ Sunman, J. Org. Chem. 50, 1110 (1985) or J. Casanova, P. Devi, Synth. Commun. 23, 245 (1993) , Alternative methylation processes include, but are not limited to, the use of methanol, dimethyl sulfate (DMS), dimethylsulfoxide (DMSO), or alkyl halides as alkylating agents. With regard to such methods, reference is made to the diverse literature known to the person skilled in the art on this subject.

In addition, depending on the desired target compound, the N-methyl groups can be introduced into the molecular structure, for example by using monomethyalmin as the N-methyl building block, for example by transition-metal-catalyzed reaction, for example using Raney metals such as Raney metal. Cobalt or Raney nickel, with hydroxyl group-bearing compounds such as diols or aminoalcohols. Such aminations of alcohols with monomethylamine have been described many times in the literature, for example in US 5639916 or DE 4230402 , Depending on the process conditions and the reaction procedure chosen, it is also possible for various by-products to occur, for example as a result of incomplete or only partial reaction of the starting materials, as well as side reactions, for example between the selected starting materials, for example between polyamines, polyols and / or aminoalcohols.

Depending on the manufacturing process, a nitrogen-containing compound of the formula (I), preferably a nitrogen-containing compound of the formula (II), (III) or (IV), in particular a nitrogen-containing compound of the formula (III), depending on the quality of the selected process and number of corresponding purification steps in technical quality, hereinafter also referred to as technical product mixture, are present, so for example, have intermediate and / or by-products as minor components and / or other impurities.

In this case, the use corresponds to at least one nitrogen-containing compound of the formula (I), preferably at least one nitrogen-containing compound of the formula (II), (III) or (IV), in particular a nitrogen-containing compound of the formula (III), as a technical Product mixture is used, 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 up to 95 wt. %, preferably ≦ 70 wt .-%, in particular ≦ 30 wt .-%, preferably ≦ 10 wt .-%, particularly preferably ≦ 5 wt % of a preferred embodiment of this invention.

• (a) zumindest eine stickstoffhaltige Verbindung der Formel (I), insbesondere zumindest eine stickstoffhaltige Verbindung nach der Formel (II), (III), oder (IV), 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.-%,
• (b) optional 1-(3-Aminopropyl)pyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20–95 Gew.-%, insbesondere 30–70 Gew.-%,
• (c) optional 1-(2-Aminoethyl)pyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20–95 Gew.-%, insbesondere 30–70 Gew.-%,
• (d) optional 1-(2-Hydroxyethyl)pyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20–95 Gew.-%, insbesondere 30–70 Gew.-%,
• (e) optional 1-(3-Hydroxypropyl)pyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20–95 Gew.-%, insbesondere 30–70 Gew.-%,
• (f) 2-(2-(Pyrrolidin-1-yl)ethoxy)ethanol, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20–95 Gew.-%, insbesondere 30–70 Gew.-%,
• (g) 1,1'-(Oxybis(ethan-2,1-diyl))dipyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20–95 Gew.-%, insbesondere 30–70 Gew.-%,
• (h) optional Ethylendiamin (EDA), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%,
• (i) optional 1,4-Butandiol, vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%,
• (j) optional Monoethylenglycol (MEG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%,
• (k) optional Diethylenglycol (DEG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%,
• (l) optional 1,2-Propylenglycol (PG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%,
• (m) optional Dipropylenglycol (DPG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%,
• (n) optional Diethanolamin, vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%,
• (o) optional Triethanolamin, vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%, und/oder
• (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 inventive use of a technical product mixture, wherein the technical product mixture contains

• (a) at least one nitrogen-containing compound of the formula (I), in particular at least one nitrogen-containing compound of the formula (II), (III), or (IV), more preferably at least one nitrogen-containing compound of the formula (III), advantageously in one Total amount of ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
• (b) optionally 1- (3-aminopropyl) pyrrolidine, advantageously in an amount ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
• (c) optionally 1- (2-aminoethyl) pyrrolidine, advantageously in an amount of ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
• (d) optionally 1- (2-hydroxyethyl) pyrrolidine, advantageously in an amount of ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
• (e) optionally 1- (3-hydroxypropyl) pyrrolidine, advantageously in an amount of ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
• (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,
• (g) 1,1 '- (oxybis (ethane-2,1-diyl)) dipyrrolidine, advantageously in an amount of ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight .
• (h) optionally ethylenediamine (EDA), advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
• (i) optionally 1,4-butanediol, advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
• (j) optionally monoethylene glycol (MEG), advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
• (k) optionally diethylene glycol (DEG), advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
• (I) optionally 1,2-propylene glycol (PG), advantageously in an amount of ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
• (m) optionally dipropylene glycol (DPG), advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
• (n) optionally diethanolamine, advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
• (O) optional triethanolamine, advantageously in an amount ≤ 95 wt .-%, in particular 20-90 wt .-%, preferably 30-80 wt .-%, and / or
• (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.

For the purposes of the abovementioned preferred embodiment, particularly preferred technical product mixtures in the context of the present invention are those compositions in which at least one nitrogen-containing compound of the formula (I), in particular of the formula (II), (III) or (IV), preferably according to the Formula (III), and / or a corresponding quaternized and / or protonated compound is used in combination:
with b), c), d), e), f), g), h), i), j), k), l), m), 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) , b), c), d), e), f), g) and l), b), c), d), e), f) and l) or in combination with b), c) , d), e), g) and l). In this case, combinations with b) are particularly preferred, with c) with j), with k), with l) and with m).

The compounds of the formula (I), (II), (III) and / or (IV) described above and / or corresponding quaternized and / or protonated compounds are preferably used in the preparation of polyurethane systems according to the invention, preferably for the production of polyurethane coatings, polyurethane adhesives, Polyurethane sealants, polyurethane elastomers or used in particular for the production of polyurethane foams as catalysts. The compounds of 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 of 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 of conventional metal-containing catalysts according to the prior art.
or (IV), in particular at least one nitrogen-containing compound of the formula (III),

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), (III) or (IV), in particular at least one nitrogen-containing compound of the formula (III ), an appropriately quaternized and / or protonated compound, or mixtures of the nitrogen-containing compound according to formula (I), (II), (III) and / or (IV) with corresponding quaternized and / or protonated compounds as catalyst in the preparation of polyurethane systems, in particular polyurethane foams. In particular, said nitrogen-containing compound 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 of hot, cold, ester flexible polyurethane foams or rigid polyurethane foams, the respectively necessary substances such as isocyanates, polyols, stabilizers, surfactants, etc .. is selected accordingly to obtain the particular desired type of polyurethane, in particular polyurethane foam type.

In the preparation according to the invention of polyurethane systems, in particular polyurethane foams, preferably at least one nitrogen-containing compound of the formula (I), preferably at least one nitrogen-containing compound of the formula (II), (III) or (IV), in particular at least one nitrogen-containing compound according to 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, with each other.

Further details on the starting materials used, catalysts and auxiliaries and additives can be found, for example, in US Pat Kunststoffhandbuch, volume 7, polyurethanes, Carl Hanser Verlag Munich, 1st edition 1966, 2nd edition, 1983 and 3rd edition, 1993 , The following compounds, components and additives are given by way of example only and may be replaced and / or supplemented by other materials known to those skilled in the art.

The compounds of the formula (I), (II), (III) and / or (IV) to be used according to the invention and / or a correspondingly quaternized and / or protonated compounds, in total amount, are preferably present in a proportion by mass of from 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 used.

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

As isocyanate components, one or more organic polyisocyanates having two or more isocyanate functions are preferably used. The polyol components used are preferably one or more polyols having two or more isocyanate-reactive groups.

Isocyanate suitable isocyanates in the context of this invention are all isocyanates containing 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.

By way of example, mention may be made here of alkylene diisocyanates having 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 (HMDI), cycloaliphatic diisocyanates, such as cyclohexane-1,3- and 1,4-diisocyanate, and any desired mixtures of these isomers, 1-isocyanato-3,35-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI for short), 2,4- and 2,6-hexahydrotoluylene diisocyanate and the corresponding isomer mixtures, and preferably aromatic di- and polyisocyanates, such as, for example, 2,4- and 2,6-toluene diisocyanate (TDI) and the corresponding mixtures of isomers, mixtures of 2,4'- and 2,2 'Diphenylmethane diisocyanates (MDI) and Polyphenylpolymethylene polyisocyanates (crude MDI) and mixtures of crude 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 toluene diisocyanate (2,4- and 2,6-toluene diisocyanate (TDI), in pure form or as isomeric mixtures of different composition), 4,4'-diphenylmethane diisocyanate (MDI), the so-called "crude MDI" or "polymeric MDI" (in addition to the 4,4'- also contains the 2,4'- and 2,2'-isomers of MDI and höherkernige products) and the "pure MDI" designated binuclear product predominantly 2,4'- and 4,4'-isomer mixtures or their prepolymers. Examples of particularly suitable isocyanates are, for example, in EP 1712578 . EP II61474 . WO 00/58383 . US 2007/0072951 . EP 1678232 and the WO 2005/085310 which are incorporated herein by reference in their entirety.

Suitable polyol components in the context of the present invention are all organic substances having a plurality of isocyanate-reactive groups, 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, especially Polyetherpolycarbonatpolyole and / or polyols of natural origin, so-called "natural oil based polyols" (NOPs). Typically, the polyols have a functionality of 1.8 to 8 and number average molecular weights in the range of 500 to 15,000. Usually, the polyols having OH numbers in the range of 10 to 1200 mgKOH / g are used. The number average molecular weights are usually determined by gel permeation chromatography (GPC), in particular using polypropylene glycol as the reference substance and tetrahydrofuran (THF) as the eluent. The OH numbers can in particular according to the DIN standard DIN 53240: 1971-12 be determined.

Polyetherpolyols can be prepared by known processes, for example by anionic polymerization of alkylene oxides in the presence of alkali metal 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 bonded 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; preferably ethylene oxide and 1,2-propylene oxide are used. The alkylene oxides can be used individually, cumulatively, in blocks, alternately one after another or as mixtures. In particular, compounds having at least 2, preferably 2 to 8 hydroxyl groups or having at least two primary amino groups in the molecule are used as starting molecules. As starter molecules can be used for. As water, 2-, 3- or 4-hydric alcohols such as ethylene glycol, 1,2-propanediol and 1,3, 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, resoles such. B. oligomeric condensation products of phenol and formaldehyde and Mannich condensates of phenols, formaldehyde and dialkanolamines and melamine, or amines such as aniline, EDA, TDA, MDA and PMDA, more preferably TDA and PMDA. The choice of the suitable starter molecule depends on the respective field of application of the resulting polyether polyol in polyurethane production (for example, other 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 polybasic aliphatic or aromatic carboxylic acids, preferably having 2 to 12 carbon atoms. Examples of aliphatic carboxylic acids are succinic, glutaric, adipic, suberic, azelaic, sebacic, decanedicarboxylic, maleic and fumaric acids. 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 polybasic carboxylic acids with polyhydric alcohols, preferably diols or triols having 2 to 12, more preferably having 2 to 6 carbon atoms, preferably trimethylolpropane and glycerol.

Polyether polycarbonate polyols are polyols containing carbon dioxide bonded as carbonate. Since carbon dioxide is by-produced in large quantities in many processes in the chemical industry, the use of carbon dioxide as a comonomer in alkylene oxide polymerizations is of particular interest from a commercial point of view. Partial replacement of alkylene oxides in polyols with carbon dioxide has the potential to significantly reduce the cost of producing polyols. In addition, the Using CO ₂ as a comonomer ecologically very advantageous, since this reaction represents the conversion of a greenhouse gas to a polymer. The preparation of Polyetherpolycarbonatpolyolen by addition of alkylene oxides and carbon dioxide to 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, as they are for example in US-A 3900424 or US-A 3953383 are described. Furthermore, mono- and binuclear metal complexes have been used successfully for the copolymerization of CO 2 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 referred to as DMC catalysts ( US-A 4500704 . WO 2008/058913 ). Suitable alkylene oxides and H-functional starter substances are those which are also used for the preparation 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, and already many, in view of the long-term limited availability of fossil resources, namely oil, coal and gas, and in light of rising crude oil prices Applications described ( WO 2005/033167 ; US 2006/0293400 . WO 2006/094227 . WO 2004/096882 . US 2002/0103091 . WO 2006/116456 and EP 1678232 ). In the meantime, a number of these polyols from various manufacturers are available on the market ( WO2004 / 020497 . US2006 / 0229375 . WO2009 / 058367 ). Depending on the basic raw material (eg soybean oil, palm oil or castor oil) and the subsequent workup, polyols with different properties can be obtained. Essentially, two groups can be distinguished: a) Polyols based on renewable raw materials, which are modified to the 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 workup and properties can replace the petrochemically based polyol only to a certain extent ( WO2009 / 058367 ).

