WO2016020137A1

WO2016020137A1 - Nitrogen-containing compounds suitable for use in the production of polyurethanes

Info

Publication number: WO2016020137A1
Application number: PCT/EP2015/065804
Authority: WO
Inventors: Thomas Günther; Michael Fiedel; Olga FIEDEL; Martin Glos; Roland Hubel
Original assignee: Evonik Degussa Gmbh
Priority date: 2014-08-05
Filing date: 2015-07-10
Publication date: 2016-02-11
Also published as: DE102014215381B4; DE102014215381A1

Abstract

The present invention relates to the use of nitrogen-containing compounds according to formula (I) and/or of corresponding quaternized and/or protonated compounds for producing polyurethanes, to compositions containing said compounds, and to polyurethane systems, in particular polyurethane foams, obtained using the compounds.

Description

Nitrogen containing compounds suitable for use in the production of polyurethanes

The present invention is in the field of nitrogen containing compounds, especially amines, and polyisocyanate polyaddition products, especially 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 used 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, it is also possible to distinguish between cold flexible foams and hot flexible foams, such as e.g. in EP 2042534 A1, which is incorporated herein by reference in its entirety.

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 well as the use of corresponding quaternized compounds as well as the use of appropriate mixtures each solves the task mentioned. 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 polyisocyanate polyaddition products, preferably polyurethanes, in particular polyurethane foams, wherein the nitrogen-containing compound of formula (I) is sufficient

(I)

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 one another 0 to 3, preferably a = 0 to 2 and b = 1 to 3, in particular a and b> 1,

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 equal or different from one another, is a linear, branched or cyclic, aliphatic, saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, in particular 2 to 12, preferably 2 to 6, preferably 2 or 3 carbon atoms, particularly preferably 2 carbon atoms is

R 3 is H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical optionally substituted by one or more heteroatoms or interrupted by one or more heteroatoms and having from 1 to 30 carbon atoms,

, ^R 5

* -N

Y = ^R 4 or * - ° ^R 6,

, ^R 5

* -N

for Y = ^R 4,

R ₄ , R 5 are identical or different, are H, 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

where ^K 4 is in particular -NH,

is wherein R.7, Rs, 9 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 hetero atoms or interrupted by one or more hetero atoms hydrocarbon radical having 1 to 30 carbon atoms .

for Y = * ^"0R 6,

R 6 is H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical optionally substituted by one or more heteroatoms or interrupted by one or more heteroatoms,

where * 6 is preferably equal to * -OH or

In particular, Y is * -OH, or more preferably * -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 upholstered furniture, an amine emission of> 0 μg m ³ and <40 μg m ³ , preferably <10 μg m ³ , more 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 Polyurethanaltweichschaum, 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 R 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 ^ g / g and <40 ^ g / g, preferably <10 ^ g / g, particularly preferably <5 ^ g / g, according to the VDA 278 analytical method in the version of October 201 1, "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, in particular in automotive interiors, for example as a headliner, interior lining of doors, cut-out sun visors, steering wheels and / or seating systems, an amine emission, hereinafter also Fog emission or Fog value according to VDA 278 (Fog: highly volatile substances which condense easily at room temperature and z to contribute to fogging on the windscreen), of> 0 g / g and <40 g / g, preferably <10 μg / g, more preferably <5 μg g, according to the VDA 278 Analytical Procedure in the October 201 1 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 in the automotive industry, it may, depending on the vehicle manufacturer specification limits on the total emissions of volatile organic compounds (VOC _ges , and / or Fog _ges ), for example VOC _ges ^ 100 μg g and / or Fog _ges ^ 250 μg g. It is all the more important that the contribution of the amines to the total emission (VOCAmin and / or FogAmin) 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, have a DMF emission of> 0 ppm and <5 ppm, preferably <1 ppm, more preferably <0.1 ppm in particular, the provision of flexible polyurethane foams, especially polyurethane hot foams, which are particularly low in emissions of dimethylformamide. "DMF emission" in the context of the present invention is not a subset of "Armin emission.""Lowemissions" with respect to emissions of aldehydes, in particular In particular, for the purposes of the present invention, formaldehyde, in particular, means that the polyurethane system, preferably the polyurethane foam, in particular the flexible polyurethane foam, the limits for aldehyde emissions set by the foam manufacturers and the furniture industry in Europe and the USA within the framework of the voluntarily imposed program "CertiPUR", in particular for formaldehyde emissions and / or that the replacement of the conventional catalysts, in particular of amines, especially of tertiary amines, containing one or more N-methyl or N, N-dimethyl groups, according to the prior art by nitrogen compounds to be used according to the invention in the formulation of a corresponding polyurethane system leads to an improvement of the aldehyde, especially formaldehyde-related emissions. The limit for formaldehyde emissions according to "CertiPUR" for example for mattresses at 0.1 mg / m ³ as measured by ASTM Method D51 16-97 "Small Chamber Test" when conditioning over 16 hours. The person skilled in various analytical methods for the determination of aldehyde emissions are known. By way of example, VDA 275, VDA 277 or even VDA 278 may be mentioned here, as well as various chamber test methods. VDA is the Association of the Automotive Industry (www.vda.de). "VDA 275", according to the July 1994 version, provides a measuring method for the determination of aldehyde, in particular the formaldehyde release by the modified bottle method, wherein as derivatization of aldehydes in addition to the commonly used acetylacetone (via photometric detection) and 2.4 - Dinitrophenylhydrazine (2,4-DNP) (detection by HPLC after external calibration) can be used to determine acetaldehyde and propionaldehyde better in addition to formaldehyde In the context of this invention is based on both process interpretations of this VDA 275 as a preferred method for the determination of aldehyde -, In particular formaldehyde emissions, reference is made.

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

Polyurethane flexible foams, prepared using the aforementioned nitrogen-containing compounds, which are lower emissions emissions of aldehydes, especially formaldehyde, even with different requirements than corresponding nitrogen-containing catalysts or corresponding polyurethane systems in which instead of nitrogen-containing compounds according to the invention conventional catalysts, especially tertiary amines, containing one or more N-methyl or N, N-dimethyl groups, according to the prior art. For commercially available amines or PU systems containing commercial amines, otherwise, for example, due to their industrial production formaldehyde than Contain contamination, for example, were used in the amine-making 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 can be observed especially in the case of polyurethane foams, preferably soft-block foams, in particular in the sense of a dry heat aging according to the DIN standard DIN EN ISO 2440 / A1: 2009-01, in particular at a temperature of 70, 100, 120, 125 and / or 140 ° C and an aging time of 2, 4, 16, 22, 24, 48, 72 and / or 168 hours, preferably at 2, 24 and / or 168 hours, if in the expansion according to the invention nitrogen-containing compounds according to formula (I) as alternatives are used 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 discolorations of plastics, especially plastic covers, in automotive interiors as such lead 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 according to the invention without adversely affecting the desired material properties, for example, the openness of the foam or the space weight distribution over the foam block, is possible over comparable or for those applications usually used 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 example, be preferred if, for example, a slower polyurethane reaction is to be achieved or if the reaction mixture should have an improved flow behavior during use. As organic acids, for example, all the organic acids mentioned below, 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 even polymeric acids such as polyacrylic or polymethacrylic acids are used. As inorganic acids, for example, phosphorus-based acids, sulfur-based acids or boron-based acids can be used.

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

The objects according to the invention are described below by way of example, without the invention being restricted to these exemplary embodiments. 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. In addition to the polyurethane, it is also possible to form further functional groups, for example 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. It can hereby give the name, polyurethane as well Other functional groups are formed, such 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.

