DE102014215380B4 - Nitrogen-containing compounds suitable for use in the manufacture of polyurethanes - Google Patents

Abstract

Use of at least one nitrogen-containing compound and/or a corresponding quaternized and/or protonated compound for producing rigid polyurethane foams which lead to less discoloration of plastics, characterized in that the nitrogen-containing compound satisfies the formula (IVc).

Description

The present invention is in the field of nitrogen-containing compounds, in particular amines, and polyurethanes. It relates to the use of at least one nitrogen-containing compound of the formula (IVc), corresponding to quaternized and/or protonated compounds, for the production of rigid polyurethane foams as claimed in claim 1.

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

All reaction products starting from isocyanates, in particular from polyisocyanates, and corresponding isocyanate-reactive molecules are understood here as polyurethanes. This also includes, inter alia, polyisocyanurates, polyureas and isocyanate or polyisocyanate reaction products containing allophanate, biuret, uretdione, uretimine or carbodiimide. The use of the tertiary amines in the production of polyisocyanate polyaddition products is preferred.

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

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

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. Rigid polyurethane foams are mainly used as insulating materials, for example in refrigerator systems or for the thermal insulation of buildings. Flexible polyurethane foams are used in a large number of technical applications in industry and in the private sector, for example for noise insulation, for the manufacture of mattresses or for upholstering furniture. A particularly important market for various types of PU foams, such as conventional flexible foams based on ether or ester polyols, flexible cold foams, also referred to below as cold foams (often also referred to as "high resilience" (HR) foams), and rigid foams, as well as foams with their properties The automotive industry represents what lies between these classifications. Here, for example, rigid foams can be used as headliners, ester foams for the interior lining of the doors and for punched sun visors, cold and flexible foams for seating systems and mattresses.

With regard to flexible foams, a distinction can also be made between cold flexible foams and hot flexible foams, such as in EP 2042 534 A1 described, which is incorporated herein by reference in its entirety.

There is still a need for further alternative nitrogen-containing catalysts which are suitable for the production of polyurethanes, in particular polyurethane foam, which preferably leads to less discoloration of plastics.

JP H08-259655 A discloses the use of amine catalysts, such as hydroxyethylpyrrolidine, for the production of polyurethane foams.

WO 2005/111109 A1 discloses nitrogen-containing compounds, such as N-aminopropylpyrrolidine, as catalysts for the production of polyurethane foams.

DE 10 2009 003 274 A1 discloses the combined use of amines and polyether-siloxane copolymers in the production of polyurethane foams.

EP 0 495 249 A1 discloses the use of N-(aminoalkyl)pyrrolidines as catalysts for the production of flexible polyurethane foams.

A specific object of the present invention was therefore to provide an alternative catalyst for the production of polyisocyanate reaction products, preferably polyurethanes, in particular polyurethane foams, which preferably lead to less discoloration of plastics.

Surprisingly, it has been found that compounds of the formula (IVc) below, the corresponding quaternized and/or protonated compounds, solve this problem, i.e. both the use of the compounds of the formula (IVc) and the use of the corresponding protonated compounds and the use of the corresponding quaternized compounds and the use of corresponding mixtures each solves the stated task.

The present invention relates to the use of at least one nitrogen-containing compound and/or a corresponding quaternized and/or protonated compound for producing rigid polyurethane foams which lead to less discoloration of plastics, the nitrogen-containing compound of the formula (IVc) being sufficient

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

The nitrogen-containing compound of the formula (IVc) used according to the invention and correspondingly quaternized and/or protonated compounds, and mixtures of the aforementioned, are suitable as catalysts for the production of polyisocyanate reaction products, preferably polyurethanes, in particular polyurethane foams, and can be both the gel and also catalyze the blowing reaction during foaming, and advantageously other isocyanate reactions, as described below.

The invention makes it possible to provide rigid polyurethane foams which lead to less discoloration of plastics.