Another class of usable polyols are the so-called Füllkörperpolyole (polymer polyols). These are characterized in that they contain solid organic fillers to a solids content of 40% or more in disperse distribution. Can be used, inter alia, SAN, PHD and PIPA polyols. SAN polyols are highly reactive polyols containing 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 in dispersed form, for example, by in situ reaction of an isocyanate with an alkanolamine in a conventional polyol. The solids content, which is preferably between 5 and 40%, based on the polyol, depending on the application, is responsible for an improved cell opening, so that the polyol is in particular controllably foamable with TDI and no shrinkage of the foams occurs. The solid acts as an essential process aid. Another function is to control the hardness via the solids content, because higher solids contribute to a higher hardness of the foam. The formulations containing solids-containing polyols are significantly less intrinsically stable and therefore, in addition to the chemical stabilization by the crosslinking reaction, rather require physical stabilization as well. Depending on the solids content of the polyols, these z. B. alone or z. B. be used in admixture with the above unfilled polyols.

Another class of employable polyols are those which are obtained as prepolymers by reacting polyol with isocyanate in a molar ratio of 100: 1 to 5: 1, preferably 50: 1 to 10: 1. Such prepolymers are preferably dissolved in polymer, wherein the polyol preferably corresponds to the polyol used to prepare the prepolymers.

Another class of employable polyols 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, in particular amino groups, preferably tertiary amine functions, urea groups and / or heterocycles containing nitrogen atoms. The use of such autocatalytic polyols in the production of polyurethane systems, in particular of polyurethane foams, preferably of flexible polyurethane foams, the required amount of optionally additionally used catalysts can be optionally reduced depending on the application and / or adapted to specific desired foam properties. Suitable polyols are, for example, in WO 0158976 (A1) . WO 2005063841 (A1) . WO0222702 (A1) . WO 2006055396 (A1) . WO 03029320 (A1) . WO 0158976 (A1) . US 6924321 (B2) . US6762274 (B2) . EP 2104696 (B1) . WO 2004060956 (A1) or WO 2013102053 (A1) and can be obtained, for example, under the trade names Voractiv ^™ and / or SpecFlex ^™ Activ from Dow.

Depending on the required properties of the resulting foams, corresponding 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 in the art and can, for example, the EP-A-0380993 or US-A-3346557 which are referred to in their entirety.

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

According to a further preferred embodiment of the invention, in particular for the production of flexible slab foams, it is necessary to use dihydric and / or trifunctional polyether alcohols which have secondary hydroxyl groups, preferably more than 50%, particularly preferably more than 90%, in particular those with a propylene oxide block or random propylene and ethylene oxide block at the chain end or those based only on propylene oxide blocks. Such polyether alcohols preferably have a functionality of 2 to 8, more preferably 2 to 4, number average molecular weights in the range of 500 to 8000, preferably 800 to 5000, more preferably 2500 to 4500 and usually OH numbers in the range of 10 to 100, preferably 20 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, more preferably 2 to 3, number average molecular weights in the range of 200-4000, preferably 400-3000, more preferably 600-2500, and usually OH numbers in the range of 10-1000, preferably 20 -500, more 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, more preferably 2 to 3, number average molecular weights in the range of 200-1500, preferably 300-1200, more preferably 400-1000, and usually OH numbers in the range of 100-500, preferably 150 -300, more 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%, more preferably over 90%, especially those having a propylene oxide block or random Propylene and ethylene oxide block at the chain end or those based only on propylene oxide blocks. Such polyether alcohols preferably have a functionality of 2 to 8, more preferably 3 to 8, number average molecular weights in the range of 500 to 2000, preferably 800 to 1200 and usually OH numbers in the range of 100 to 1200, preferably 120 to 700, particularly preferably 200 to 600 mgKOH / g. Depending on the required properties of these inventively preferred foams in addition to the polyols described herein additionally polyether, such as 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.

According to a further preferred embodiment of the invention, in particular for the production of viscoelastic polyurethane foams, it is preferred to use mixtures of different, preferably two or three, polyfunctional polyester alcohols and / or polyether alcohols. 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 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 to polyol, expressed as the index of the formulation, d. H. the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (eg 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 from 100 stands for a molar ratio of the reactive groups of 1 to 1.

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

The term "additional catalysts" in the context of this invention comprises in particular the use of compounds which are different from the nitrogen-containing compounds according to the invention of the formula (I), (II), (III) and / or (IV) and / or corresponding protonated and / or or quaternized compounds, and at the same time capable of catalyzing isocyanate reactions, in particular the reactions mentioned below, and / or in the preparation of polyisocyanate reaction products, in particular in the preparation of polyurethane systems, particularly preferably in the preparation of polyurethane foams Catalysts, co-catalysts or activators are used.

The term "premixed catalyst combination", hereinafter also referred to as the catalyst combination, comprises in the context of this invention in particular finished mixtures of nitrogen-containing compounds according to the invention of the formula (I), (II), (III) and / or (IV), corresponding protonated and / or quaternized compounds, additional catalysts, and optionally further ingredients or additives such as water, organic solvents, acids for blocking the amines, emulsifiers, surfactants, blowing agents, antioxidants, flame retardants, stabilizers and / or siloxanes, preferably polyether siloxanes, the already present as such before foaming and need not be added as individual components during the foaming process.

As additional catalysts in the context of this invention, for example, any catalysts for the reactions isocyanate-polyol (urethane formation) and / or isocyanate-water (amine and carbon dioxide formation) and / or the isocyanate dimerization (uretdione formation) isocyanate Trimerization (isocyanurate formation), isocyanate isocyanate with CO ₂ cleavage (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 in the context 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 inventive nitrogen-containing compounds of the formula (I) to (IV), which catalyze one of the above isocyanate reactions and / or Production of polyurethanes, in particular polyurethane foams can be used.

The term "nitrogen-containing compounds of the formula (I)" in the context of this invention in each case comprises the corresponding protonated and / or quaternized compounds and mixtures of these compounds. The term "nitrogen-containing compounds of the formula (I), (II), (III) and / or (IV)" in the context of this invention in each case comprises 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), (III) or (IV), in particular at least one nitrogen-containing compound of the formula (III)" for the purposes of this invention also the joint use of such nitrogen-containing compounds, ie z. B. also the combined use of nitrogen-containing compounds of the formula (III) and (IV).

Examples of suitable additional nitrogen-containing compounds as catalysts for the purposes of the present invention are the amines triethylamine, N, N-dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, N, N-dimethylaminoethylamine, N, N, N ', N'-tetramethylethylene-1, 2-diamine, N, N, N ', N'-tetramethylpropylene-1,3-diamine, N, N, N', N'-tetramethyl-1,4-butanediamine, N, N, N ', N'- Tetramethyl-1,6-hexanediamine, N, N, N ', N ", N" -pentamethyldiethylenetriamine, N, N, N'-trimethylaminoethylethanolamine, N, N-dimethylaminopropylamine, N, N -diethylaminopropylamine, 1- (2 -Aminoethyl) pyrrolidine, 1- (3-aminopropyl) pyrrolidine, N, N-dimethylaminopropyl-N ', N'-dipropan-2-olamine, 2 - [[3- (dimethylamino) propyl] methylamino] ethanol, 3- ( 2-dimethylamino) ethoxy) propylamine, N, N-bis [3- (dimethylamino) propyl] amine, N, N, N ', N ", N" -pentamethyldipropylenetriamine, 1- [bis [3- (dimethylamino ) propyl] amino] -2-propanol, N, N-bis [3- (dimethylamino) propyl] -N ', N'-dimethylpropane-1,3-diamine, triethylenediamine, 1,4-diazabicyclo [2.2.2] octane-2-methanol, N, N'-dimet hylpiperazine, 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'-di-morpholinodiethyl 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'- (2-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-tri azabicyclo [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) isophorone dicarbamate, 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 in the context 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 preparation of polyurethanes, in particular polyurethane foams in addition to the nitrogen-containing compounds of the formula ( I) to (IV) can be used. They can be selected for example from the group of the 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 the metal chelate complexes.

For the purposes of this invention, the expression "organometallic or organometallic compounds" includes in particular the use of metal-containing compounds which have a direct carbon-metal bond, here also as metal organyls (eg tin organyls) or organometallic or organometallic compounds (eg B. organotin compounds). For the purposes of this invention, the expression "organometallic or organometallic salts" includes in particular the use of salt-active organometallic or organometallic compounds, that is to say internal compounds in which either the anion or cation is of organometallic nature (eg organotin oxides, organotin compounds). Chlorides or organotin carboxylates). For the purposes of this invention, the term "organic metal salts" includes 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 (eg. tin (II) carboxylates). The term "inorganic metal salts" in the context of this invention includes in particular the use of metal-containing compounds or metal salts in which neither anion nor cation is an organic compound, for. Metal chlorides (eg stannous chloride), pure or mixed metal oxides (eg tin oxides) containing several metals and / or metal silicates or aluminosilicates. The term "coordination compound" in the context of this invention in particular comprises the use of metal-containing compounds which consist of one or more central particles and one or more Ligands are constructed, wherein the central particles are charged or uncharged metals (eg., Metal or tin-amine complexes). For the purposes of this invention, the term "metal chelate complexes" includes in particular the use of metal-containing coordination compounds which have ligands with at least two coordination or bonding sites to the metal center (eg metal or tin-polyamine or metal or metalloid complexes) Tin-polyether complexes).

Suitable metal-containing compounds, in particular as defined above, as additional catalysts in the context 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, especially 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 in the context of the present invention may for example be selected from the group of salts of inorganic acids such as hydrochloric acid, carbonic acid, sulfuric acid, nitric acid and phosphoric acid and / or other halogen-containing acids. The resulting inorganic metal salts, for example metal chlorides, metal sulfates, metal phosphates, preferably metal chlorides such as stannous chloride, in the preparation of polyurethane systems, in particular of polyurethane foams, usually only in combination with other organometallic salts, organic metal salts or nitrogen-containing catalysts and not as the only catalysts, in pure form or mixed in a solvent used.

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

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 in the context of the present invention can be selected, for example, from the group of salts of organic acids.

The term "organic acids" in the context of this invention includes all organic chemical, ie 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 may, 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 of alcohols, ie organic compounds one or more hydroxyl groups (* - OH), so-called alcoholates, and / or of thiols, ie organic compounds carrying one or more thiol groups (* -SH, also referred to as mercapto groups in higher priority functional group molecules), so-called thiolates (or mercaptides ), and / or of mercaptoacetic acid esters as a special case of thiols, ie organic compounds bearing one or more mercaptoacetic acid ester groups (* -O-CO-CH ₂ -CH ₂ -SH), so-called mercaptoacetates, and or sulfuric acid esters, ie organic compounds which carry one or more sulfate groups (* -O-SO ₃ H), see above sulfates, and / or of sulfonic acids, ie organic compounds which carry one or more sulfonic acid groups (* -SO ₂ -OH), so-called sulfonates, and / or of phosphoric acid esters (alkyl phosphates), ie organic compounds which 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 containing 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 in the context of the present invention are, for example, all linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally with one or more heteroatoms, preferably with hydroxy groups (* -OH), primary, secondary or tertiary amino groups (* -NH ₂ , * -NHR, * -NR ₂ ) or mercapto groups (* -SH), substituted, or interrupted by one or more heteroatoms mono-, di- or poly-carboxylic acids. Particularly suitable for the purposes of the present invention are carboxylic acids whose carbobyl carbon atom is a hydrogen atom or a linear, branched or cyclic, aliphatic saturated or unsaturated, optionally 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 is interrupted by one or more hetero atoms interrupted hydrocarbon radical. Particularly suitable for the purposes of the present invention are those aliphatic carboxylic acids which have in the 2-position, ie on the carbon atom in addition to the carbonyl, disubstituted (tertiary) or trisubstituted (quaternary) carbons, or corresponding hydrocarbon radicals. Preferred for the purposes of the present invention are those aliphatic carboxylic acids which have one or two methyl, ethyl, n-propyl, iso-propyl, n-butyl and / or iso-butyl branch (s) in the 2-position. Particularly preferred for the purposes of the present invention are those aliphatic carboxylic acids, especially monocarboxylic acids, which in addition to the described branching 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) substituted. In particular, suitable carboxylic acids can be selected from the group of the 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 Koch 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 (isoheptanoic acid), pivalic acid, caproic acid, 2-ethylhexanoic acid (iso-octanoic acid), oleic 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, Pe nadecanoic, palmitic, margaric, stearic, oleic, linoleic, alpha-linolenic, phytanic, icosenoic, erucic, ricinoleic, vernolic, arachidonic, arachidonic, oxalic, glycolic, glyoxylic, malonic, lactic, citric, succinic, fumaric, maleic, malic, tartaric , Glutaric acid, adipic acid, sorbic acid, cinnamic acid, salicylic acid, benzoic acid, terephthalic acid, phthalic acid, isophthalic acid, nicotinic acid, carbamic acid, pyrrolidine-2-carboxylic acid and cyclohexanecarboxylic 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 purpose are, for example, methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, neopentyl alcohol, phenols and / or nonylphenol.