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

R3 selected from the following residues:

For

preferably, * ^{O 0} P ^NH 2 or

or 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 Rio, RH , R12, R13, Ri4, R15, Ri6 are identical 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 interrupted by one or more heteroatoms hydrocarbon radical having 1 to 30 Carbon atoms, wherein R3 in particular out

^NH 2 ode

Furthermore, it corresponds to a preferred embodiment of the invention, if at least one nitrogen-containing compound of the formula (I) is used

where R 1, R 2, equal to or different from one another, are a carbon of 1 to 30,

preferably 2 or 3 carbon atoms, expressed by

q is the same or

* -PH not equal to each other 2 or 3 and R17 is the same or different from each other * -H or '3,

* -PH and wherein R3 is in particular selected from the following radicals: * -H _J ^ ^M 3 _J

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 wherein Y is in particular selected from the following radicals: ^» -OH, ^IN 2 _!

* -NO

or \ - /,

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

(II).

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 Ri, R2, R3 as previously defined,

where q is particularly preferably used 2,

wherein this compound satisfies in particular the formula (III)

(III)

with n, a, b, R3, Y as previously defined,

eson ers evorzug * - o er

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.

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,

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

again

and / or ^Ν Ο ^ ^/ ^^^ OH are preferably used, there is also a preferred embodiment of this invention.

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, R3, Y as previously defined,

again

Furthermore, it corresponds to a preferred embodiment of this 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 = 1 and b = 1,

, preferably

and or

voorr7ziuiogsswweeiissfie

is used, with n, q, R3, 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,

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,

, preferably

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

again

are particularly preferred.

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, where a = 2 and b = 1 used becomes,

, preferably and / or

and or

, is preferably used, with n, q, R3, Y as already defined above,

again

e preferential use.

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

and or

and or ^{I Π q}

is used, with η, q, R3, Υ 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.

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, R3, Y as previously defined,

particularly preferred compounds being selected from the group comprising

u and / ooddeerr

with m, n, q equal or different from each other 2 to 6, in particular 2 or 3, preferably 2. 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, R1, R2, R3 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

R18, R19 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 R20 = H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally with one or more heteroatoms substituted or interrupted by one or more heteroatoms Kohlenwasserstoffre 0 carbon atoms, preferably a radical selected from 2 ₀ = therein m = 2-6, preferably with o, p is the same or u

equal to each other 2 or 3, with s, t equal to or different from each other 2 or 3 and Ri6 as previously defined, preferably * -H, ^ ^Π 3, * or I.

* MM * -Ν I * ^_N

and Y '= * -OH, * NH _{2 j} ^ or \ - /.

The present invention also includes the use of several different nitrogen-containing compounds of the formulas (I), (II), (III) and / or (IV), for example, with regard to all their objects and preferred embodiments thereof. the joint use of nitrogen-containing compounds of the formulas (III) and (IV), and the use of the corresponding protonated compounds as well as the use of the corresponding quaternized compounds and the use of corresponding mixtures of all of the aforementioned nitrogen-containing compounds of the formula (I), (II ), (III) and / or (IV), corresponding protonated and / or quaternized compounds.

The above-described nitrogen-containing compounds of the formula (I), (II), (III) and / or (IV) according to the invention are generally accessible via customary processes for the production of Armin. 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 Encyclopedia 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). Preferably used amino alcohols or hydroxyl-bearing amines can be prepared, 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 of diols, in particular of glycols such as monoethylene glycol (MEG), diethylene glycol (DEG), 1,2-propylene glycol (PG), Dipropylene glycol (DPG), with ammonia or amines by known methods, as described, for example, by Beller et al. in Chem. Asian J. 2007, 2, 403-410, by Milstein et al. in Angew. Chem. 2008, 120, 8789-8792, by Watson and Williams in Science 2010, Vol. 329, pp. 635-636 or by Börner et al. in ChemCatChem 2010, 2, 640-643. Preferred amino alcohols for the purposes of this invention are, for example, monoethanolamine (MEA), 1- (2-hydroxyethyl) pyrrolidine, diethanolamine (DEOA), triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine. The amino alcohols described 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, in particular with alkyl chlorides (nucleophilic substitution), as for example by Aitken et al. in Tetrahedron, 2002, Vol. 58, 29, pp. 5933-5940 and Tijskens et al. in Journal of Organic Chemistry, 1995, Vol. 60, 26, p. 8371-8374, and / or by reaction of pyrrolidine with bischloroalkyl ethers, and / or by reaction of pyrrolidine with epoxides (alkoxylation) or epoxide-bearing compounds , in particular with ethylene oxide (EO) and / or propylene oxide (PO), as described, for example, by Reppe et al. in Justus Liebigs Annalen der Chemie, 1955, Vol. 596, p. 1 149 or by Moffett et al. in Journal of Organic Chemistry, 1949, Vol. 14, pp. 862-866 and in Org. Synth. Coli., 1963, Vol. IV, p. 834ff, and / or by reaction of pyrrolidine with alcohols and / or polyols, preferably diols, in particular glycols, for example in a transition metal catalyzed embodiment as described by Jenner et al. in Journal of Organometallic Chemistry, 373 (1989), 343-352. Furthermore, the pyrrolidine function can also be carried out by reacting 1,4-butanediol with primary amines, such as, for example, again by Jenner et al. in Journal of Organometallic Chemistry, 373 (1989), 343-352, and / or by reaction of 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, as for example in DE 701825C described, are introduced. In this case, depending on the process conditions and the selected reaction regime also diverse by-products, for example by incomplete or only partial reaction of the starting materials, as well as by side reactions, for example between the selected starting materials, for example between polyamines, polyols, in particular of 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 N-methylation. Here, for example, the reductive methylation of primary and secondary amines using formaldehyde and formic acid in the sense of Eschweiler-Clarke methylation is known, which is a special case of the Leuckart-Wallach reaction (R. Leuckart, Ber. 18, 2341 (1885 ), O. Wallach, Ann. 272, 99 (1892)). Descriptions of Eschweiler-Clarke methylation can be found, inter alia, in W. Eschweiler, Ber. 38, 880 (1905) and H.T. Clarke, et al., J. Am. Chem. Soc. 55, 4571 (1933) and other synthetic applications e.g. also in E. Farkas, C.J. 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 are widely described in the literature, for example in US 5639916 or DE 4230402. Depending on the process conditions and the selected reaction regime also diverse by-products, for example by incomplete or only partial reaction of the starting materials, as well as by side reactions, for example occur between the selected starting materials, for example between polyamines, polyols and / or amino alcohols. 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% by weight, in particular <30% by weight, preferably <10% by weight, more preferably < 5% by weight of a preferred embodiment of this invention.