The presence of polyurethane systems, especially polyurethane foams, especially in automobile interiors, can usually cause other plastic parts, especially those made of PVC, to become discolored. For example, discoloration of plastic covers, for example the plastic cover of headliners in automobiles, can occur. It was found within the scope of this invention that the presence of polyurethane systems, in particular foams, is the cause of this discoloration. Surprisingly, it has now been found that the rigid polyurethane foams provided according to the invention lead to less discoloration of these plastics compared to prior art polyurethane systems containing conventional amine catalysts. Our invention thus enables the provision of rigid polyurethane foams, preferably for use in the automotive industry, in particular in automotive interiors, for example as headliners, interior door panels, punched sun visors, steering wheels and / or seat systems, the rigid polyurethane foams provided according to the invention in particular leading to less discoloration of plastics , in particular plastic covers, especially in automobile interiors, compared to the use of conventional polyurethane systems. This can be shown in particular using a PVC discoloration test in accordance with Volkswagen test specification VW PV 3937.

Advantageously, the present invention also makes it possible to reduce or avoid emissions caused by catalysis in the production of polyurethane foams.

In particular, an additional advantage of the invention is that the nitrogen-containing compound of the formula (IVc) used according to the invention, correspondingly quaternized and/or protonated compounds, and mixtures of the aforementioned, are advantageously low in emissions, preferably free of typical undesirable emissions from the resulting polyurethane foams, viz advantageously low in emissions with regard to emissions of nitrogenous compounds, also referred to below as amine emissions, advantageously low in emissions with regard to emissions of dimethylformamide (DMF), and advantageously low-emission in terms of aldehyde emissions, especially in terms of formaldehyde emissions.

In the context of the present invention, “low-emission” with regard to amines includes in particular that the polyurethane foam has an amine emission of ≧0 μg/m ³ and ≦40 μg/m ³ , preferably ≦10 μg/m ³ , particularly preferably ≦5 μg /m ³ , determined according to the test chamber method based on the DIN standard DIN EN ISO 16000-9:2008-04, 24 hours after test chamber loading, and/or that the polyurethane foam, preferably for the production of polyurethanes for use in in the automotive industry, especially in automotive interiors, for example as headliners, interior door panels, punched sun visors, steering wheels and/or seat systems, amine emissions, hereinafter also referred to as VOC emissions or VOC values according to VDA 278 (VOC = Volatile Organic Compounds). ), of ≧0 μg/g and ≦40 μg/g, preferably ≦10 μg/g, particularly preferably ≦5 μg/g, according to the VDA 278 analysis method in the version from October 2011, “Thermodesorpti Analysis of organic emissions to characterize non-metallic automotive materials" (30 minutes at 90 °C), and/or that of polyurethane foam, preferably for the production of polyurethanes for use in the automotive industry, especially in automotive interiors, for example as headliners, interior door panels, stamped sun visors, steering wheels and/or seat systems, an amine emission, also referred to below as fog emission or fog value according to VDA 278 (fog: non-volatile substances that condense easily at room temperature and contribute to fogging on the windshield), from ≧0 μg/g and ≦40 μg/g, preferably ≦10 μg/g, particularly preferably ≦5 μg/g, according to the VDA 278 analysis method in the October 2011 version (60 minutes at 120° C.). VDA is the Association of the Automotive Industry (www.vda.de). Depending on the area of application of the polyurethane foams, for example when used in the automotive industry, there may be limits for the total emissions of volatile organic compounds (VOC _tot and/or fog _tot ) depending on the vehicle manufacturer's specifications, for example VOC _tot ≤ 100 µg/g and/or Fog _tot ≤ 250 µg/g. It is all the more important that the contribution of the amines to the total emissions (VOC _amine and/or fog _amine ) is as small as possible. The determination methods selected for the purposes 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-emission" with regard to emissions of dimethylformamide (DMF) means in the context of the present invention in particular that the nitrogen-containing compound of the formula (IVc) according to the invention and / or corresponding polyurethane foams, produced using the aforementioned compounds, a DMF emission of ≥ 0 ppm and ≦5 ppm, preferably ≦1 ppm, particularly preferably ≦0.1 ppm.