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

Particularly suitable organometallic salts and organic metal salts, as defined above, as additional catalysts in the context of the present invention are, for example, organotin, tin, zinc, bismuth and potassium salts, in particular corresponding metal carboxylates, -alcoholates, -thiolates and -Mercaptoacetate 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- ethylhexylmercaptoacetate, dimethyltin-bis-2-ethylhexylmercaptoacetate, dibutyltin bis-2-ethylhexylmercaptoacetate, dioctyltin bis-isooctylmercaptoacetate, stannous acetate, stannous-2-ethylhexanoate (stannous octoate), tin ( II) -isononanoate (tin (II) -3,5,5-trimethylhexanoate), stannous (II) neodecanoate, stannous ricinoleate, zinc (II) acetate, zinc (II) 2-ethylhexanoate (zinc (II) -o ctoat), zinc (II) isononanoate (zinc (II) -3,5,5-trimethylhexanoate), zinc (II) neodecanoate, zinc (II) ricinoleate, bismuth acetate, bismuth 2-ethylhexanoate, bismuth octoate, bismuth isononanoate, Bismuth neodecanoate, potassium formate, potassium acetate, potassium 2-ethylhexanoate (potassium octoate), potassium isononanoate, potassium neodecanoate and / or potassium ricinoleate.

In the preparation of polyurethanes according to the invention, depending on the nature of the application, in particular in the preparation of polyurethane foams, it may be preferable to exclude the use of organometallic salts, for example of dibutyltin dilaurate.

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

In addition to additional amines and metal-containing compounds and ammonium salts can be used as additional catalysts. Suitable examples are ammonium formate and / or ammonium acetate.

Suitable additional catalysts are, for example, in DE 102007046860 . EP 1985642 . EP 1985644 . EP 1977825 . US 2008/0234402 . EP 06563821 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 of 0.01 to 10.0 pphp, more preferably in the range of 0.02 to 5.00 pphp (= parts by weight based on 100 parts by weight of polyol) or 0.10 to 10.0 pphp for potassium salts.

Depending on the application, it may be preferred according to the invention if, in the case of using additional catalysts and / or premixed catalyst combinations as defined above, from the sum of all the nitrogen-containing compounds used, ie the sum of the nitrogen-containing compounds of the formula (I) according to the invention ( II), (III) and / or (IV) and the additional nitrogen-containing catalysts according to the prior art, compared with 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 more preferably 1: 0.1 to 0.1: 1 results.

It may be preferred according to the invention that additional catalysts and / or premixed catalyst combinations, as defined above, are free of dimethylamine-carrying nitrogen-containing compounds. Free of dimethylamine-carrying nitrogen-containing compounds are catalyst combinations in the context of this invention, preferably when less than 75 wt .-%, in particular less than 50 wt .-%, preferably less than 30 wt .-%, particularly preferably less than 10 wt. % of the catalysts in the catalyst mixture include dimethylamine-bearing nitrogen-containing compounds. Particular preference is given to catalyst combinations which contain no, that is to say 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 according to formula (I), (II), (III) and / or (IV) and / or additional nitrogen-containing catalysts with additional metal-containing catalysts, in particular potassium, Zinc and / or tin catalysts, it may be preferable to store these components separately from each other and then to supply the isocyanate and polyol reaction mixture simultaneously or sequentially.

• a) einer oder mehreren zusätzlichen (also nicht erfindungsgemäßen) stickstoffhaltigen Verbindungen als zusätzliche Katalysatoren, vorzugsweise wie oben definiert und beispielhaft beschrieben,
• b) einem oder mehreren zusätzlichen metallhaltigen Katalysatoren, insbesondere einer oder mehrerer Zinn-, Zink-, Bismuth- und/oder Kaliumverbindungen, vorzugsweise wie oben definiert und beispielhaft beschrieben,
• c) einer oder mehrerer Säuren zur Blockierung der enthaltenden Amine, vorzugsweise wie oben beschrieben,
• d) Wasser
• e) einem oder mehreren organischen Lösungsmitteln, vorzugsweise wie im Folgenden definiert und beispielhaft beschrieben,
• f) einem oder mehreren chemischen oder physikalischen Treibmitteln, vorzugsweise wie im Folgenden beschrieben,
• g) einem oder mehreren Stabilisatoren gegen oxidativen Abbau, beispielsweise Antioxidantien, vorzugsweise wie im Folgenden beschrieben,
• h) einem oder mehreren Flammschutzmitteln, vorzugsweise wie im Folgenden beschrieben, und/oder
• i) einem oder mehreren Schaumstabilisatoren auf der Basis von Siloxanen und/oder Polydialkylsiloxan-Polyoxyalkylen-copolymeren, vorzugsweise wie im Folgenden definiert und beschrieben, und/oder
• 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), (III) oder (IV) auch als technische Produktmischung eingesetzt werden. Geeignete technische Produktmischungen sind in der Beschreibung erläutert. It corresponds to a preferred embodiment of the invention, if in the context of the inventive use at least one nitrogen-containing compound of formula (I), preferably of the formula (II), (III) or (IV), in particular of the formula (III), and / or a corresponding quaternized and / or protonated compound in combination with

• a) one or more additional (not according to the invention) nitrogen-containing compounds as additional catalysts, preferably as defined above and described by way of example,
• 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,
• c) one or more acids for blocking the amines containing, preferably as described above,
• d) water
• e) one or more organic solvents, preferably as defined and exemplified below,
• f) one or more chemical or physical blowing agents, preferably as described below,
• g) one or more stabilizers against oxidative degradation, for example antioxidants, preferably as described below,
• h) one or more flame retardants, preferably as described below, and / or
• i) one or more foam stabilizers based on siloxanes and / or polydialkylsiloxane-polyoxyalkylene copolymers, preferably as defined and described below, and / or
• j) one or more further additives, for example selected from the group of surfactants biocides, dyes, pigments, fillers, antistatic additives, crosslinkers, chain extenders, cell openers, and / or fragrances

is used, wherein advantageously before the preparation of the polyurethane, in particular the polyurethane foam, first a composition is prepared, for example in the sense of a predosing of the individual components in the mixing head or z. B. as a premixed catalyst combination, in particular as defined above, comprising the aforementioned combination. In particular, said nitrogen-containing compound of formula (I), (II), (III) or (IV) can also be used as a technical product mixture. Suitable technical product mixtures are explained in the description.

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

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

Suitable solvents are all suitable according to the prior art substances in question. Depending on the application, aprotic-apolar, aprotic-polar and protic solvents can be used. Suitable aprotic-nonpolar solvents can be selected, for example, from the following classes of substance 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 classes of substance 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 classes of substance 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 the company 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 containing as alkyl radicals butyl / methyl, methyl / methyl or butyl / butyl radicals, preferably those obtainable from diol-initiated polyethers, glycols, glycerol, Carboxylic 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), cyclohexanoates, preferably diisononylcyclohexanoate ( DINCH).

Particularly preferred are solvents are compounds that can be processed easily 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 generate no 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 PDO-propanediol), tetramethylene glycol (butanediol BDO), butyl diglycol (BDG), neopentyl glycol, 2-methyl-l, 3-propanediol (CXT ORTEGOL ^®), 3-methyl-1,5-pentanediol and higher homologs thereof such as polyethylene glycol Other particularly preferred OH-functional compounds are polyethers having average molecular weights of from 200 to 4500, in particular from 400 to 2000, preferably water, allyl, butyl or nonyl-initiated polyethers, in particular those based on propylene oxide (PO) and / or ethylene oxide blocks (EO).

If nitrogen-containing compounds according to the invention of formula (I), (II), (II) and / or (IV) or premixed catalyst combinations of the compounds of the invention with additional catalysts, as defined above, dissolved or used in combination with a solvent, the mass ratio is of catalyst or catalyst combination to solvent preferably from 100 to 1 to 1 to 4, preferably from 50 to 1 to 1 to 3 and more preferably from 25 to 1 to 1 to 2.

As additives, it is possible to use all substances known from the state of the art which are used in the production of polyurethanes, in particular polyurethane foams, for example propellants, preferably water for the formation of CO ₂ and, if necessary, further physical blowing agents, crosslinkers 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 catalytically active substances, in particular as defined above.

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

It is also possible to use suitable physical blowing agents. These are, for example, liquefied CO ₂ , and volatile liquids, for example hydrocarbons having 3, 4 or 5 carbon atoms, preferably cyclo, iso and n-pentane, hydrofluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, chlorofluorocarbons, preferably HCFC 141 b, hydrofluoroolefins (HFO) or hydrohaloolefins such. B. 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 can be used which react with isocyanates to evolve gas, such as formic acid.

Crosslinkers and chain extenders are low molecular weight, isocyanate-reactive, polyfunctional compounds. Suitable are, 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. The use concentration is usually between 0.1 and 5 parts, based on 100 parts of polyol, but may vary depending on the formulation thereof. When crude MDI is used in foam molding, this also assumes a crosslinking function. The content of low molecular weight crosslinkers can therefore be correspondingly reduced with increasing amount 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). Preference is given to compounds of the following classes of substances or classes of substances containing the following functional groups, particular preference being given to substituents on the respective basic bodies which possess isocyanate-reactive groups: 2- (2'-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, benzoic acids and Benzoates, phenols, in particular containing aromatic tert-butyl and / or methyl substituents, benzofuranones, diarylamines, triazines, 2,2,6,6-tetramethylpiperidines, hydroxylamines, alkyl and aryl phosphites, sulfides, zinc carboxylates, diketones. As phenols, for example, esters based on 3- (4-hydroxyphenyl) propionic acid, such as triethylene glycol 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). 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. As 2-hydroxybenzophenones, for example, 2-hydroxy-4-n-octoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone or 2,4-dihydroxybenzophenone are preferred. As benzoates, for example, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate or tannins are preferred.

Suitable flame retardants in the context of this invention are all substances which, according to the prior art, will be considered suitable for this purpose. Preferred flame retardants are, for example, liquid organic phosphorus compounds, such as halogen-free organic phosphates, for. 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. Dimethylmethanephosphonate (DMMP), dimethylpropanephosphonate (DMPP), or solids such as ammonium polyphosphate (APP) and red phosphorus. Furthermore, halogenated compounds, for example halogenated polyols, and solids such as expanded graphite and melamine are 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. Also suitable as surfactants according to the invention are polymeric emulsifiers, such as polyalkylpolyoxyalkylpolyacrylates, polyvinylpyrrolidones or polyvinyl acetates.

As biocides, for example, commercially available products may be used, such as chlorophen, benzisothiazoline, hexahydro-1,3,5-tris (hydroxyethyl-s-triazine), chloromethylisothiazoline, methylisothiazoline or 1,6-dihydroxy-2,5-dioxohexane, which are described in US Pat the trade names BIT 10, Nipacide BCP, Acticide MBS, Nipacide BK, Nipacide CI, Nipacide FC are known.

In order to influence the foaming properties of polyurethane foams, in particular siloxanes or organomodified siloxanes can be used in their preparation, wherein the substances mentioned in the prior art can be used. Preferably, such compounds are used, which are particularly suitable for the respective foam types (rigid foams, hot foams, viscoelastic foams, ester foams, cold foams (HR foams), semi-rigid foams). Suitable (organomodified) siloxanes are described, for example, in the following publications: EP 0839852 . EP 1544235 . DE 102004001408 . EP 0839852 . WO 2005/118668 . US 20070072951 . DE 2533074 . EP 1537159 EP 533202 . US 3933695 . EP 0780414 . DE 4239054 . DE 4229402 . EP 867465 , The preparation of these compounds can be carried out as described in the prior art. Suitable examples are for. In US 4147847 . EP 0493836 and US 4855379 described.