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 of> 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 of> 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 of <95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,

(i) optionally 1,4-butanediol, advantageously in an amount of <95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,

(j) optionally monoethylene glycol (MEG), advantageously in an amount of <95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,

(k) optionally diethylene glycol (DEG), advantageously in an amount of <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 wt .-%, in particular 20-90 wt .-%, preferably 30-80 wt .-%,

(m) optionally dipropylene glycol (DPG), advantageously in an amount of <95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,

(n) optionally diethanolamine, advantageously in an amount of <95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,

(O) optionally triethanolamine, advantageously in an amount of <95 wt .-%, in particular 20- 90 wt .-%, preferably 30-80 wt .-%, and / or

(p) optionally monoethanolamine (MEA), advantageously in an amount of <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), I), 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), b), c), d), e), f) and j), 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 I), with c) and I), with d) and I), with e) and I), with f) and I), with g) and I), with b), c) and I ), with b), c), d) and I), with b), c), d), e) and I), with c), d) and I), with c), d), e) and I), with d), b) and I), with d), e) and I), with d), b), e) and I), with e), b) and I), with e) , c) and I), with e), b) and I), with f) and I), with g) and I), with f), g) and I), with f), g) and I) , with b), c), d), e), f), g) and I), with b), c), d), e), f) and I) or in combination with b), c) , d), e), g) and I). In this case, particular preference is given to combinations with b), with c) with j), with k), with I) 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 in particular for the production of polyurethane foams used 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 ), a correspondingly quaternized and / or protonated Compound, or mixtures of the nitrogen-containing compound of formula (I), (II), (III) and / or (IV) with corresponding quaternized and / or protonated compounds as a catalyst in the preparation of polyurethane systems, in particular polyurethane foams, is used. 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 information on the starting materials, catalysts and auxiliaries and additives used can be found, for example, in 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 only by way of example and can be replaced and / or supplemented by other substances known to the person skilled in the art.

The compounds of the formula (I), (II), (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.

Examples which may be mentioned here are 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 hexamethylene diisocyanate 1,6 (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-hexa-hydrotoluylene diisocyanate and the corresponding isomer mixtures, and preferably aromatic diisocyanates 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-hexanoisocyanate , 2'-diphenylmethane diisocyanates (MDI) and Polyphenylpolymethylenpolyisocyanate (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 higher nuclear products) and the dinuclear product referred to as "pure MDI" Examples of particularly suitable isocyanates are described, for example, in EP 1712578, EP 1 161474, WO 00/58383, US 2007/0072951, EP 1678232 and WO 2005 / 085310, the entire contents of which are incorporated herein by reference.

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 Füllkörperpolyole (polymer polyols) such as SAN, PHD and PIPA polyols, which are characterized in that they are solid organic fillers to a solids content of 40% or more in disperse distribution, and / or autocatalytic polyols containing catalytically active functional groups, especially amino groups, and / or natural-based polyols (NOPs) Polyols have a functionality of 1.8 to 8 and number average molecular weights in the range of 500 to 15000. Usually, the polyols are used with OH numbers in the range of 10 to 1200 mgKOH / g The number average molecular weights are usually by gel permeation chromatography (GPC), in particular with Polypropylene glycol as Refere nesubstanz and tetrahydrofuran (THF) as eluent. The OH numbers can be determined in particular according to the DIN standard DIN 53240: 1971-12. 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 containing preferably 2 or 3 reactive hydrogen atoms bound 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. For example, water, 2-, 3- or 4-hydric alcohols such as ethylene glycol, propanediol-1, 2 and -1, 3, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, castor oil, etc., higher polyfunctional polyols, can be used as starter molecules. in particular sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resoles such as 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. Besides, the use is Of CO 2 as a comonomer ecologically very advantageous, since this reaction represents the conversion of a greenhouse gas to a polymer. The preparation of Polyetherpolycarbonat- polyols 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 in this case: The first generation represented heterogeneous zinc or aluminum salts, as described for example in US-A 3900424 or US-A 3953383. 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 201 1/163133). 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 (WO 2005/033167, US 2006/0293400, WO 2006/094227, WO 2004/096882, US 2002/0103091, WO 2006/1 16456 and EP 1678232) In the meantime, a number of these polyols from various manufacturers are 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 work-up connected thereto, polyols with different properties can be obtained, whereby essentially two groups can be distinguished: a) Polyols based on renewable raw materials, which are modified so that they are 100% for the production of Polyu rethanen can be used (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 polyurea also in dispersed form contain. 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 may be e.g. alone or e.g. 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 usable 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 described, for example, in WO0158976 (A1), WO2005063841 (A1), WO0222702 (A1), WO2006055396 (A1), WO03029320 (A1), WO0158976 (A1), US6924321 (B2), US6762274 (B2), EP2104696 (B1) , WO2004060956 (A1) or WO2013102053 (A1) and can be obtained, for example, 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 2007/1 1 1828, US 2007/0238800, US 6359022 or WO 96/12759. Other polyols are known to those skilled in the art and can be found, for example, in EP-A-0380993 or US-A-3346557, to which reference is made in its 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, particularly preferably 2 to 3, number average molecular weights in the range from 200 to 4000, preferably 400 to 3000, particularly preferably 600 to 2500 and usually OH numbers in the range of 10 to 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, 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 used. According to a further preferred embodiment of the invention, in particular for the production of viscoelastic polyurethane foams, mixtures of different, preferably two or three, polyfunctional polyester alcohols are preferably used and / or polyether alcohols used. Usually, the polyol combinations used here consist of a low molecular weight "crosslinker" polyol, for example a rigid foam polyol with high functionality (> 3) and / or a conventional high molecular weight block foam or HR polyol and / or a "hypersoft polyether - Polyol with high content of ethylene oxide blocks and with cell-opening properties.

A preferred ratio of isocyanate to polyol, expressed as the index of the formulation, i. as a stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (eg, OH groups, NH groups) multiplied by 100, is in the range of 10 to 1000, preferably 40 to 350, particularly preferably 70 to 140. An index of 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 In the context of this invention, the term "premixed catalyst combination", hereinafter also referred to as a catalyst combination, comprises in particular finished mixtures of nitrogen-containing compounds of the formula (I), (II), (III) according to the invention. and / or (IV), accordingly he 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 Polyethersiloxanes, which are present as such before the foaming and during the foaming process need not be added as individual components.

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 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 (I II) "in the context of this invention also includes the common use such nitrogen-containing compounds, ie, for example, the joint use of nitrogen-containing compounds of the formula (III) and (IV). Examples of suitable additional nitrogen-containing compounds as catalysts for the purposes of the present invention are the amines triethylamine, Ν, Ν-dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, Ν, Ν-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, Ν, Ν, Ν'-trimethylaminoethylethanolamine, Ν, Ν-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] oc tane-2-methanol, Ν, Ν'-dimethylpiperazine, 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'-dimorpholino-diethyl ether, Ν, Ν'-dimethylpiperazine, N- (2-hydroxyethyl) piperazine, N- (2-aminoethyl) piperazine, Ν, Ν-dimethylbenzylamine, N, N-dimethylaminoethanol, Ν , Ν-diethylaminoethanol, 1- (2-hydroxyethyl) pyrrolidine, 3-dimethylamino-1-propanol, 'HS-hydroxypropyl-' pyrrolidine, N, N-dimethylaminoethoxyethanol, Ν, Ν-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-triazabicyclo [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 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. The term "organometallic or organometallic compounds" for the purposes of this invention, in particular the use of metal-containing compounds which have a direct carbon-metal bond, here as metal organyls (eg tin organyls) or organometallic or organometallic compounds (eg organotin compounds For the purposes of this invention, the expression "organometallic or organometallic salts" comprises in particular the use of salt-active organometallic or organometallic compounds, that is to say ionic 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 In the context of this invention, the term "inorganic metal salts" encompasses in particular the use of metal-containing compounds or of metal salts in which neither anion nor cation is an organic compound, for example metal chlorides (eg tin (II) chloride). , pure or mixed, ie containing several metals, metal oxides (eg tin oxides) 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 are composed of one or more central particles and one or more ligands, wherein the central particles are charged or uncharged metals (eg metal or tin-amine complexes In the context of this invention, the term "metal chelate complexes" encompasses in particular the use of metal-containing coordination compounds which have ligands with at least two coordination or bonding sites to the metal center (eg metal or tin-polyamine or metal or 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 tin (II) chloride, in the preparation of polyurethane systems, in particular 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 armin, 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 which carry 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 Mercaptoessigsäu reEstern as a special case of thiols, ie organic compounds which carry one or more mercaptoacetic acid ester groups ( ^* -0-CO-CH2-CH2-SH) wear, so-called mercaptoacetates, and / or of Sulfuric acid esters, ie organic compounds which carry one or more sulfate groups ( ^* -0-S03H), so-called sulfates, and / or of sulfonic acids, ie organic compounds, the e ine or more sulfonic acid groups ( ^* - SO 2 OH), so-called sulfonates, and / or Phoshporsäureestern (alkyl phosphates), ie organic compounds which are mono- or dihydric alkyl esters of orthophosphoric acid represent ( ^* -0-PO ( OH) 2 or ^* -O-PO (OR) OH), so-called phosphates, and / or of phosphonic acids, ie organic compounds which carry one or more phosphonic acid groups ( ^* -PO (OH) 2), so-called phosphonates , and / or phosphorous acid esters, organic compounds which are alkyl esters of phosphonic acid ( ^* -P (OR) 2 (OH) or ^* -P (OR) (OH) 2), so-called phosphites.