"Low-emission" with regard to emissions of aldehydes, in particular formaldehyde, means in the context of the present invention in particular that the polyurethane foam, the limits for aldehyde emissions set by the foam manufacturers and the furniture industry in Europe and the USA as part of the voluntarily imposed "CertiPUR" program, 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 nitrogenous compounds to be used according to the invention in the formulation of a corresponding polyurethane system leads to an improvement in emissions caused by aldehydes, in particular formaldehyde. According to "CertiPUR", the limit for formaldehyde emissions for mattresses, for example, is 0.1 mg/m ³ measured according to ASTM method D5116-97 "Small Chamber Test" with conditioning for 16 hours. Various analytical methods for determining aldehyde emissions are known to those skilled in the art. Examples include VDA 275, VDA 277 or VDA 278, as well as various chamber test methods. VDA is the Association of the Automotive Industry (www.vda.de). "VDA 275", according to the version from July 1994, provides a measurement method for determining the release of aldehydes, in particular formaldehyde, according to the modified bottle method, whereby 2.4 -Dinitrophenylhydrazine (2,4-DNP) (detection via HPLC after external calibration) can be used to be able to better determine acetaldehyde and propionaldehyde in addition to formaldehyde. Within the scope of this invention, reference is made to both process designs of this VDA 275 as preferred processes for determining aldehyde, in particular formaldehyde, emissions.

Advantageously, the present invention thus makes it possible to provide polyurethane foams which, with regard to emissions of nitrogenous compounds, also referred to below as amine emissions, are particularly low in emissions, preferably free of such emissions, even with different requirements.

Advantageously, the present invention thus makes it possible to provide polyurethane foams, produced using the aforementioned nitrogen-containing compounds, which are particularly low in emissions of dimethylformamide (DMF), even with different requirements, and are preferably free of such emissions.

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

Advantageously, the present invention also contributes to the provision of low odor polyurethane foams. Low-odor here means that the resulting polyurethane system has as little product odor as possible, especially when using the nitrogen-containing compounds of the invention as alternative catalysts to catalysts according to the prior art, which can be checked in particular by an olfactory test by a panel of people trained in odors.

Advantageously, the present invention also contributes to improving the aging behavior, in particular the heat resistance and/or aging resistance on tempering (heat aging), of polyurethane foams. Such aging phenomena are often closely linked to the choice of the catalyst system for the production of the polyurethane systems and generally lead to material fatigue. With the nitrogen-containing compounds according to the invention, the heat resistance and/or durability of the corresponding polyurethane systems can advantageously be improved here compared with polyurethane systems which have been produced using conventional catalysts according to the prior art. This effect can advantageously be observed in particular in the case of polyurethane foams, in particular in the sense of dry thermal aging according to DIN standard DIN EN ISO 2440/A1:2009-01, in particular at a temperature of 70, 100, 120, 130 and/or 140°C and an aging time of 2, 4, 16, 22, 24, 48, 72 and/or 168 hours, preferably 2, 24 and/or 168 hours, if nitrogen-containing compounds of the formula (IVc) according to the invention are used as alternatives to structurally related catalysts during foaming be used according to the state of the art.

Advantageously, the present invention allows for a wider processing latitude in the manufacture of polyurethane systems, particularly semi-rigid polyurethane foams (rigid open-cell foams, for example for use as headliners in automobile interiors). This means that advantageously a greater range of variation in the use concentration of the nitrogen-containing compounds according to the invention is possible without negatively affecting the desired material properties, for example the open-cell nature of the foam or the density distribution over the foam block, compared to comparable amine catalysts or those commonly used for such applications according to the prior art Technology. This means an enormous reduction in workload for the user.

For the possible quaternization of the compound of the formula (IVc), all reagents known as quaternization reagents can be used. Preferred quaternizing agents are alkylating agents, such as e.g. B. dimethyl sulfate, methyl chloride or benzyl chloride, preferably methylating agents such as dimethyl sulfate used in particular.

It is also possible to quaternize with alkylene oxides such as, for example, ethylene oxide, propylene oxide or butylene oxide, preferably with subsequent neutralization with inorganic or organic acids.

If quaternized, the compound of the formula (IVc) can be monoquaternized or polyquaternized. The compound of the formula (IVc) is preferably only singly quaternized. In the case of simple quaternisation, the compound of formula (IVc) is preferably quaternised on a nitrogen atom which is part of a ring, preferably a pyrrolidine ring.

The compound of the formula (IVc) can be converted into the corresponding protonated compounds by reaction with organic or inorganic acids. These protonated compounds can be preferred, for example, if, for example, a slower polyurethane reaction is to be achieved or if the reaction mixture is to have improved flow behavior in use.

Organic acids which can be used are, for example, all of 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 else polymeric acids such as polyacrylic acid, for example. or polymethacrylic acids can be used. As the inorganic acid, for example, phosphorus-based acid, sulfur-based acid or boron-based acid can be used.