As (foam) stabilizers, it is possible to use all stabilizers known from the prior art. Preference is given to using foam stabilizers based on polydialkylsiloxane-polyoxyalkylene copolymers, as are generally used in the production of urethane foams. These compounds are preferably constructed so that z. B. a long-chain copolymer of ethylene and propylene oxide is connected to a Polydimethylsiloxanrest. The link between the polydialkylsiloxane and the polyether part can take place via an SiC linkage or a Si-OC bond. Structurally, the or the different polyethers may be terminally or pendantly attached to the polydialkylsiloxane. The alkyl radical or the various alkyl radicals may be aliphatic, cycloaliphatic or aromatic. Very particularly advantageous are methyl groups. The polydialkylsiloxane may be linear or contain branches. Suitable stabilizers, in particular foam stabilizers, are inter alia in US 2834748 . US2917480 as in US3629308 described. Suitable stabilizers are available 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

-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 inventive use of the nitrogen-containing compounds of the formula (I), (II), (III) and / or (IV) and / or the corresponding quaternized and / or protonated compounds in the preparation of polyurethane foams , in particular, have the following structure:

wherein
a is independently 0 to 500, preferably 1 to 300 and in particular 2 to 150,
b is independently 0 to 60, preferably 1 to 50 and in particular 1 to 30,
c is independently 0 to 10, preferably 0 or> 0 to 5,
d is independently 0 to 10, preferably 0 or> 0 to 5,
with the proviso that per molecule of the formula (V) the average number Σd of the T units [SiR ³ R ⁴ O] and the mean number Σc of the Q units [SiR ³ R ³ O] per molecule are each not greater than 50 in that the mean number Σa of the D units [SiRRO] per molecule is not greater than 2000 and the mean number Σb of the R ¹ carrying siloxy units per molecule is not greater than 100,
R is independently at least one radical from the group of linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having 1 to 20 carbon atoms, but is preferably a methyl radical,
R ^{2 is} independently R ¹ or R,
R ¹ is different from R and independently of one another an organic radical and / or a polyether radical, the 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

-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 is 0 to 100, preferably> 0, in particular 1 to 50,
z is 0 to 100, preferably> 0, in particular 1 to 10,
R 'is independently an optionally substituted, for example, alkyl, aryl or haloalkyl or haloaryl substituted, alkyl or aryl group having 1 to 12 carbon atoms, wherein within a radical R ¹ and / or a molecule of formula (V) with each other different substituents R 'may be present, and
R '' is independently a hydrogen radical or an alkyl group having 1 to 4 C atoms, a group -C (O) -R '''withR''' = alkyl radical, a group -CH ₂ -O-R ', a Alkylaryl group, such as. A benzyl group, the group -C (O) NH-R ',
R ^{IV is} a linear, cyclic or branched, also more substituted, z. B. halogen-substituted, 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 heteroatom-substituted, functionalized, organic, saturated or unsaturated radical selected from the group of the alkyl, aryl, chloroalkyl, chloroaryl, fluoroalkyl, cyanoalkyl, acryloxyaryl, May be acryloxyalkyl, methacryloxyalkyl, methacryloxypropyl or vinyl radical,
with the proviso that at least one substituent of R ¹ , R ² and R ^{4 is} not equal to R. The various monomer units of the structural units indicated in the formulas (siloxane chains or polyoxyalkylene chain) can be constructed in blocks with any number of blocks and any sequence or statistical distribution. The indices used in the formulas are to be regarded as statistical averages.

The preparation of the siloxanes of the formula (V) can be carried out by the known methods, such as. B. the noble metal-catalyzed hydrosilylation reaction of compounds containing a double bond, with corresponding hydrogen siloxanes such as in EP 1 520 870 , described. The font EP 1 520 870 is hereby incorporated by reference and is considered part of the disclosure of the present invention.

As compounds which have at least one double bond per molecule, z. For example, α-olefins, Vinylpolyoxyalkylene and / or Allylpolyoxyalkylene be used. Preferably, vinylpolyoxyalkylenes and / or allylpolyoxyalkylenes are used. Particularly preferred Vinylpolyoxyalkylene are z. B. vinylpolyoxyalkylenes having a molecular weight in the range of 100 g / mol to 8,000 g / mol, which may be constructed blockwise or randomly distributed from the monomers propylene oxide, ethylene oxide, butylene oxide and / or styrene oxide and which are both hydroxy-functional and by a methyl ether or a Acetoxy function may be endcapped. Particularly preferred Allylpolyoxyalkylene are z. B. allylpolyoxyalkylenes having a molecular weight in the range of 100 g / mol to 5,000 g / mol, which may be constructed blockwise or randomly distributed from the monomers propylene oxide, ethylene oxide, butylene oxide and / or styrene oxide and both hydroxy-functional as by a methyl ether or a Acetoxy function can be end-capped. Particularly preferred compounds which have at least one double bond per molecule, the α-olefins mentioned in the examples, allyl alcohol, 1-hexenol, Vinylpolyoxyalkylene and / or Allylpolyoxyalkylene and Allylglycidylether and vinylcyclohexene oxide used.

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

In a particularly preferred embodiment of the present invention (in particular within the scope of the use according to the invention), siloxanes of the formula (V) are used in which R ¹ independently of one another is 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 independently of one another be different and methyl, ethyl and / or phenyl Represent remnants. R '' is independently a hydrogen radical or an alkyl group having 1 to 4 C atoms, a group -C (O) -R '''withR''' = alkyl radical, a group -CH ₂ -O-R ', a Alkylaryl group, such as. B. a benzyl group, the group -C (O) NH-R ', R ^{IV is} a linear, cyclic or branched, optionally substituted, z. B. substituted with halogens, hydrocarbon radical having 1 to 50, preferably 9 to 45, 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, wherein R ^{1 is} independently 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 in which x is 0 to 100, preferably> 0, in particular 1 to 50, y is 0 to 100, preferably> 0, in particular 1 to 50, R 'is methyl and R "independently of one another radical or an alkyl group having 1 to 4 C atoms, a group C (O) -R '''withR''' = alkyl radical, a group -CH 2 -O-R ', an alkylaryl group, such as. B. a benzyl group, the group C (O) NH-R ', wherein the molar proportion of oxyethylene units based on the total amount of oxyalkylene units mind. 70% of the oxalkylene units, ie x / (x + y)> 0 , 7 is. Under this condition, it is preferred that, in addition, the polyoxyalkylene chain end up carrying a hydrogen. Under these conditions, according to a further preferred embodiment of the invention (in particular within the scope of the inventive use) siloxanes of the formula (V) are used in which the oxalkylene units present in the radical R ¹ are exclusively oxyethylene units and the radical R "is not Is hydrogen.

In a further preferred embodiment of the present invention (in particular within the scope of the use according to the invention), preferably for the production of flexible slabstock siloxanes, siloxanes of the formula (V) are used in which R ₁ independently of one another is 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 in which x is 0 to 100, preferably> 0, in particular 1 to 50, y is 0 to 100, preferably> 0, in particular 1 to 50, R 'is methyl and R "independently of one another 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. B. a benzyl group, the group C (O) NH-R 'means, wherein 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 is.

In a further preferred embodiment of the present invention (in particular within the scope of the use according to the invention), siloxanes of the formula (V) are used in which, among others, olefins are used in the hydrosilylation, whereby R ^{1 is} at least 10 mol%, preferably at least 20 mol, %, more preferably at least 40 mol% of CH ₂ -R ^IV , wherein R ^{IV is} a linear or branched hydrocarbon having 9 to 17 carbon atoms.

In a further preferred embodiment of the present invention (in particular within the scope of the use according to the invention) siloxanes of the formula (V) are used in which the terminal, or also alpha and omega mentioned, positions on the siloxane are at least partially functionalized with radicals R ¹ . In this case, 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 within the scope of the inventive use) siloxanes of the formula (V) are used in which a maximum of 50%, preferably not more than 45%, particularly preferably not more than 40% of the total average molecular weight of the siloxane on the statistical average added molecular weight of all, optionally different, radicals R ¹ in the siloxane omitted.

In a further preferred embodiment of the present invention (in particular within the scope 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 in greater number than the structural elements with the Index b, in such a way that the quotient a / b is at least equal to seven, preferably greater than 10, particularly preferably greater than 12.

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

The siloxanes can also be used in the context of the present invention (in particular within the context of the use according to the invention) as part of compositions with various carrier media become. 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 preparation of polyurethane systems, preferably polyurethane foams, as much of the siloxanes of the formula (V) is added that the mass fraction of compounds of formula (V) on the finished polyurethane system, preferably the polyurethane foam from 0.01 to 10 wt. -%, preferably from 0.1 to 3 wt .-% is.

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

It may be advantageous if, in the preparation of the polyurethane system, a composition is prepared and / or used which comprises at least one nitrogen-containing compound according to the invention of the formula (I), (II), (II) and / or (IV) as defined above , and / or a corresponding quaternized and / or protonated compound, at least one polyol component, optionally at least one isocyanate component and optionally one or more blowing agents, and this composition is reacted. Particular preference is given to using those compositions which have the substances or components described above for use in the production of polyurethanes, in particular polyurethane foams.

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

Another object of the invention is the use of the above-described nitrogen-containing compound of formula (I), (II), (III) and / or (IV), and / or a corresponding quaternized and / or protonated compound, for the production of low-odor Polyurethanes, preferably of low-odor polyurethane foams, in particular odor-poor polyurethane foams. For the term "low odor" reference is made to the preceding description and the explanations there. With respect to preferred embodiments of this subject matter, reference is also made to the preceding description, in particular to the said preferred embodiments.

Another object of the invention is the use of the above-described nitrogen-containing compound of formula (I), (II), (III) and / or (IV), and / or a corresponding quaternized and / or protonated compound, for the production of age-resistant Polyurethane systems, in particular polyurethane foams. With regard to the term "aging-resistant", reference is made to the preceding description and the explanations and test methods described there. In terms of preferred embodiments of this subject is also made to the preceding description, in particular to the said preferred embodiments.

Another object of the invention is the use of the above-described nitrogen-containing compound of the formula (I), (II), (III) and / or (IV), and / or a corresponding quaternized and / or protonated compound, for the production of discoloration-minimized Polyurethane systems, in particular of polyurethane foams, preferably of polyurethanes for use in the automotive industry, in particular in automotive interiors, for example as a headliner, 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 lead in particular to lower 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 non-inventive amines, as can be demonstrated, 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 respect to preferred embodiments of this subject matter, reference is also made to the preceding description, in particular to the said preferred embodiments.

Another object of the invention is the use of the above-described nitrogen-containing compound of formula (I), (II), (III) and / or (IV), and / or a corresponding quaternized and / or protonated compound, for the preparation of polyurethane systems with a broad processing play, in particular of semi-hard polyurethane foams (open-cell rigid foams, in particular for use as a headliner in automobile interiors). "Wide processing clearance" means that advantageously a greater variation in the use concentration of the nitrogen-containing compounds according to the invention without adversely affecting the desired material properties, for example the open-cell foam or the space-weight distribution over the foam block, is possible compared to comparable amine catalysts or those usually used 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 respect to preferred embodiments of this subject matter, reference is also made to the preceding description, in particular to the said preferred embodiments.

The invention furthermore relates to a composition comprising at least one polyol component, the composition comprising at least one nitrogen-containing compound of the formula (I), (II), (III) and / or (IV) as defined and described above, and / or the corresponding quaternized compounds and / or protonated compounds, wherein the composition preferably has at least one isocyanate component, and wherein the nitrogen-containing compound of formula (I), (II), (III) and / or (IV) preferably as a technical product mixture, as described above, included and wherein the composition preferably comprises additional amine catalysts other than formula (I), (II), (III) and / or (IV).

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

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

The composition of the invention may additionally comprise one or more propellants as described above. In addition to or instead of blowing agents, the composition of the invention may comprise further additives / auxiliaries or additives which are used in the preparation of polyurethane systems, preferably polyurethane foams. A selection of suitable auxiliaries / additives / additives, such. As foam stabilizers or flame retardants, has been described above in the preparation of the polyurethane systems, in particular the polyurethane foams.

The processing of the compositions according to the invention into polyurethane systems, in particular polyurethane foams, can be carried out by all methods familiar 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. In this case, discontinuous processes, for example for the production of molded foams, refrigerators, automobile seats, and panels, or continuous processes, for example in insulation boards, metal composite elements, block foams or spraying can be used.

All processes known to those skilled in the art for producing polyurethane foams can be used. For example, the foaming process can take place both horizontally and vertically, in discontinuous or continuous plants. Likewise, the compositions used according to the invention can be used for CO ₂ technology. The use in low-pressure and high-pressure machines is possible, wherein the compositions can be metered either directly into the mixing chamber or even before the mixing chamber of one of the then passing into the mixing chamber components are admixed. The admixture can also be done in the raw material tank.

By means of the use according to the invention of nitrogen-containing compounds of the formula (I), (II), (III) and / or (IV), and / or the corresponding quaternized and / or protonated compounds, the polyurethane systems according to the invention described below are obtainable.