Suitable carboxylic acids 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 ( ^* -NH2, ^* -NHR, ^* -NR2) or mercapto groups ( ^* -SH), substituted, or is interrupted by one or more heteroatoms interrupted hydrocarbon radical. Particularly suitable in Sense of the present invention are those aliphatic carboxylic acids which in the 2-position, ie on the carbon atom in addition to the carbonyl, disubstituted (tertiary) or trisubstituted (quaternary) carbons, or corresponding hydrocarbon radicals possess. 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 ( ^* -NH2, ^* -NHR, ^* -NR2) or mercapto groups ( ^* -SH). 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, Pentadecanoic, 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 by one or more Heteroatoms interrupted 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.

Suitable thiols, mercaptoacetic acid esters, sulfuric acid esters, sulfonic acids, phosphoric acid esters (alkyl phosphates), phosphonic acids and / or phosphoric acid esters are, for example, all linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more heteroatoms, or by one or more heteroatoms 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 (tin (II) octoate), Tin (II) isononanoate (stannous) -3,5,5-trimethylhexanoate), stannous neodecanoate, stannous ricinoleate, zinc (II) acetate, zinc (II) 2-ethyl - hexanoate (zinc (II) octoate), zinc (II) isononanoate (zinc (II) -3,5,5-trimethylhexanoate), zinc (II) neodecanoate, zinc (II) ricinoleate, bismuth acetate, bismuth 2-ethylhexanoate, Bismuth octoate, 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 mentioned, for example, in DE 102007046860, EP 1985642, EP 1985644, EP 1977825, US 2008/0234402, EP 0656382 B1 and US 2007/0282026 A1 and the patents cited therein.

Suitable amounts of additional catalysts depend on the type of catalyst and are preferably in the range 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% by weight, in particular less than 50% by weight, preferably less than 30% by weight, particularly preferably less than 10% by weight of the catalysts in the catalyst mixture 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.

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 as a premixed Catalyst combination, in particular as defined above, containing 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 substance classes or substance classes containing the following functional groups: alcohols, polyols, (poly) alkylene glycols, amines, carboxylic acids, in particular fatty acids and / or primary and secondary amides. Preferred solvents are, for example, mineral oils, hexane, pentane, heptane, decane or mixtures of saturated hydrocarbons, such as. B. Kaydol products of Fa. 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 having 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-propanediol PDO), tetramethylene glycol (butanediol BDO), butyl diglycol (BDG), neopentyl glycol, 2-methyl-1, 3-propanediol (CXT ORTEGOL ^®), 3-methyl-1, 5-pentanediol and higher Homologs thereof such as polyethylene glycol (PEG) with average molecular weights between 200 and 3000. Further particularly preferred OH-functional compounds are polyethers having average molecular weights of 200 to 4500, especially 400 to 2000, herein preferably water, allyl, butyl or Nonyl-started polyethers, especially 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 prior art which are used in the preparation of polyurethanes, in particular polyurethane foams, such as, for example, blowing agents, preferably water for formation of CO2 and, if necessary, other 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, preferred HCFC 141 b, hydrofluoroolefins (HFO) or hydrohaloolefins such as 1234ze, 1233zd (E) or 1336mzz, oxygen-containing compounds such as methyl formate, acetone and dimethoxymethane, or chlorohydrocarbons, 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 examples are 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 using compounds of the following classes of substances or substance classes containing the following functional groups, particular preference being given to substituents on the respective basic bodies which have groups reactive toward isocyanate: 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. Examples of phenols which can be used are 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, e.g. Triethyl phosphate (TEP), halogenated phosphates, e.g. Tris (1-chloro-2-propyl) phosphate (TCPP) and tris (2-chloroethyl) phosphate (TCEP) and organic phosphonates, e.g. 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 can be used, such as chlorophene, benzisothiazoline, hexahydro-1, 3,5-tris (hydroxyethyl-s-triazine), chloromethylisothiazoline, methylisothiazoline or 1,6-dihydroxy-2,5-dioxohexane, the the trade names BIT 10, Nipacide BCP, Acticide MBS, Nipacide BK, Nipacide Cl, Nipacide FC.

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 documents: EP 0839852, EP 1544235, DE 102004001408, EP 0839852, WO 2005/1 18668, US 20070072951, DE 2533074, EP 1537159, EP 533202, US Pat. No. 3,933,695, 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.

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 such that, for example, a long-chain copolymer of ethylene oxide and propylene oxide is bonded to a polydimethylsiloxane radical. 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 described inter alia in US Pat. No. 2,834,748, US Pat. No. 2,917,480 and US Pat. No. 3,629,308. Suitable stabilizers are available from Evonik Industries AG under the trade name TEGOSTAB ^®. Suitable siloxanes which in the inventive use of the nitrogen-containing compounds according to the formula (I), (II), (III) and / or (IV) and / or the corresponding quaternized and / or protonated compounds can be used in the preparation of polyurethane foams, have in particular the following structure:

R R R-R R

R = -O- -SiO- -SiO- -SiO- -SiO-R "

RRR ~ R ^J R

(V) 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 formula (V), the mean number £ d of T units

[SiR ³ R ⁴ 0] and the mean number £ c of the Q units [SiR ³ R ³ 0] per molecule are each not greater than 50, the mean number £ a of the D units [SiRRO] per molecule is not greater than

2000 and the mean number £ b of the R ¹ -supporting siloxy units per molecule is not greater than 100,

R independently of one another 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 preferably one

Methyl radical is,

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, 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 " -0- (C ₂ H ₄ O-) x- (C ₃ H ₅ O-) y R '

-CH ₂ -R ^IV

-CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH (OH) -CH ₂ OH

H is CH ₂ - CH ₂ - CH ₂ O CH ₂ C

-CH _{2 is} -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 "independently of one another are 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 ', an alkylaryl group, such as For example, a benzyl group, the group -C (0) NH-R ', R ^{IV is} a linear, cyclic or branched, also more substituted, for example with

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,

may be functionalized, organic, saturated or unsaturated radical selected from the group of the alkyl, aryl, chloroalkyl, chloroaryl, fluoroalkyl, cyanoalkyl, acryloxyaryl, acryloyloxyalkyl, methacryloxyalkyl, methacryloxypropyl or vinyl radical, with with the proviso that at least one substituent of R ¹ , R ² and R ^{4 is} not equal to R. The different monomer units of the components given in the formulas