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

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

In the context of the present invention, polyurethane (PU) is understood to mean in particular a product obtainable by reaction of polyisocyanates and polyols or compounds having isocyanate-reactive groups. In addition to the polyurethane, other functional groups can also be formed, such as uretdiones, carbodiimides, isocyanurates, allophanates, biurets, ureas and/or uretimines. For the purposes of the present invention, PU is therefore understood to mean both polyurethane and polyisocyanurate, polyureas and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret and uretimine groups. In the context of the present invention, polyurethane foam (PU foam) is understood to mean foam which is obtained as a reaction product based on polyisocyanates and polyols or compounds with isocyanate-reactive groups. In addition to the polyurethane that gives the product its name, other functional groups can also be formed, such as allophanates, biurets, ureas, carbodiimides, uretdiones, isocyanurates or uretimines. For the purposes of the present invention, PU foams are therefore understood to mean both polyurethane foams (PUR foams) and polyisocyanurate foams (PIR foams). Preferred polyurethane foams are rigid polyurethane foams.

worin

a

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

b

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

c

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

d

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

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

R

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

R2

unabhängig voneinander R¹ oder R ist,

R1

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

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

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

x

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

x'

0 oder 1,

y

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

z

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

R'

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

R''

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

RIV

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

R4

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

mit der Maßgabe, dass mindestens ein Substituent aus R¹, R² und R⁴ nicht gleich R ist,
zur Herstellung von Polyurethanhartschaumstoffen,
wobei die zumindest eine stickstoffhaltige Verbindung nach der Formel (IVc) genügt,
und wobei vorzugsweise das Siloxan nach der Formel (V) mindestens einen Rest R₁ enthält,
wobei dieser Rest R₁ bevorzugt ein Polyetherrest ist. Die verschiedenen Monomereinheiten der in den Formeln angegebenen Bausteine (Siloxanketten bzw. Polyoxyalkylenkette) können untereinander blockweise aufgebaut sein mit einer beliebigen Anzahl an Blöcken und einer beliebigen Sequenz oder einer statistischen Verteilung unterliegen. Die in den Formeln verwendeten Indices sind als statistische Mittelwerte zu betrachten. Preference is also given to the use according to the invention of at least one nitrogen-containing compound of the formula (IVc) as described above, in particular according to one of the described embodiments, together with at least one siloxane of the formula (V),

wherein

a

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

i.e

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

with the proviso that per molecule of formula (V) the average number Σd of T units [SiR ³ R ⁴ O] and the average number Σc of Q units [SiR ³ R ³ O] per molecule is not greater than 50 , the average number Σa of D units [SiRRO] per molecule is not greater than 2000 and the average number Σb of siloxy units carrying R ¹ per molecule is not greater than 100,

R

independently of one another is 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 a methyl radical,

R2

is independently R ¹ or R,

R1

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

-CH ₂ -CH ₂ -CH ₂ -O-(CH ₂ -CH ₂ O-) _x -(CH ₂ -CH(R')O-) _y -R" -CH ₂ -CH ₂ -O-(CH ₂ -CH ₂ O-) _x -(CH ₂ -CH(R')O-) _y -R" -O-(C ₂ H ₄ O-) _x -(C ₃ H ₅ O-) _y -R' _-CH2 -R ^IV -CH ₂ -CH ₂ -(O) _x' -R ^IV _{-CH2 -CH2 -CH2} -O- _CH2 -CH(OH) _-CH2 OH

or -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -C(CH ₂ OH) ₂ -CH ₂ -CH ₃ is what

x

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

x'

0 or 1,

y

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

e.g

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

R'

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

R''

independently a hydrogen radical or an alkyl group having 1 to 4 carbon atoms, a group -C(O)-R''' with R''' = alkyl radical, a group -CH ₂ -O-R', an alkylaryl group, such as e.g. B. a benzyl group, the group -C(O)NH-R' means,

RIV

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

R4

independently of one another R, R ¹ and/or a heteroatom-substituted, functionalized, organic, saturated or unsaturated radical selected from the group of alkyl, aryl, chloroalkyl, chloroaryl, fluoroalkyl, cyanoalkyl, acryloxyaryl, acryloxyalkyl , methacryloxyalkyl, methacryloxypropyl or vinyl radical,

with the proviso that at least one substituent from R ¹ , R ² and R ⁴ is not the same as R,
for the production of rigid polyurethane foams,
wherein the at least one nitrogen-containing compound of the formula (IVc) is sufficient,
and where preferably the siloxane of the formula (V) contains at least one radical R ₁ ,
where this radical R ₁ is preferably a polyether radical. The various monomer units of the building blocks given in the formulas (siloxane chains or polyoxyalkylene chains) can be built up in blocks with one another, with any number of blocks and any sequence or subject to a statistical distribution. The indices used in the formulas are to be regarded as statistical mean values.