• (a) zumindest eine stickstoffhaltige Verbindung der Formel (I), insbesondere zumindest eine stickstoffhaltige Verbindung nach der Formel (II), (III), oder (IV), 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.-%,
• (b) optional 1-(3-Aminopropyl)pyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20–95 Gew.-%, insbesondere 30–70 Gew.-%,
• (c) optional 1-(2-Aminoethyl)pyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20–95 Gew.-%, insbesondere 30–70 Gew.-%,
• (d) optional 1-(2-Hydroxyethyl)pyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20–95 Gew.-%, insbesondere 30–70 Gew.-%,
• (e) optional 1-(3-Hydroxypropyl)pyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20–95 Gew.-%, insbesondere 30–70 Gew.-%,
• (f) 2-(2-(Pyrrolidin-1-yl)ethoxy)ethanol, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20–95 Gew.-%, insbesondere 30–70 Gew.-%,
• (g) 1,1'-(Oxybis(ethan-2,1-diyl))dipyrrolidin, vorteilhafterweise in einer Menge ≥ 5 Gew.-%, bevorzugt 20–95 Gew.-%, insbesondere 30–70 Gew.-%,
• (h) optional Ethylendiamin (EDA), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%,
• (i) optional 1,4-Butandiol, vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%,
• (j) optional Monoethylenglycol (MEG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%,
• (k) optional Diethylenglycol (DEG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%,
• (l) optional 1,2-Propylenglycol (PG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%,
• (m) optional Dipropylenglycol (DPG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%,
• (n) optional Diethanolamin, vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%,
• (o) optional Triethanolamin, vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%,
• (p) optional Monoethanolamin (MEA), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20–90 Gew.-%, bevorzugt 30–80 Gew.-%, und/oder
• (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 of polyurethane foams containing

• (a) at least one nitrogen-containing compound of the formula (I), in particular at least one nitrogen-containing compound of the formula (II), (III), or (IV), more preferably at least one nitrogen-containing compound of the formula (III), advantageously in one Total amount of ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
• (b) optionally 1- (3-aminopropyl) pyrrolidine, advantageously in an amount ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
• (c) optionally 1- (2-aminoethyl) pyrrolidine, advantageously in an amount of ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
• (d) optionally 1- (2-hydroxyethyl) pyrrolidine, advantageously in an amount of ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
• (e) optionally 1- (3-hydroxypropyl) pyrrolidine, advantageously in an amount of ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
• (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,
• (g) 1,1 '- (oxybis (ethane-2,1-diyl)) dipyrrolidine, advantageously in an amount of ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight .
• (h) optionally ethylenediamine (EDA), advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
• (i) optionally 1,4-butanediol, advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
• (j) optionally monoethylene glycol (MEG), advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
• (k) optionally diethylene glycol (DEG), advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
• (I) optionally 1,2-propylene glycol (PG), advantageously in an amount of ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
• (m) optionally dipropylene glycol (DPG), advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
• (n) optionally diethanolamine, advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
• (o) optionally triethanolamine, advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
• (P) optionally monoethanolamine (MEA), advantageously in an amount ≤ 95 wt .-%, in particular 20-90 wt .-%, preferably 30-80 wt .-%, and / or
• (q) optionally trimethylene glycol, butyl diglycol, neopentyl glycol, 2-methyl-1,3-propanediol, N, N-dimethylcyclohexylamine, N, N-dimethylaminopropylamine, triethylenediamine, 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 wt .-%, in particular 20-90 wt .-%, preferably 30-80 wt .-%.

Within the meaning of the abovementioned subject matter 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), (III) or (IV), 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 1), 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), e), b) and j), e), c) and j), e), b) and j), f) and j), 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 further subject of the present invention is therefore a polyurethane system obtainable by a use as described above.

These polyurethane systems according to the invention are preferably polyurethane foams, preferably rigid polyurethane foams, flexible polyurethane foams, viscoelastic foams, highly elastic foams so-called "high resilience foams" (HR), semi-rigid polyurethane foams, thermoformable polyurethane foams or integral foams. The term polyurethane is in turn here as a generic term for a di- or polyisocyanates and polyols or other isocyanate-reactive species, such as. As amines to understand polymer produced, wherein the urethane bond does not have to be exclusive or predominant type of bond. Also, polyisocyanurates and polyureas are expressly included.

The polyurethane system according to the invention, in particular polyurethane foam, is preferably characterized in 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, wherein it preferably has a mass fraction nitrogen-containing compounds of the formula (I), (II), (III) and / or (IV), and / or the corresponding quaternized and / or protonated compounds or of the radicals obtained by reacting these on the finished polyurethane foam of 0.005 to 10 wt. -%, preferably from 0.05 to 3 wt .-%, particularly preferably 0.1 to 1 wt .-%, having.

In a preferred embodiment, the polyurethane foams according to the invention or produced according to the invention are open-celled polyurethane foams, in particular flexible foams, particularly preferably hot-melt foams. Open cell in the context of the present invention means that a foam has a good air permeability (= porosity). The air permeability of the foam can be determined by a dynamic pressure measurement on the foam. The dynamic pressure measurement can be based on EN 29053 respectively. If the measured back 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 mm, determined in accordance with the measuring method described in the examples.

A preferred composition for the production of polyurethane or polyisocyanurate foam in the context of the present invention has a density (RG) of preferably 5 to 800, in particular 5 to 300, preferably 5 to 150, particularly preferably from 10 to 90 kg / m ³ and in particular has the following composition: component weight proportion polyol 100 (Amine) catalyst 0.05 to 5 Potassium trimerization 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 retardants 0 to 70 fillers 0 to 150 other additives 0 to 20 Isocyanate index: greater than 15

Another object of the invention is the use of polyurethane systems, in particular of polyurethane foams, as described above, as refrigerator insulation, insulation board, sandwich element, pipe insulation, spray foam, 1- & 1,5-component foam foam, imitation wood, model foam, floral foam, packaging foam, mattress , Furniture upholstery, molded foam, pillows, rebonded foam, sponge foam, automobile upholstery, headrest, instrument panel, automotive interior trim, automotive headliner, sound absorbing material, steering wheel, shoe sole, carpet back foam, filter foam, sealant, sealant and adhesive, or for making such products ,

In the examples given below, the present invention is described by way of example, without the invention, the scope of application of which is apparent from the entire description and the claims, to be limited to the embodiments mentioned in the examples.

Examples

Preparation of nitrogen-containing compounds according to the invention

Synthesis Example 1: Preparation of a compound of the formula (III), using the example of the compound of the formula (IIIa)

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

In a 250 ml four-necked flask equipped with KPG stirrer, reflux condenser, temperature probe and inert gas inlet 35.0 g (0.187 mol) of 1,2-bis (2-chloroethoxy) -ethane were submitted. After inerting the reaction apparatus with nitrogen was heated to 50 ° C. At a reaction temperature of 50 ° C was started by means of a dropping funnel with the dosage of an amount of 60.0 g (0.84 mol) of pyrrolidine. The dosage was within 30 minutes, the exotherm of the reaction leading to a temperature increase up to 73 ° C. After completion of the dosing was heated to 90 ° C and held for 5 hours, the reaction temperature. After complete reaction time, the reaction mixture was allowed to cool to room temperature calmly. It was found on the following day that formed by quaternization by-products were crystallized in the reaction mixture. To separate them, the batch was heated to 60 ° C and added to 150 ml of heptane. It was then filtered off through a fluted filter and the solvent and volatile components were distilled off on a rotary evaporator at 105 ° C and <1 mbar. It was thus possible to obtain 42.11 g of a clear, slightly yellowish product of the formula (IIIa). The 13 C NMR analysis met expectations and confirmed product formation.

Synthesis Example 2: Preparation of a compound of the formula (III), using the example of the compound of the formula (IIIb)

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

The technical teaching of EP 1945222 B1 Following (Intermediate 11) an amount of 18.67 g (263 mmol) of pyrrolidines and 375 ml of acetonitrile were initially charged in an apparatus consisting of a 1 L multi-neck flask equipped with KPG stirrer, reflux condenser, dropping funnel and temperature sensor with inert gas feed. It was heated to the 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 a little ethyl acetate. The filtrate was then concentrated by evaporation on a rotary evaporator, the residue taken up with a little diethyl ether, provided with filter aid (Celite ^© ) and filtered again. The filtrate was concentrated again sharply on a rotary evaporator so that 41.16 g (81% of theory) of a slightly yellow oil could be obtained as a product of the formula (IIIb). Analysis by 1H and 13C NMR spectroscopy was in line with expectations and confirmed product formation.

Synthesis Example 3: Preparation of a compound of the formula (III), using the example of the compound of the formula (IIIc)

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

The technical teaching of G. Jenner et al. ( 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 sensor 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 thermo-oil, whereby a pressure increase could be observed. The reaction temperature was then maintained under stirring for 9 hours. After the reaction time was allowed to cool to room temperature and the reaction mixture analyzed by gas chromatography. Analysis showed, besides unreacted 1- (2-aminoethyl) pyrrolidine, a small proportion of the mono-attached product and the product of formula (IIIc).

The crude reaction mixture was provided with a little filter aid (Celite ^© ), filtered through a fluted filter and then subjected to fine distillation. It was thus possible in a clear fraction (1 mbar / 85-90 ° C) 23.2 g of the mono-deposited product in a purity of 97.2% and in a likewise clear, slightly yellowish and at room temperature oil-like viscous fraction (0.5-0.8 mbar / 128-138 ° C) 61.3 g of the di-annealed product of formula (IIIc) are obtained. The NMR spectroscopy as well as the GC and GC / MS analyzes confirmed the product formation.

Synthesis Example 4: Preparation of a compound of the formula (III), using the example of the compound of the formula (IIId) and (IIIe)

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

The technical teaching of G. Jenner et al. (Journal of Organometallic Chemistry, 373, 1989, 343-352) Subsequently, in a 500 ml laboratory autoclave, equipped with a stirrer, a heatable jacket, pressure transducer and temperature probe and inert gas inlet, 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 thermo-oil, whereby a pressure increase could be observed. The reaction temperature was then maintained under stirring for 9 hours. After the reaction time was allowed to cool to room temperature and the The reaction mixture was analyzed by gas chromatography. The analysis showed not only unreacted 1- (2-aminoethyl) pyrrolidine but also a mono-attached product as well as the di-annealed product. The crude reaction mixture was provided with a little filter aid (Celite ^© ), filtered through a pleated filter and then subjected to fine distillation by means of short-path evaporator. It could thus in a slightly yellowish, but clear fraction at 0.8-1 mbar and a jacket temperature of 100 ° C, an amount of 44.2 g of the mono-attached product according to the formula (IIId) in a purity of 95.5 % be won. Furthermore, in a likewise clear, but clearly orange and viscous at room temperature fraction, at a pressure of 0.05-0.09 mbar and a jacket temperature of 160 ° C, an amount of 51.3 g of the di-annealed product of formula (IIIe) are won. The NMR spectroscopic as well as the GC and GC / MS analyzes confirmed the product formation.

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 Chemistry GmbH

In a 1000 ml laboratory autoclave, equipped with a stirrer, a heatable jacket, pressure sensor and temperature probe and inert gas inlet was under cooling by means of a dry ice / IPA cooling mixture, a quantity of 333.4 ml of a 3 molar solution of ethylene oxide in THF (corresponding to 1 mol Ethylene oxide) and an additional 35.56 g (0.5 mol) of pyrrolidine are added. The autoclave previously purged with nitrogen was then heated over the jacket with a thermo-oil to 100 ° C, whereby a pressure increase could be observed. It was then kept under stirring for 6 hours, the reaction temperature. After the reaction time was allowed to cool to room temperature, the pressure vessel was depressurized and purged with nitrogen. The solvent was removed several hours on a rotary evaporator at a bath temperature of 50 ° C in a membrane pump vacuum. The crude reaction mixture was then analyzed by gas chromatography, wherein in addition to 15.1% unreacted pyrrolidine also 42.9% of the desired mono-ethoxylated pyrrolidine and 26.7% of di-ethoxylated pyrrolidine and 10.7% tri-ethoxylated pyrrolidine and 4 in total , 6% of other by-products or solvent residues were found. It was then carried out to isolate the desired mono- and di-ethoxylated pyrrolidine a fine distillation. It was thus possible 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 di-ethoxylated target product 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol are obtained in a GC purity of 94.2%. The NMR spectroscopic as well as the GC and GC / MS analyzes confirmed the product formation.