(Siloxane chains or polyoxyalkylene chain) may be constructed in blocks with each other with any number of blocks and any sequence or a statistical distribution subject. 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 known methods, such as, for example, the noble metal-catalyzed hydrosilylation reaction of compounds containing a double bond with corresponding hydrogen siloxanes as described, for example, in EP 1 520 870. The document 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 mean number E d of the T units and the mean number Ec of the Q units per molecule are each not greater than 20, the average number E a of D Units per molecule is not greater than 1500 and the average number E b of the R1-bearing 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 "

-CH2-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 "independently of one another are 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 ', an alkylaryl group, such as B. a benzyl group, the group -C (0) NH-R ', R ^{IV is} a linear, cyclic or branched, optionally substituted, for example, halogen-substituted, hydrocarbon radical having from 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 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 "is independently a hydrogen radical or an alkyl group having 1 to 4 carbon atoms, a group C (0) -R "'with R'" = alkyl group, a group -CH 2 -O-R ', an alkylaryl group, such as a benzyl group, the group C (0) NH-R ', where the molar proportion of oxyethylene units based on the total amount of oxyalkylene units is at least 70% of the oxalkylene units, ie x / (x + y)> 0.7 According to a further preferred embodiment of the invention (in particular within the scope of the use according to the invention) siloxanes of the formula (V) are used in which the oxalkylenes present in radical R 1 are used. Units are exclusively oxyethylene units and while the radical R "no hydrogen i st.

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 "is independently a hydrogen radical or an alkyl group having 1 to 4 carbon atoms, a group C (0) -R "'with R'" = alkyl group, a group -CH 2 -O-R ', an alkylaryl group, such as a benzyl group, the group C (0) NH-R ', where the molar proportion of oxyethylene units, based on the total amount of oxyalkylene units is at most 60% of the oxalkylene units, ie x / (x + y) <0.6.

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 R1 is at least 10 mol%, preferably at least 20 mol%, especially preferably at least 40 mol% of CH2-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 R1. 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 R1 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 scope of the use according to the invention) siloxanes of the formula (V) are used in where the oxalkylene units contained in the radical R1 are exclusively oxyethylene units and the radical R "is not hydrogen.

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

Preferably, the composition for the 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 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 foam materials, namely advantageously low emissions with respect to emissions of nitrogen-containing compounds, as previously also called amine emissions, advantageously low emissions with respect to emissions of dimethylformamide (DMF), and / or advantageously low emissions with regard to aldehyde emissions, in particular formaldehyde emissions. With regard to the term "low-emission", reference is made to the preceding description and the explanations there, in particular test methods.For preferred embodiments of this subject matter, reference is also made to the preceding description, in particular to the cited 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. Reference is made to the foregoing description and the accompanying explanations for the term "low odor." With regard 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 given there, With regard 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 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, like this for example, by a PVC discoloration test can be shown. 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 broad processing play, in particular of semi-hard polyurethane foams (open-cell rigid foams, in particular for use as headliners in automobile interiors). "Broad processing play" means that advantageously a larger variation of the use concentration of the nitrogen-containing compounds according to the invention without negatively influencing the desired material properties, for example off-line of the foam or the distribution of the weight-density over the foam block, is possible in comparison to comparable prior art amine catalysts or customarily used for such applications 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 is

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

(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 of> 5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,

(o) optionally triethanolamine, advantageously in an amount of <95% by weight, in particular 20-90% by weight, preferably 30-80% by weight, (P) optionally monoethanolamine (MEA), advantageously in an amount of <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, Ν, Ν-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, Ν, Ν-diethylaminoethanol, bis (2-dimethylaminoethyl ether), Ν, Ν Dimethylaminoethoxyethanol, N, N, N'-trimethyl-N '- (2-hydroxyethyl) bis (2-aminoethyl) ether, tris (dimethylaminopropyl) hexahydro-1,3,5-triazine, 1,8-diaza- bicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, 1, 5,7-triazabicyclo [4.4.0] dec-5-ene, N-methyl- 1, 5,7-triazabicyclo [4.4.0] dec-5-ene, 1, 4,6-triazabicyclo [3.3.0] oct-4-ene, 1,1,3,3-tetramethylguanidine and / or 2, 4,6-tris (dimethylaminomethyl) phenol, advantageously in a total amount of <95% by weight, in particular 20-90% by weight, preferably 30-80% by weight.

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 q), with a), b), c), d), e), f), g) and q), with a) and q), with b) and q), with c) and q), with d) and q), with e) and q), with f) and q), with g) and q), with f), g) and q), with b), d) and q), with c ), d) and q), with c), f), g) and q), with b), f), g) and q), with c), g) and q), with b), g) and q),

with b) and j), with c) and j), with d) and j), with e) and j), with f) and j), with g) and j), with b), c) and j ), with b), c), d) and j), with b), c), d), e) and j), with c), d) and j), with c), d), e) and j), with d), b) and j), with d), e) and j), with d), b), e) and j), with e), b) and j), with e) , c) and j), with e), b) and j), with f) and j), with g) and j), with f), g) and j), with f), g) and j) , with b), c), d), e), f), g) and j), with b), c), d), e), f) and j), with b), c), d ), e), g) and j),

with b) and k), with c) and k), with d) and k), with e) and k), with f) and k), with g) and k), with b), c) and k ), with b), c), d) and k), with b), c), d), e) and k), with c), d) and k), with c), d), e) and k), with d), b) and k), with d), e) and k), with d), b), e) and k), with e), b) and k), with e) , c) and k), with e), b) and k), with f) and k), with g) and k), with f), g) and k), with f), g) and k) , with b), c), d), e), f), g) and k), with b), c), d), e), f) and k), with b), c), d ), e), g) and k), with b) and m), with c) and m), with d) and m), with e) and m), with f) and m), with g) and m), with b), c) and m ), with b), c), d) and m), with b), c), d), e) and m), with c), d) and m), with c), d), e) and m), with d), b) and m), with d), e) and m), with d), b), e) and m), with e), b) and m), with e) , c) and m), with e), b) and m), with f) and m), with g) and m), with f), g) and m), with f), g) and m) , with b), c), d), e), f), g) and m), with b), c), d), e), f) and m), with b), c), d ), e), g) and m),

with b) and I), with c) and I), with d) and I), with e) and I), with f) and I), with g) and I), with b), c) and I ), with b), c), d) and I), with b), c), d), e) and I), with c), d) and I), with c), d), e) and I), with d), b) and I), with d), e) and I), with d), b), e) and I), with e), b) and I), with e) , c) and I), with e), b) and I), with f) and I), with g) and I), with f), g) and I), with f), g) and I) , with b), c), d), e), f), g) and I), with b), c), d), e), f) and I), with b), c), d ), e), g) and I),

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 I), with a), b), c), d), e), f), g), q) and I), with a), q) and I), with b), q ) and I), with c), q) and I), with d), q) and I), with e), q) and I), with f), q) and I), with g), q ) and I), with f), g) q), and I), with b), d), q) and I), with c), d), q) and I), with c), f) , g), q) and I), with b), f), g), q) and I), with c), g), q) and I), with b), g), q) and I )

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. Polyisocyanates and polyols or other isocyanate-reactive species, such as amines, polymer to be understood, wherein the urethane bond is not exclusive or predominant type of binding. 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 carried out in accordance with EN 29053. 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 percentage

Polyol 100

(Amine) catalyst 0.05 to 5

Tin catalyst 0 to 5, preferably 0.001 to 2

Potassium trimerization catalyst 0 to 10

Siloxane 0.1 to 15, preferably 0.2 to 7

Water 0 to <25, preferably 0.1 to 15

Blowing agent 0 to 130 Flame retardant 0 to 70

Fillers 0 to 150

further 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 canned foam, wood imitation, model foam, floral foam, packaging foam, mattress , Furniture upholstery, foam molded furniture, pillows, rebonded foam, sponge foam, automotive upholstery, headrest, instrument panel, automotive interior trim, automotive headliner, sound absorbing material, steering wheel, shoe sole, carpet back foam, filter foam, caulking foam, 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) - 1 12-26-5 Sigma-Aldrich ethane,> 97% Chemie GmbH

Pyrrolidine,> 99% 123-75-1 Sigma-Aldrich

Chemie GmbH A 250 ml four-necked flask equipped with KPG stirrer, reflux condenser, temperature measuring probe and inert gas inlet was charged with 35.0 g (0.187 mol) of 1,2-bis (2-chloroethoxy) -ethane. 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 was allowed to cool to room temperature. 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 42.1 1 g of a clear, slightly yellowish product according to the formula (purple) can be obtained. 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 supplier

2- [2- (2-chloroethoxy) ethoxy] ethanol, 5197-62-6 Sigma-Aldrich

96% Chemie GmbH

Pyrrolidine,> 99% Sigma-Aldrich

Chemistry GmbH

Potassium carbonate, anhydrous 584-08-7 Sigma-Aldrich

Chemistry GmbH

Acetonitrile, anhydrous 99.8% Sigma-Aldrich

Chemistry GmbH

Ethyl acetate, anhydrous 99% Sigma-Aldrich

Chemistry GmbH

Diethyl ether, anhydrous 99% Sigma-Aldrich

Chemistry GmbH

The technical teaching of EP 1945222 B1 (Intermediate 1 1) following were in an apparatus consisting of a 1 L multi-necked flask equipped with KPG stirrer, reflux condenser, dropping funnel and temperature sensor with inert gas inlet amount of 18.67 g (263 mmol) pyrrolidines and 375 ml of acetonitrile submitted. 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 1 H 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 (Never)

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

Chemie GmbH The technical teaching of G. Jenner et al. (Journal of Organometallic Chemistry, 373, 1989, 343-352) following were in a 500 ml laboratory autoclave, equipped with a stirrer, a heated jacket, pressure sensor and temperature probe and inert gas supply a lot of 159.57 g (1.4 mol) of 1- (2-aminoethyl) pyrrolidine, 37.24 g (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. The analysis showed, in addition to unreacted 1- (2-aminoethyl) pyrrolidine, a small proportion of the mono-attached product and the products of the formula (Never). 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 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 according to formula (Never) 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 (Never)

Chemical CAS supplier

1- (2-aminoethyl) pyrrolidine 7154-73-6 ABCR

N-methyldiethanolamine Ss99%, 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) following were in a 500 ml laboratory autoclave equipped with a stirrer, a heated jacket, pressure sensor and temperature probe and inert gas inlet amount of 1 13.98 g (1 mol) of 1- (2-aminoethyl) pyrrolidine, 71.5 g (600 mmol) of N-methyldiethanolamine, 1.17 g (4.5 mmol) of ruthenium (III) chloride trihydrate (0.75 g) 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. The analysis showed unreacted 1- (2-aminoethyl) pyrrolidine as well as mono-attached products 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. 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 of 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 dian-coated product of formula (Nie ) be 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, 3M in THF 75-21 -8 Sigma-Aldrich

Chemie GmbH In a 1000 ml laboratory autoclave, equipped with a stirrer, a heatable jacket, pressure sensor and temperature probe and inert gas inlet was added with 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 (acc. 1 mol of ethylene oxide) and added an additional 35.56 g (0.5 mol) of pyrrolidine. 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 , 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) following were in a 500 ml laboratory autoclave, equipped with a stirrer, a heated jacket, pressure sensor and temperature probe and inert gas inlet a quantity of 159.23 g (1 mol) of 2- ( 2- (pyrrolidin-1-yl) ethoxy) ethanol, 75.1 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 (1 1, 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. The 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 the 2 methylamino-ethanol of. The crude reaction mixture was therefore with little ethanol and filter aid (Celite ^®) provided, filtered through a fluted 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, 2M 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) following were in a 500 ml laboratory autoclave, equipped with a stirrer, a heated jacket, pressure sensor and temperature probe and inert gas inlet an amount of 79.62 g (0.5 mol) 2 (2- (pyrrolidin-1-yl) ethoxy) 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 GC / 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 with little ethanol and filter aid (Celite ^®) provided, filtered through a fluted filter and the solvent was then removed on a rotary evaporator. The residue was then subjected to fractional precision distillation, whereby the desired product of 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 parts by mass (pphp)

PolyoM ¹ »100 parts

Water 2.60 parts

Cyclopentane 13.1 parts

Amine 0.80 or 1.50 parts (see Table 2)

TEGOSTAB ^® B 8460 ²⁾ 1, 50 parts of

Desmodui ^ 44V20L ³ > 198.5 parts) 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 quantity of blowing agent which was vaporized during the mixing process was determined and supplemented again. Now the isocyanate (MDI) was added, the reaction mixture was stirred with the described stirrer at 3000 rpm for 5 s and immediately transferred to a box lined with paper (27 cm x 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 according to 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).

Cream time gel time rise time tack-free time

Amin

[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⁾ 8 121 179 196

FORMULA (IIIa ^* ) ¹⁾ 20 160 235 325

FORMULA (IIIb ^* ) ¹⁾ 39 176 277 290

FORMULA (lllc ^* ) ¹⁾ 62 282 435 510

FORMULA (llld ^* ) ¹⁾ 53 214 378 432

FORMULA (llle ^* ) ¹⁾ 55 219 390 420

FORMULA (Ulf ^* ) ¹ »20 136 203 218

FORMULA (lg ^* ¹⁾ 17 128 227 278) 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 according to the formula (IIIb) has a slight improvement in terms of final curing.

Flexible foam - application tests

Physical properties of flexible polyurethane foams:

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 increase results from the difference in the foam height after direct blowing and after 3 minutes, after blowing off the foam. The foam height is determined by a needle attached to a centimeter measure at the maximum in the middle of the

Foam head measured. 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 carried out by measuring the core density as described in ASTM D 3574-1.1 under test A. 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 x 100 mm

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 scaled

Glass tube adjusted so that no pressure difference is built up and readable. For the measurement of the test specimen with a dimension of 250 x 250 x 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. Compressive hardness CLD, 40% according to DIN EN ISO 3386. The measured values are given in kilopascals (kPa).

Measurement of foam emissions (VOC and Fog value) in accordance with the test specification VDA 278 in the version of October 201 1:

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 emissions, the emissions of the individual components of inventive catalyst combinations or their Zer- or reaction products, was determined in accordance with the test specification VDA 278 in the version of October 201 1. In the following, the implementation of the corresponding thermal desorption with subsequent gas chromatography / mass spectrometry coupling (GC / MS) is described.

Measurement technique: Thermodesorption was performed with a thermal desorber "TDS2" with sample changer from Gerstel, Mülheim, in combination with an Agilent 7890/5975 GC / MSD system.

The measurement conditions for VOC measurements are given in Tables 3 and 4.