Synthesis Example 6: Preparation of a compound of the formula (III), using the example of the compound of the formula (IIIf)

chemical CAS supplier 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol 4076-32-8 2-methylamino-ethanol,> 98% 109-83-1 Sigma-Aldrich Chemistry GmbH Ruthenium (III) chloride trihydrate, techn. 13815-94-6 Sigma-Aldrich Chemistry GmbH Triphenylphosphine, 99% 603-35-0 Sigma-Aldrich Chemistry 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 used in a 500 ml laboratory autoclave equipped with a stirrer, a heatable jacket, pressure sensor and temperature probe and 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) of triphenylphosphine. The autoclave was sealed, rendered inert with nitrogen, and the jacket was heated to 190 ° C. with a thermo-oil, whereby a pressure increase could be observed. The reaction temperature was then maintained under stirring for 9 hours. After the reaction time was allowed to cool to room temperature and the reaction mixture analyzed by gas chromatography. GC and GC / MS analysis showed not only unreacted 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol but also 38% of the desired product, but also significant amounts of by-products from the intermolecular reaction of 2 methylamino-ethanol of. 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. Subsequently, a fractional fine distillation was carried out so that the desired product according to the formula (IIIf) could be obtained in 23% yield. The NMR spectroscopic as well as the GC or GC / MS analyzes confirmed the desired product formation.

Synthesis Example 7: Preparation of a compound of the formula (III), using the example of the compound of the formula (IIIg)

chemical CAS supplier 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol 4076-32-8 Methylamine, 2 M in THF 74-89-5 Sigma-Aldrich Chemistry GmbH Ruthenium (III) chloride trihydrate, techn. 13815-94-6 Sigma-Aldrich Chemistry GmbH Triphenylphosphine, 99% 603-35-0 Sigma-Aldrich Chemistry 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) in a 500 ml laboratory autoclave equipped with a stirrer, a heatable jacket, pressure sensor and temperature probe and inert gas feed ethanol, 250 ml (corresponding to 0.5 mol) of a solution of methylamine (2M in THF), 491 mg (1.875 mmol) of ruthenium (III) chloride trihydrate (0.375 mol% based on 2- (2- pyrrolidin-1-yl) ethoxy) ethanol) and 1.48 g (5.7 mmol) of triphenylphosphine. The autoclave was sealed, rendered inert with nitrogen and the jacket heated with a thermo-oil to 130 ° C with a pressure increase could be observed It was then kept under stirring for 12 hours, the reaction temperature. After the reaction time was allowed to cool to room temperature and the reaction mixture analyzed by gas chromatography. GC and GO / MS analysis showed significant levels of unreacted 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol, but also 23% desired product levels, among various other by-products. The crude reaction mixture was therefore washed with ethanol and little filter aid (Celite ^© ). provided, filtered through a pleated filter and the solvent is then removed on a rotary evaporator. The residue was then subjected to a fractional fine distillation, whereby the desired product of the formula (IIIg) could be recovered in a 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 - foaming examples

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

For the performance testing of the nitrogen-containing compounds according to the invention, the foam formulation indicated in Table 1 was used. Table 1: Formulation 1 for rigid foam applications. Formulation 1 Mass parts (pphp) Polyol 1 ¹⁾ 100 parts water 2.60 parts cyclopentane 13.1 parts Amin 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 having an OH number of 471 mgKOH / g.
²⁾ Polyether-modified polysiloxane.
³⁾ polymeric MDI from Bayer, 200 mPa · s, 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 nitrogenous catalysts (amines). For this purpose, polyol 1, conventional or inventive nitrogen-containing catalyst (amine), water, foam stabilizer and blowing agent were weighed into a beaker and mixed with a paddle stirrer of 6 cm diameter for 30 seconds at 1000 rev / min. By reweighing, 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 and 14 cm height). To evaluate the catalytic properties, the following characteristic parameters were determined: cream time, gel time (thread cessation time), rise time and tack-free time.

The results of the evaluation of the catalytic properties of the nitrogen-containing compound according to the invention of the formula (III) are summarized in Table 2. As comparative catalysts of the prior art, N, N-dimethylcyclohexylamine (DMCHA), dimethylaminoethoxyethanol (DMEE), pentamethyldiethylenetriamine (PMDETA) and bis (2-dimethylaminoethyl ether) (BDE) were used. Table 2: Results of foaming according to Formulation 1 (Table 1). Amin 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⁾ 20 160 235 325 FORMULA (IIIb *) ¹⁾ 39 176 277 290 FORMULA (IIIc *) ¹⁾ 62 282 435 510 FORMULA (IIId *) ¹⁾ 53 214 378 432 FORMULA (IIIe *) ¹⁾ 55 219 390 420 FORMULA (IIIf *) ¹⁾ 20 136 203 218 FORMULA (IIIg *) ¹⁾ 17 128 227 278 ¹⁾ 1.50 parts of catalyst used.
^{2) used} 0.80 parts of catalyst.
³⁾ Time information in seconds [s].
* each obtained according to the aforementioned synthesis examples

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

Flexible foam - application tests

Physical properties of flexible polyurethane foams:

• 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.
• 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.
• 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.
• 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.
• e) Stauchhärte CLD, 40% nach DIN EN ISO 3386 . Die Angabe der Messwerte erfolgt in Kilopascal (kPa).

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

• a) Slumping of the foam after the end of the climbing phase (= relapse): The relapse, or the rise is the difference of the foam height after direct blowing and after 3 minutes. after blowing off the foam. The foam height is measured by a needle attached to a centimeter measure at the maximum in the middle of the foam cap. A negative value here describes the backsetting of the foam after blowing off, a positive value correspondingly describes the rising of the foam.
• b) Foam Height: The final height of the foam is determined by subtracting or adding the fallback or rising to or from the foam height after blow off. The foam height is given in centimeters (cm).
• c) Density (RG): The determination is made as in ASTM D 3574-11 described under Test A, by measuring the core density. The density is given in kg / m ³ .
• 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 of 0 to 300 mm. The back pressure was measured by means of an apparatus comprising a nitrogen source, reducing valve with pressure gauge, flow control screw, wash bottle, flow meter, T-piece, support nozzle and a graduated glass tube in 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 admission pressure by reducing valve to 1 bar and adjusting the flow rate to 480 l / h. The amount of water is adjusted in the scaled glass tube so that no pressure difference is built up and readable. For the measurement of the test specimen with a dimension of 250 × 250 × 50 mm, the support nozzle is placed edge-matching at the corners of the specimen and placed once at the (estimated) center of the specimen (each on the side with the largest surface). It is read when a constant dynamic pressure has set. The evaluation is carried out by averaging over the five obtained measured values.
• e) compressive strength CLD, 40% after DIN EN ISO 3386 , The values are given in kilopascals (kPa).

• 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.
• b) Die Messbedingungen für VOC-Messungen sind in Tabellen 3 und 4 angegeben.

Tabelle 3: Messparameter Thermodesorption für den VOC-Analysenlauf. Thermodesorption Gerstel TDS2 Desorptionstemperatur 90°C Desorptionsdauer 30 min Fluss 65 ml/min Transferline 280°C Kryofokussierung KAS 4 Liner Glasverdampferrohr mit silanisierter Glaswolle Temperatur –150°C Tabelle 4: Messparameter Gaschromatographie/Massenspektrometrie für den VOC-Analysenlauf. GC Kapillar-GC Agilent 7890 Injektor PTV Split 1:50 Temperaturprogramm –150°C; 1 min; ⇗10°C/s; 280°C Säule Agilent 19091B-115, Ultra 2, 50 m* 0,32 mm dF 0,5 μm 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 19091 B-115, Ultra 2, 50 m* 0,32 mm dF 0,5 μm 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 of October 2011 :
The method is used to detect non-metallic material emissions that are used in automotive moldings. 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 catalysis-related emissions, the emissions of the individual constituents of inventive catalyst combinations or their decomposition or reaction products was based on the test specification VDA 278 in the version of October 2011 determined. In the following, the implementation of the corresponding thermal desorption with subsequent gas chromatography / mass spectrometry coupling (GC / MS) is described.

• a) Measurement Technique: Thermodesorption was performed with a thermal desorber "TDS2" with a sample changer from Gerstel, Mülheim, in conjunction with an Agilent 7890/5975 GC / MSD system.
• b) The measurement conditions for VOC measurements are given in Tables 3 and 4.

Table 3: Measurement parameters thermal desorption for the VOC analysis run. Thermal desorption Gerstel TDS2 desorption 90 ° C desorption time 30 min River 65 ml / min transfer Line 280 ° C cryofocussing KAS 4 liner Glass evaporator tube with silanized glass wool temperature -150 ° C Table 4: Measurement parameters gas chromatography / mass spectrometry for the VOC analysis run. GC Capillary GC Agilent 7890 injector PTV Split 1:50 temperature program -150 ° C; 1 min; ⇗10 ° C / s; 280 ° C pillar Agilent 19091B-115, Ultra 2, 50 m * 0.32 mm dF 0.5 μm River 1.3 ml / min const. flow temperature program 50 ° C; 2 minutes; ⇗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 total ion current Chromatogram by calculation as toluene equivalent

• c) Calibration: For calibration, 2 μl of a mixture of toluene and hexadecane in methanol (0.125 mg / ml each) was added to a purified adsorption tube filled with ^Tenax® TA (mesh 35/60) and measured (desorption 5 min, 280 ° C) 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 of foam were placed in three subsamples in a thermodesorption tube. It was ensured that the foam is not compressed.
• f) Sample Preparation for Fog Measurement: The same foam sample was used as for VOC measurement. With regard to the measuring arrangement, first the VOC measurement and then the Fog measurement were carried out, whereby a constant distance between the corresponding VOC and Fog measurements was ensured by means of an autosampler system.
• g) Measurement conditions for fog measurements are given in Tables 5 and 6.

Table 5: Measurement parameters thermal desorption for the fog analysis run. Thermal desorption Gerstel TDS2 desorption 120 ° C desorption time 60 min River 65 ml / min transfer Line 280 ° C cryofocussing 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 19091 B-115, Ultra 2, 50 m * 0.32 mm dF 0.5 μm River 1.3 ml / min const. flow temperature program 50 ° C; 2 minutes; ⇗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 total ion current Chromatogram by calculation as hexadecane equivalent

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

• 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.
• 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 0,5 μm 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): Of the foams obtained, the emission, in particular the catalysis-related emissions, the emissions of the individual components of inventive catalyst combinations or their decomposition or reaction products, at room temperature based on DIN standard DIN EN ISO 16000-9: 2008-04 certainly. The sample was taken after 24 hours. For this purpose, 2 liters of Prüfkammeratmosphäre was added at a flow rate of 100 ml / min with a Tenax ^® TA (mesh35 / 60) filled adsorption. The following describes the performance of thermal desorption followed by gas chromatography / mass spectrometry coupling (GC / MS).

• a) Measurement Technique: Thermodesorption was performed with a thermal desorber "TDS2" with a sample changer from Gerstel, Mülheim, in conjunction with an Agilent 7890/5975 GC / MSD system.
• b) The measurement conditions are given in Tables 7 and 8.

Table 7: Measurement parameters thermal desorption for PC measurement. Thermal desorption Gerstel TDS2 desorption 280 ° C desorption time 5 min River 65 ml / min transfer Line 280 ° C cryofocussing 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 River 1.3 ml / min const. flow temperature program 50 ° C; 2 minutes; ⇗3 ° C / min; 92 ° C; ⇗5 ° C / min; 160 ° C; ⇗10 ° C / min; 280 ° C, 20 min detector Agilent MSD 5975 evaluation Evaluation of total ion current Chromatogram by calculation as toluene equivalent

• c) The calibration was 2 .mu.l of a mixture of toluene and hexadecane in methanol (depending 0.125 mg / ml) to a purified, optionally with Tenax ^® TA (mesh35 / 60) filled adsorption and measured (desorption 5 min; 280 ° C).

Flexible foam - foaming examples

Example 2 Production of Flexible Polyurethane Foams (Soft Block Foam)

For the performance testing of the nitrogen-containing compounds according to the invention, the foam formulation given in Table 9 was used. Table 9: Formulation 2 for soft block foam applications. Formulation 2 Mass parts (pphp) Polyol 1 ¹⁾ 100 parts water 3.00 parts Tin catalyst ²⁾ 0.20 parts Amin 0.20 parts TEGOSTAB ^® BF 2370 ³⁾ 0.80 parts Desmodur ^® T 804) 38.1 parts ¹⁾ Polyol 1: Glycerol-based polyether polyol having an OH number of 48 mgKOH / g.
²⁾ COSMOS ^® 29, available from Evonik Industries: tin (II) salt of 2-ethylhexanoic acid.
³⁾ Polyether-modified polysiloxane.
⁴⁾ tolylene diisocyanate T 80 (80% 2,4-isomer, 20% 2,6-isomer) from Bayer, 3 mPa · s, 48% NCO, functionality 2.

In the foaming 500 g of polyol were used; the other formulation components were converted accordingly. In this case, 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. Those given in formulations as shown in Table 9 were used with various nitrogenous 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 rev / min. After addition of the isocyanate (TDI), the reaction mixture was stirred for 7 s at 2500 rpm and immediately transferred to a box lined with paper (27 cm × 27 cm base and 27 cm height). To evaluate the catalytic properties, the following characteristic parameters were determined: cream time, rise time, rise height, blow-off strength (= blow-off) and back-foaming of the foam after the end of the rise phase (= relapse).

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

The results of the evaluation of the catalytic properties of the nitrogen-containing compound according to the invention of the formula (III) and of the physical properties of the resulting flexible slab foams are summarized in Table 10. As comparative catalysts of the prior art triethylenediamine were 33% by weight solution in dipropylene glycol (TEGOAMIN ^® 33, available from Evonik Industries), N, N-dimethylethanolamine (TEGOAMIN ^® DMEA, commercially available from Evonik Industries) bis (2-dimethylaminoethyl ether), 70 wt .-% solution in dipropylene glycol (BDE TEGOAMIN ^®, available from Evonik Industries) and N, N, N'-trimethyl-N '- (2-hydroxyethyl) bis (2- aminoethyl) ether (Jeffcat ZF-10 ^®, are used obtainable from Huntsman). In each case 0.20 pphp (= parts by weight based on 100 parts by weight of polyol) of amine was used. Table 10: Results of foaming according to Formulation 2 (Table 9). Amin Rise time relapse height RG porosity CLD 40% [S] [cm] [cm] [kg / m] ³ [mm] ¹⁾ [KPa] TEGOAMIN ^® 33 120 0.1 28.6 31.6 24 4.4 TEGOAMIN ^® DMEA 137 0.1 28.0 31.2 17 3.8 TEGOAMIN ^® BDE 93 0.6 29.0 30.9 12 3.5 Jeffcat ^® ZF-10 108 0.6 29.0 30.7 10 3.5 FORMULA (IIIa *) 120 0.3 28.7 31.2 18 3.7 FORMULA (IIIb *) 150 0.0 27.5 31.6 36 4.2 FORMULA (IIIc *) 133 0.2 28.0 31.3 20 4.0 FORMULA (IIId *) 119 0.4 28.6 31.0 16 3.9 FORMULA (IIIe *) 128 0.2 28.4 31.4 21 3.9 FORMULA (IIIf *) 112 0.4 28.8 31.0 15 3.7 FORMULA (IIIg *) 115 0.3 28.7 31.2 18 3.9 ¹⁾ = (dynamic pressure in mm water column).
* each obtained according to the aforementioned synthesis examples

As can be seen from Table 10, the compounds of the formula (III) have, in part, a high catalytic activity in the hot flexible foam. In the chosen formulation it was possible with all compounds of the formula (III) to produce sufficient open-cell flexible foams. 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 as TEGOAMIN ^® DMEA, with particular compound of the formula (IV) compared to TEGOAMIN ^® DMEA has a slightly increased gel selectivity. The compounds of the formula (IIIa) and (IIId) are with respect to the rise time comparable 33. with TEGOAMIN ^® However, interpret the received physical measurement values indicate that it is here to catalysts which, although having a balanced selectivity, but the fuels Slightly prefer reaction.

Example 3: Emissions of 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 specified in Table 11, which contains a low-emission polyol and a low-emission tin catalyst, was used for the performance testing of flexible slab foams. Table 11: Formulation 3, foam emissions in soft block foam applications. Formulation 3 Mass parts (pphp) Polyol 1 ¹⁾ 100 parts water 3.00 parts Tin catalyst ²⁾ 0.60 parts Amin 0.15 parts TEGOSTAB ^® BF 2370 ³⁾ 0.80 parts Desmodur ^® T 80 ⁴⁾ 41.6 parts ¹⁾ Polyol 1: Low-emission glycerol-based polyether polyol having an OH number of 56 mgKOH / g.
²⁾ COSMOS ^® EF, available from Evonik Industries: tin (II) salt of ricinoleic acid.
³⁾ Polyether-modified polysiloxane.
⁴⁾ tolylene diisocyanate T 80 (80% 2,4-isomer, 20% 2,6-isomer) from Bayer, 3 mPa · s, 48% NCO, functionality 2.

In the foaming 500 g of polyol were used; the other formulation components were converted accordingly. In this case, 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. Those used in formulations as shown in Table 11 were used with various nitrogenous 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 rev / min. After addition of the isocyanate (TDI), the reaction mixture was stirred for 7 s at 2500 rpm and immediately transferred to a box lined with paper (27 cm × 27 cm base and 27 cm height) and the resulting foam after blowing off with polyethylene film hermetically sealed. After a curing period of 24 hours, a defined foam cube (7 cm × 7 cm × 7 cm) was cut from the resulting foam block, which was completely enclosed with aluminum foil and further sealed with polyethylene film.

The emission behavior of the foams described above was subsequently measured at room temperature after the test chamber test in accordance with the DIN standard DIN EN ISO 16000-9: 2008-04 as described above. The results are shown in Table 12. Table 12: Emissions of flexible slab foams according to Formulation 3 (Table 11). Content of volatile organic compounds after the Test chamber test Amin PK _ges ¹⁾ PK _amine ¹⁾ [μg / m ³ ] [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 _total = total emission; PK _amine = amine emissions of all volatile organic compounds in the test chamber test.
* each obtained according to the aforementioned synthesis examples

Table 12 shows that the slabstock foams obtained using the nitrogen-containing compounds according to formula (III) reduced amine emissions as described above after the Prüfkammertest, having, when using conventional catalysts such as TEGOAMIN ^® BDE or TEGOAMIN ^® 33 . as used herein formulation could even how to TEGOAMIN ^® DMEA and Jeffcat ^® ZF-10 also, most small amine emissions <10 ug / m ³ are obtained in most cases, the resulting foams were even free of such emissions. Also regarding the amine emissions according to the VDA 278, as described above , A partial reduction of the amine emissions with appropriate catalyst-exchange TEGOAMIN ^® BDE or TEGOAMIN ^® was observed 33rd

Example 4: Preparation of HR foams (block / molded)

For the performance testing of the nitrogen-containing compounds according to the invention, the foam formulation indicated in Table 13 was used. Table 13: Formulation 4 for Cold Foam Applications (HR Block / Molded). Formulation 4 Mass parts (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 Amin 0.25 parts TEGOSTAB ^® B 8716 LF2 ³⁾ 1.00 parts Desmodur ^® T 80 ⁴⁾ 44.0 parts ¹⁾ Polyol 1: sorbitol / glycerol-based polyether polyol having 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⁾ tolylene diisocyanate T 80 (80% 2,4-isomer, 20% 2,6-isomer) from Bayer, 3 mPa · s, 48% NCO, functionality 2.

Here, the same foaming methods as in the conventional flexible polyurethane foam in Examples 2 and 3 were used.

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

For foaming polyol, water, amine, and silicone stabilizer were mixed well with stirring. After addition of the isocyanate was 4 s with a stirrer at 3000 U / min. stirred and the mixture in a paper-lined wooden box (27 cm × 27 cm and 27 cm height) poured. The resulting foam was subjected to the performance tests described below.

The results of the evaluation of the catalytic properties of the compound according to the invention of the formula (III) and the physical properties of the resulting foams are summarized in Table 14. As comparative catalysts of the prior art triethylenediamine were 33% by weight solution in dipropylene glycol (TEGOAMIN ^® 33, available from Evonik Industries), N, N-dimethylethanolamine (TEGOAMIN ^® DMEA, commercially available from Evonik Industries) bis (2-dimethylaminoethyl ether), 70 wt .-% solution in dipropylene glycol (BDE TEGOAMIN ^®, available from Evonik Industries) and N, N, N'-trimethyl-N '- (2-hydroxyethyl) bis (2- aminoethyl) ether (Jeffcat ZF-10 ^®, are used obtainable from Huntsman). In each case, 0.25 pphp (= parts by weight based on 100 parts by weight of polyol) of amine were used. Table 14: Results of foaming according to Formulation 4 (Table 13). Amin gel time Rise time height relapse Cell number 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 to 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

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

QUOTES INCLUDE IN THE DESCRIPTION

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Claims (26)

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

with n = 1 to 30, in particular 1 to 12, preferably 2 to 6, preferably 2 or 3, particularly preferably 2, a, b equal to or different from 0 to 3, with the proviso that a + b = 2 or 3 , wherein the ether or amine building blocks, if present, can occur cumulatively, alternately, blockwise or disorderly, R ₁ , R _{2 are the} same or different, 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, more preferably having 2 carbon atoms, R ₃ = H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally with one or is a hydrocarbon radical of 1 to 30 carbon atoms which is substituted by several heteroatoms or interrupted by one or more heteroatoms,

R ₄ , R _{5 is the} same or different H, is a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more hetero atoms or interrupted by one or more hetero atoms hydrocarbon radical or R ₄ and R ₅ to a Cycle, preferably bridged to a pyrrolidine radical, a morpholine radical, an imidazole radical or a piperazine radical, wherein

in particular equal to * -NH ₂ ,

where R ₇ , R ₈ , R _{9 are} identical or different and denote H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more hetero atoms or interrupted by one or more hetero atoms hydrocarbon radical having 1 to 30 carbon atoms is, for Y = * -OR ₆ R ₆ is H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more hetero atoms or interrupted by one or more hetero atoms hydrocarbon radical, wherein * -OR ₆ preferably equal to * -OH or

In particular, Y is * -OH, * -NH ₂ ,

or

preferably * -OH, * -NH ₂ or

particularly preferred * -OH or

Use according to Claim 1, characterized in that at least one nitrogen-containing compound of the formula (I) where R _{3 is} selected from the following radicals: * -H, * -CH ₃ ,

with m = 1 to 12, in particular 1 to 6, preferably 2 or 3, particularly preferably 2, with o, p, s, t being equal to or not equal to 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 are the} same or different from each other 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 having 1 to 30 carbon atoms, wherein the R _{3 is} in particular selected from: * -H, * -CH ₃ ,

Use according to claim 1 and 2, characterized in that at least one nitrogen-containing compound of formula (I) is used wherein R ₁ , R _{2 are the} same or different from each other, a hydrocarbon radical having 1 to 30, preferably 2 or 3 carbon atoms, expressed by

with q equal to or different from each other 2 or 3 and R _{17 are the} same or different from each other * -H or * -CH ₃ , and wherein R _{3 is} in particular selected 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 equal to or not equal to 1 to 6, in particular 2 or 3, preferably 2, and Y is in particular selected from the following radicals: * -OH, * -NH ₂ ,

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

Use according to one of claims 1 to 3, characterized in that at least one nitrogen-containing compound of the formula (I), preferably of the formula (II), with n, q and R ₁ , R ₂ , R ₃ as defined in the preceding claims, where q is particularly preferably 2, is used, and wherein this compound satisfies in particular the formula (III)

with n, a, b, R ₃ , Y as defined in the preceding claims, in which R ₃ particularly preferably * -H, * -CH ₃ ,

Y particularly preferably * -OH or

Use according to one of claims 1 to 4, characterized in that 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 = 2 and a, b is the same or not equal to each other 0, 1 or 2, wherein the ether and amine building blocks, if any, may occur cumulatively, alternately, blockwise or disorderly. Use according to one of claims 1 to 5, characterized in that 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 = 0, namely in particular a connection

is used, with n, q, Y as defined in claim 1-4, in turn

are preferably used. Use according to one of claims 1 to 5, characterized in that 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 = 0 and b = 2, namely in particular a connection

is used, with n, q, R ₃ , Y as defined in claim 1-4, in turn

are preferably used. Use according to one of claims 1 to 5, characterized in that 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 = 1 and b = 1, namely in particular a connection

is used, with n, q, R ₃ , Y as defined in claim 1-4, in turn

are preferably used. Use according to one of claims 1 to 4, characterized in that at least one nitrogen-containing compound of the formula (I), preferably of the formula (II), in particular of the formula (III) is used, where with a + b = 3 and a, b equal to or not equal to each other 0, 1, 2 or 3, wherein the ether and amine building blocks, if any, can occur cumulatively, alternately, blockwise or disorderly. Use according to one of claims 1 to 4 or 9, characterized in that 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 = 3 and b = 0 used becomes, in particular a connection

is used, with n, q, Y as defined in claim 1-4, in turn

are particularly preferred. Use according to one of claims 1 to 4 or 9, characterized in that 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 used becomes, in particular a connection

is used, with n, q, R ₃ , Y as defined in claim 1-4, in turn

are preferably used Use according to one of claims 1 to 4 or 9, characterized in that 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 = 1 and b = 2 used becomes, in particular a connection

is used, with n, q, R ₃ , Y as defined in claim 1-4, in turn

with m, n, q equal or different from each other 2 to 6, in particular 2 or 3, preferably 2, are preferably used. Use according to one of claims 1 to 4 or 9, characterized in that 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 = 0 and b = 3, in particular a connection

is used with n, q, R ₃ , Y as defined in claim 1-4, with particularly preferred compounds are selected from the group include

with m, n, q equal or different from each other 2 to 6, in particular 2 or 3, preferably 2. Use according to one of the preceding claims, characterized in that

such that the nitrogen-containing compound of the formula (I) of the formula (IV) satisfies

with a, b, n, R ₁ , R ₂ , R ₃ as defined in the preceding claims, c, d are equal or different from each other 0 to 6, in particular 0 to 3, preferably 1 or 2, with the proviso that the ethers or amine building blocks a, b, c and d, if present, can occur cumulatively, alternately, in blocks or in disorder, R ₁₈ , R _{19 are} identical or different, 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 2 Carbon atoms, with R ₂₀ = H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more hetero atoms or interrupted by one or more hetero atoms hydrocarbon radical having 1 to 30 carbon atoms, preferably a radical selected from

where m = 2-6, preferably 2 or 3,

with o, p equal or different from each other 2 or 3,

with s, t equal to or different from each other 2 or 3 and R ₁₆ as defined in the preceding claims, preferably * -H,