Table 3: Measurement parameters thermal desorption for the VOC analysis run.

Thermodesorption Gerstel TDS2

Desorption temperature 90 ° C

Desorption time 30 min

Flow 65 ml / min

Transfer line 280 ° C

Cryofocusing KAS 4

Liner glass evaporator tube with silanized

glass wool

Temperature -150 ° C

Table 4: Measurement parameters gas chromatography / mass spectrometry for the VOC Analytical run.

GC capillary GC Agilent 7890

Injector PTV Split 1: 50

Te m pe ra tu rp ra m m -150 ° C; 1 min; ^ 10 ° C / s; 280 ° C

Column Agilent 19091 B-1 15, Ultra 2, 50 m

0.32 mm dF Ο, δμηι

Flow 1, 3 ml / min const. flow

Te m pe ra tu rp rog ra m m 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

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 minutes, 280 ° C.). ,

^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.

Sample preparation for VOC measurement: 15 mg of foam were placed in three subsamples in a thermodisorption tube. It was ensured that the foam is not compressed.

Sample preparation for the fog measurement: The same foam sample was used as for the 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.

The measurement conditions for fog measurements are given in Tables 5 and 6. Table 5: Measurement parameters thermal desorption for the fog analysis run.

Thermodisorption Gerstel TDS2

Desorption temperature 120 ° C

Desorption time 60 min

Flow 65 ml / min

Transfer line 280 ° C

Cryofocusing KAS 4

Liner glass evaporator tube with silanized

glass wool

Temperature -150 ° C

Table 6: Measurement parameters gas chromatography / mass spectrometry for the analysis run.

GC capillary GC Agilent 7890

Injector PTV Split 1: 50

Te m pe ra tu rp ra m m -150 ° C; 1 min; ^ 10 ° C / s; 280 ° C

Column Agilent 19091 B-1 15, Ultra 2, 50 m ^*

0.32 mm dF Ο, δμηι

Flow 1, 3 ml / min const. flow

Te m pe ra tu rp rog ra m m 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

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 Zer- or reaction products, at room temperature based on the DIN Regulation DIN EN ISO 16000-9: 2008-04. The sample was taken after 24 hours. For this purpose, 2 liters of Prüfkammeratmosphäre with a flow rate of 100 ml / min with a Tenax ^® TA (mesh35 / 60) filled adsorption were added. in the The following describes the performance of thermal desorption with subsequent 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.

Thermodesorption Gerstel TDS2

Desorption temperature 280 ° C

Desorption time 5 min

Flow 65 ml / min

Transfer line 280 ° C

Cryofocusing KAS 4

Liner glass evaporator tube with silanized

glass wool

Temperature -150 ° C

Table 8: Measurement parameters gas chromatography / mass spectrometry for PK measurement.

GC capillary GC Agilent 7890

Te m pe ra tu rp ra m m -150 ° C; 1 min; ^ 10 ° C / s; 280 ° C

Column Agilent 19091 B-1 15, Ultra 2, 50 m ^*

0.32 mm dF Ο, δμηι

Flow 1, 3 ml / min const. flow

Te m pe ra tu rp rog ra m m 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 the Totalionenstrom- Chromatrogramms by calculation as toluene c) In order to calibrate 2 μΙ a mixture of toluene and hexadecane in methanol (depending 0.125 mg / ml) was added to a cleaned (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 parts by mass (pphp)

Polyol 1 ¹⁾ 100 parts

Water 3.00 parts

Tin catalyst ²⁾ 0.20 parts

Amine 0.20 parts

TEGOSTAB ^® BF 2370 ³⁾ 0.80 parts

Desmodui ^ T 80 ⁴⁾ 38.1 parts) 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 > Toluylene 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 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 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 x 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 presented on the basis of Specimen determined: 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 were triethylenediamine, 33% by weight solution in dipropylene glycol (TEGOAMIN ^® 33, available from Evonik Industries), N, N-dimethylethanolamine (DMEA TEGOAMIN ^®, 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 used (Jeffcat ZF-10 ^®, available 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).

Climbing time relapse height RG porosity CLD 40%

Amin

[s] [cm] [cm] [kg / m ³ ] [mm] ¹ »[kPa]

TEGOAMIN ^® 33 120 0.1 28.6 31 6 24 4.4

TEGOAMIN ^® DMEA 0.1 137 28.0 31 3.8 2 17

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 (purple ^* ) 120 0.3 28.7 31, 2 18 3.7

FORMULA (IIIb ^* ) 150 0.0 27.5 31, 6 36 4.2

FORMULA (Never ^* ) 133 0.2 28.0 31, 3 20 4.0

FORMULA (llld ^* ) 1 19 0,4 28,6 31, 0 16 3,9

FORMULA (Never ^* ) 128 0.2 28.4 31, 4 21 3.9

FORMULA (Ulf *) 1 12 0.4 28.8 31, 0 15 3.7

FORMULA (lg *) 1 15 0,3 28,7 31, 2 18 3,9) = (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. In terms of activity and selectivity, the highly active nitrogenous compounds of formula (III) are to be classified as similar Jeffcat® ZF-10, as catalysts that preferentially catalyze the blowing reaction. The nitrogenous compounds of the formula (IIIb), (Never) and (Never) 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 to TEGOAMIN ^® 33. 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 foaming formulation given in Table 1 1, which contains a low-emission polyol and a low-emission tin catalyst, was used for the performance testing of flexible slab foams.

Table 1 1: Formulation 3, foam emissions in soft block foam applications.

Formulation 3 parts by mass (pphp)

Polyol 1 ¹⁾ 100 parts

Water 3.00 parts

Tin catalyst ²⁾ 0.60 parts

Amine 0.15 parts

TEGOSTAB ^® BF 2370 ³⁾ 0.80 parts

Desmodui ^ T 80 ⁴⁾ 41, 6 parts) 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 1, 00 g of a substance per 100 g of polyol.

The foaming was carried out by hand mixing. The formulations given in Table 1 1 were used with various nitrogenous catalysts (amines). These were low-emission polyol, conventional or Inventive nitrogen-containing catalyst (amine), low-emission tin catalyst, water and foam stabilizer 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 x 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 out of the resulting foam block, which was completely enclosed in aluminum foil and further sealed with polyethylene film.

The emission behavior of the foams described above was subsequently investigated at room temperature after the test chamber test on the basis of 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 1 1).

Content of volatile organic compounds after the

Test chamber test

Amin PKges ¹ 'PKAmin ¹ '

[g / m ³ ] [g / m ³ ]

TEGOAMIN ^® 33 96 68

TEGOAMIN ^® DMEA 28 <10

TEGOAMIN ^® BDE 316 289

Jeffcat ZF-10 <20 <10

FORMULA (purple ^* ) <20 <10

FORMULA (lllb ^* ) <20 <10

FORMULA (Never ^* ) <20 <10

FORMULA (llld ^* ) <20 <10

FORMULA (Never ^* ) <20 <10

FORMULA (Ulf ^* ) <20 <10

FORMULA (lg ^* ) <20 <10) PKges = total emission; ΡΚΑΓ ™ = 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 of formula (III) have lower amine emissions after the test chamber test as described above than using conventional Catalysts such TEGOAMIN ^® BDE or TEGOAMIN ^® 33. As used herein formulation could even how to TEGOAMIN ^® DMEA and Jeffcat® IF 10 also, most small amine emissions <10 ug m ³ can be obtained, in most cases the obtained foams even free from such emissions. Also with regard to the amine emissions in accordance with the VDA 278, as described above, a partial reduction of the amine emissions with appropriate catalyst-exchange TEGOAMIN ^® BDE or TEGOAMIN ^® 33 was observed.