Use according to claim 1 to 14, characterized in that at least one nitrogen-containing compound of the formula (I), preferably at least one nitrogen-containing compound of the formula (II), (III) or (IV), in particular a nitrogen-containing compound according to the formula ( III), is used as a 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 of up to at 95 wt .-%, preferably ≤ 70 wt .-%, in particular ≤ 30 wt .-%, preferably ≤ 10 wt .-%, in particular preferably ≦ 5% by weight. Use according to claim 15, wherein the technical product mixture used comprises (a) at least one nitrogen-containing compound of the formula (I), in particular at least one nitrogen-containing compound of the formula (II), (III), or (IV), more preferably at least one nitrogen-containing one Compound according to formula (III), advantageously in a total amount of ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight, (b) optionally 1- (3-aminopropyl) pyrrolidine , advantageously in an amount ≥ 5 wt .-%, preferably 20-95 wt .-%, in particular 30-70 wt .-%, (c) optionally 1- (2-aminoethyl) pyrrolidine, advantageously in an amount ≥ 5 wt .-%, preferably 20-95 wt .-%, in particular 30-70 wt .-%, (d) optionally 1- (2-hydroxyethyl) pyrrolidine, advantageously in an amount ≥ 5 wt .-%, preferably 20-95 % By weight, in particular 30-70% by weight, (e) optionally 1- (3-hydroxypropyl) pyrrolidine, advantageously in an amount of ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70 wt .-%, (f) 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol, advantageously in an amount ≥ 5 wt .-%, preferably 20-95 wt .-%, in particular 30 -70% by weight, (g) 1,1 '- (oxybis (ethane-2,1-diyl)) dipyrrolidine, advantageously in an amount of ≥ 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight , (h) optionally ethylenediamine (EDA), advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight, (i) optionally 1,4-butanediol, advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight, (j) optionally monoethylene glycol (MEG), advantageously in an amount ≦ 95% by weight, in particular 20 -90 wt .-%, preferably 30-80 wt .-%, (k) optionally diethylene glycol (DEG), advantageously in an amount ≤ 95 wt .-%, in particular 20-90 wt .-%, preferably 30-80 wt .-%, (l) optionally 1,2-propylene glycol (PG), advantageously in an amount ≤ 95 wt .-%, in particular 20-90 wt .-%, preferably 30-80 wt .-%, (m) optionally Dipropylene glycol (DPG), advantageously in an amount ≤ 95 wt .-%, in particular 20-90 wt .-%, preferably 30-80 wt .-%, (n) optionally Di Ethanolamine, advantageously in an amount ≤ 95 wt .-%, in particular 20-90 wt .-%, preferably 30-80 wt .-%, (o) optionally triethanolamine, advantageously in an amount ≤ 95 wt .-%, in particular 20 -90 wt .-%, preferably 30-80 wt .-%, and / or (p) optionally monoethanolamine (MEA), advantageously in an amount ≤ 95 wt .-%, in particular 20-90 wt .-%, preferably 30 -80% by weight. Use according to one of the preceding claims, characterized in that the at least one nitrogen-containing compound of the formula (I), preferably at least one nitrogen-containing compound of the formula (II), (III) or (IV), in particular at least one nitrogen-containing compound of the formula (III), a correspondingly quaternized and / or protonated compound, as a catalyst in the preparation of polyurethanes, in particular polyurethane foams, is used, wherein said nitrogen-containing compound is preferably used as a technical product mixture according to claims 15 or 16. Use according to one of the preceding claims, characterized in that in the preparation of the polyurethane, in particular polyurethane foam, a composition is prepared which comprises at least one nitrogen-containing compound of the formula (I), preferably at least one nitrogen-containing compound of the formula (II), (III ) or (IV), in particular at least one nitrogen-containing compound of the formula (III), a corresponding quaternized and / or protonated compound, and furthermore at least one polyol component, at least one isocyanate component and optionally one or more blowing agents, and this composition is reacted, wherein said nitrogen-containing compound is preferably used as a technical product mixture according to claims 15 or 16. Use according to one of the preceding claims, characterized in that the at least one nitrogen-containing compound of the formula (I), preferably of the formula (II), (III) or (IV), in particular of the formula (III), and / or a corresponding quaternized and / or protonated compound in combination with a) one or more additional (not according to the invention) nitrogen-containing compounds as additional catalysts, preferably as defined above and exemplified, 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 exemplified, c) one or more acids for blocking the amines containing, preferably as described above, d) water e) one or more organic solvents, preferably as in Defined below and described by way of example f) one or more chemisc or physical blowing agents, preferably as described below, g) one or more stabilizers against oxidative degradation, for example antioxidants, preferably as described below, h) one or more flame retardants, preferably as described below, and / or i) one or more several foam stabilizers based on siloxanes and / or polydialkylsiloxane-polyoxyalkylene copolymers, preferably as defined and described below, and / or j) one or more further additives, for example selected from the group of surfactants biocides, dyes, pigments, fillers , Antistatic additives, crosslinkers, chain extenders, cell openers, and / or fragrances is used, wherein advantageously before the preparation of the polyurethane, in particular the polyurethane foam, first a composition is prepared, for example in the sense of a predosing of the individual components in the mixing head or z. Example, as a premixed catalyst combination comprising the aforementioned combination, said nitrogen-containing compound according to formula (I), (II), (III) or (IV) preferably as a technical product mixture, in particular according to the claims 15 or 16, can be used , Use according to one of the preceding claims, characterized in that the at least one nitrogen-containing compound of the formula (I), preferably at least one nitrogen-containing compound of the formula (II), (III) or (IV), in particular at least one nitrogen-containing compound of the formula (III), in combination with at least one solvent is used, wherein the mass ratio of total catalyst used, comprising all catalytically active compounds equal and different from the formula (I), (II), (III) or (IV), to solvent preferably from 100 to 1 to 1 to 4, preferably from 50 to 1 to 1 to 3, and more preferably from 25 to 1 to 1 to 2. Composition comprising at least one polyol component, characterized in that the composition comprises at least one nitrogen-containing compound of the formula (I), preferably at least one nitrogen-containing compound of the formula (II), (III) or (IV), in particular at least one nitrogen-containing compound of the formula (III) as defined in the preceding claims and / or the corresponding quaternized and / or protonated compounds, said composition preferably having at least one isocyanate component, and wherein the nitrogen-containing compound of formula (I), (II), (III ) or (IV) is preferably contained as a technical product mixture according to claims 15 or 16, and wherein the composition preferably comprises additional amine catalysts other than formula (I), (II), (III) or (IV). Composition according to Claim 21, characterized in that the molar ratio of the total amount of nitrogen-containing catalysts comprising the nitrogen-containing compounds of the formula (I), (II), (III) or (IV) to the total amount of the isocyanate-reactive groups of the polyol component from 4 × 10 ^-4 to 1 to 0.2 to 1. Compositions according to Claim 21 or 22, characterized in that the nitrogen-containing compounds of the formula (I), (II), (III) or (IV), corresponding quaternized and / or protonated compounds, in a proportion by mass of 0.01 to 20, 0 parts (pphp), preferably 0.01 to 5.00 parts and more preferably 0.02 to 3.00 parts based on 100 parts (pphp) of polyol component are used. Composition suitable for use in the production of polyurethanes, in particular polyurethane foams, comprising (a) at least one nitrogen-containing compound of the formula (I), in particular at least one nitrogen-containing compound of the formula (II), (III) or (IV) 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, (b) optionally 1- ( 3-aminopropyl) pyrrolidine, advantageously in an amount ≥ 5 wt .-%, preferably 20-95 wt .-%, in particular 30-70 wt .-%, (c) optionally 1- (2-aminoethyl) pyrrolidine, advantageously in an amount 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight, (d) optionally 1- (2-hydroxyethyl) pyrrolidine, advantageously in an amount ≥ 5% by weight , preferably 20-95 wt .-%, in particular 30-70 wt .-%, (e) optionally 1- (3-hydroxypropyl) pyrrolidine, advantageously in an M narrow ≥ 5 wt .-%, preferably 20-95 wt .-%, in particular 30-70 wt .-%, (f) 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol, advantageously in an amount ≥ 5 wt .-%, preferably 20-95 wt .-%, in particular 30-70 wt .-%, (g) 1,1 '- (oxybis (ethane-2,1-diyl)) dipyrrolidine, advantageously in an amount ≥ 5 wt .-%, preferably 20-95 wt .-%, in particular 30-70 wt .-%, (h) optionally ethylenediamine (EDA), advantageously in an amount ≤ 95 wt .-%, in particular 20-90 wt .-%, preferably 30-80 wt .-%, (i) optionally 1,4-butanediol, advantageously in an amount ≤ 95 wt .-%, in particular 20-90 wt .-%, preferably 30-80 wt. %, (j) optionally monoethylene glycol (MEG), advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight, (k) optionally diethylene glycol (DEG), advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight, (1) optionally 1,2-propylene glycol (PG) , advantageously in an amount ≦ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight, (m) optionally dipropylene glycol (DPG), advantageously in an amount ≦ 95% by weight, in particular 20-90 wt .-%, preferably 30-80 wt .-%, (n) optionally diethanolamine, advantageously in an amount ≤ 95 wt .-%, in particular 20-90 wt .-%, preferably 30-80 wt. -%, (o) optionally triethanolamine, advantageously in an amount ≤ 95 wt .-%, in particular 20-90 wt .-%, preferably 30-80 wt .-%, (p) optionally monoethanolamine (MEA), advantageously in one Amount ≤ 95% by weight, especially 20-90% by weight, preferably 30-80% by weight, and / or (q) optionally trimethylene glycol, butyl diglycol, neopentyl glycol, 2-methyl-1,3-propanediol, N , N-dimethylcyclohexylamine, N, N-dimethylaminopropylamine, triethylenediamine, 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) hexahydroxy 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, in particular N, N-dimethylcyclohexylamine, tris (dimethylaminopropyl) hexahydro-1,3,5-triazine, triethylenediamine, N, N-dimethylaminopropylamine , N, N-dimethylaminoethanol, bis (2-dimethylaminoethyl ether), N, N, N'-trimethyl-N '- (2-hydroxyethyl) bis (2-aminoethyl) ether and / or 2,2,4-trimethyl-2 -silamorpholine, advantageously in a total amount ≤ 95 wt .-%, in particular 20-90 wt .-%, before zugt 30-80 wt .-%. Polyurethane system, characterized in that it is obtainable by a use according to one of the preceding claims 1 to 21, wherein it is in particular a rigid polyurethane foam, a flexible polyurethane foam, a viscoelastic foam, a cold foam (also called high resilience (HR) foam), a semi-hard Polyurethane foam, a thermoformable polyurethane foam or an integral foam, wherein it preferably has a mass fraction of compounds of formula (I) or obtained by reacting these radicals on the finished polyurethane foam from 0.005 to 10 wt .-%. Use of polyurethane systems according to claim 25 as refrigerator insulation, insulation board, sandwich element, pipe insulation, spray foam, 1 & 1,5 component can foam, wood imitation, model foam, floral foam, packaging foam, mattress, furniture upholstery, molded foam furniture, pillows, "Rebonded Foam", sponge foam , Automotive seat cushion, headrest, instrument panel, automotive interior trim, automotive headliner, sound absorbing material, steering wheel, shoe sole, carpet back foam, filter foam, sealing foam, sealant and adhesive, or for making such products.