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 parts by mass (pphp)

Polyol 1 ¹⁾ 70.0 parts

Polyol 2 ² > 30.0 parts

Water 3.70 parts

Glycerol 0.50 parts

Diethanolamine (DEOA) 1.00 parts

Amine 0.25 parts

TEGOSTAB ^® B 8716 LF2 ³⁾ 1, 00 parts of

Desmodui ^ T 80 ⁴⁾ 44.0 parts) 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.

Here, the same foaming methods as in the conventional polyurethane soft foams 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 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 poured into a paper-lined wooden box (27 cm x 27 cm in footprint and 27 cm in height). 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 used (Jeffcat ZF-10 ^®, available 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).

Gelzeit climb time height relapse line number ¹ »

Amin

[s] [s] [cm] [cm] [cm ^"1 ]

TEGOAMIN ^® 33 97 189 31 3 10.5 0.3

TEGOAMIN ^® BDE 55 78 33.5 1 8 10.0

Jeffcat ZF-10 80 1 19 32.8 0.8 10.0

TEGOAMIN ^® DMEA 154,263 26.3 collapse collapse

FORMULA (purple ^* ) 97 206 30,6 0,0 10,0 - 10,5

FORMULA (lllb ^* ) 170 298 25,8 Collapse Collapse

FORMULA (Never ^* ) 156 256 26.8 -0.1 9.0

FORMULA (llld ^* ) 138 231 27,8 0,2 9,5

FORMULA (Never ^* ) 147 248 27.6 0.2 9.0

FORMULA (Ulf ^* ) 75 125 32.8 0.7 10.0

FORMULA (lllg ^* ) 71 98 33.0 1, 1 10.0) 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 partly as balanced catalysts, ie compounds catalyzing both the gel and the blowing reaction (for example the nitrogenous compound according to the formula (Never)), partially balanced catalysts with slight preference for the blowing reaction (for example the nitrogenous compounds of the formula ( purple) and (IIIb)), partially as balanced catalysts with slight preference for the gel reaction (for example, the nitrogen-containing compounds of formulas (IIId) and (Never)) or as catalysts which preferentially catalyze the blowing reaction (for example, the nitrogen-containing Compounds according to the formula (Ulf) and (lllg)), to divide. In this very critical formulation, the use amount of the nitrogen-containing compound according to the formula (IIIb) is not sufficient 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 (Ulf) and (IIIg) are comparable with Jeffcat ZF-10 ^® with respect to selectivity and activity.

Claims

claims

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

(I)

a, b are the same or different from each other 0 to 3, wherein preferably a = 0 to 2 and b = 1 to 3, with the proviso that a + b = 2 or 3, wherein the ether or amine building blocks, if present , cumulative, alternating, blockwise or disorderly,

R 1, R 2 are identical or different, are 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 with 2 carbon atoms,

R 3 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 having 1 to 30 carbon atoms,

, ^R 5

* -N

Y = ^R 4 or * - ° ^R 6,

, ^R 5

* -N

for Y = ^R 4,

R ₄ , R 5 is the same or different from each other is H, a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more heteroatoms or interrupted by one or more heteroatoms hydrocarbon radical or R ₄ and R 5 to one cycle , preferably bridged to a pyrrolidine radical, a morpholine radical, an imidazole radical or a piperazine radical

wherein R 7, Rs, 9 are identical or different and are 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,

for Y = * - ° ^R 6,

where * or N is.

In particular, Y is * -OH,

\ - /, preferably ^» -OH, ^{Ι Π} 2 or particularly preferably * -OH or

2. Use according to claim 1, characterized in that at least one nitrogen-containing compound of the formula (I) with

prefers

f

preferably, * ^{o 0} P ^NH 2, ₀ of

For

preferably 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 Rio, RH , R12, R13, Ri4, R15, Ri6 are identical 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 interrupted by one or more heteroatoms hydrocarbon radical having 1 to 30 carbon atoms,

) H, wherein the R3 is in particular selected from. "_ _H * -CH ₃ * '

3. Use according to claim 1 or 2, characterized in that at least one nitrogen-containing compound of the formula (I) is used where Ri, R2 equal to or not equal to each other is a coal with 1 to 30,

preferably 2 or 3 carbon atoms, expressed by

q is the same or

* -PH unequal to each other 2 or 3 and R17 equal or different from each other * -H or '3 iu

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 sbesondere is selected from the following radicals or

4. 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 R1, R2, R3 as defined in the preceding claims,

where q is particularly preferably used 2,

and wherein this compound satisfies in particular the formula (III)

(III)

with n, a, b, R3, Y as defined in the preceding claims, wherein R3 particularly preferably * -H _I * ^~ CH _{3 J} *

5. 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, wherein

a + b = 2 and

a, b are the same or different from each other 0, 1 or 2,

6. 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, wherein

a = 0 and b = 2,

in particular a connection

is used, with n, q, R3, Y as defined in claim 1-4,

again

are preferably used.

7. 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, wherein

a = 1 and b = 1,

, preferably

and or

, preferably

is used, with n, q, R3, Y as defined in claim 1-4 again

8. 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, wherein

with a + b = 3 and

a, b are the same or different 0, 1, 2 or 3,

9. Use according to one of claims 1 to 4 or 8, 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, wherein

a = 2 and b = 1 is used,

, preferably nd / or

and or

, preferably

e preferential use

10. Use according to one of claims 1 to 4 or 8, 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, wherein

a = 1 and b = 2 is used,

in particular a connection

and or

and or

1 ^{Π q}

is used, with n, q, R3, Y as defined in claim 1-4

again

1 1. Use according to one of claims 1 to 4 or 8, 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, wherein

a = 0 and b = 3,

in particular a connection

is used with n, q, R3, Y as defined in claim 1-4,

particularly preferred compounds being selected from the group comprising

12. Use according to claim 1 to 1 1, characterized in that at least one nitrogen-containing compound according to the formula (I), preferably at least one nitrogen-containing compound according to the formula (II), (III) or (IV), in particular a nitrogen-containing compound according to of formula (III), is used as a technical product mixture, in particular containing impurities, by-products 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 one Total amount of up to 95 wt .-%, preferably <70 wt%, in particular <30 wt .-%, preferably <10 Ge % by weight, more preferably <5% by weight.

13. 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.

14. 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 reacts wherein said nitrogen-containing compound is preferably used as a technical product mixture according to claims 15 or 16.

15. 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 according to 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 is preferably from 100 to 1 to 1 to 4, preferably from 50 to 1 to 1 to 3 and particularly preferably from 25 to 1 to 1 to 2.

16. 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, the composition preferably having at least one isocyanate component, and wherein the nitrogen-containing compound of the 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).

17. A composition according to claim 16, characterized in that the molar ratio of the total amount of the nitrogen-containing catalysts comprising the nitrogen-containing compounds of the formula (I), (II), (III) or (IV), over the Total amount of the isocyanate-reactive groups of the polyol component of 4 x 10 ^"4 to 1 to 0.2 to 1.

18. Compositions according to claim 16 or 17, 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.

19. polyurethane system, characterized in that it is obtainable by a use according to one of the preceding claims 1 to 15, 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-rigid 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% by weight.

20. Use of polyurethane systems according to claim 19 as a 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, furniture molded foam, pillows, rebonded foam , Sponge foam, automotive upholstery, 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.