The siloxane of the formula (V), siloxanes which can be used with particular preference, are described further below.

If at least one nitrogen-containing compound of the formula (IVc) is mentioned in the context of this invention, then this includes the use of the corresponding protonated compounds as well as the use of the corresponding quaternized compounds and the use of corresponding mixtures of the aforementioned nitrogen-containing compound (IVc ), corresponding protonated and/or quaternized compounds.

The above-described nitrogen-containing compound of the formula (IVc) according to the invention can in principle be obtained via conventional processes for amine production. A good overview of the production and derivatization of amines, for example with ethylene oxide and propylene oxide (alkoxylation), in particular also for the synthesis of pyrrolidine, can be found in the article "Amines, Aliphatic" in Ullmann's Encylopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2012, Vol. 2, pp. 647-698 (DOI: 10.1002/14356007.a02_001) and the references contained therein.
For illustration, the preparation and performance testing of selected compounds according to the invention and not according to the invention is described in detail in the example section.

The nitrogen-containing compound of the formula (IVc) according to the invention is commercially available (CAS No.: 7154-73-6), for example from ABCR or Sigma-Aldrich. Production can take place, for example, in the sense of a Strecker reaction via an addition of hydrocyanic acid and formaldehyde to pyrrolidine, followed by reduction of the nitrile group with hydrogen.

Depending on the desired target structure, the amines obtained in this way can also be further derivatized, for example in the sense of an alkoxylation, preferably with ethylene oxide (EO) and/or propylene oxide (PO), as already described above. Optionally, methyl groups can also be inserted into the molecular structure in the sense of an N-methylation. Here, for example, the reductive methylation of primary and secondary amines using formaldehyde and formic acid in the sense of an 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 the Eschweiler-Clarke methylation can be found, inter alia, in W. Eschweiler, Ber. 38 , 880 (1905) and HT Clarke, et al., J. Am. Chem. Soc. 55, 4571 (1933) and other synthetic applications, for example also in E. Farkas, CJ Sunman, J. Org. Chem. 50, 1110 (1985) or J. Casanova, P. Devi, Synth. community 23 , 245 (1993). Alternative methylation methods include the use of methanol, dimethyl sulfate (DMS), dimethyl sulfoxide (DMSO), or alkyl halides as the alkylating agent, among others. With regard to such methods, reference is made to the diverse literature on this subject known to the person skilled in the art.

In addition, depending on the desired target compound, the N-methyl groups can be introduced into the molecular structure, for example by using monomethylamine as an N-methyl building block, for example by transition-metal-catalyzed reaction, for example using Raney metals such as Raney Cobalt or Raney nickel, with hydroxyl-bearing compounds such as diols or amino alcohols. Such aminations of alcohols with monomethylamine are widely described in the literature, for example in US5639916 or DE 4230402 . Depending on the process conditions and selected reaction regime, a wide range of by-products can also occur, for example due to incomplete or only partial conversion of the starting materials, and due to side reactions, for example between the selected starting materials, for example between polyamines, polyols and/or amino alcohols.

Depending on the production process, a nitrogen-containing compound of the formula (IVc) can be present, depending on the quality of the process selected and the number of corresponding purification steps, in technical quality, hereinafter also referred to as technical product mixture, i.e. for example intermediates and/or by-products as secondary components and / or have other impurities.

In this case, the use corresponds to at least one nitrogen-containing compound of the formula (IVc) being used as a technical product mixture, in particular containing impurities, intermediates and/or by-products as further ingredients, in particular comprising pyrrolidine, 1-(2-chloroethyl)pyrrolidine, 1,4-butanediol, monoethylene glycol (MEG), diethylene glycol (DEG), 1-2-propylene glycol (PG), dipropylene glycol (DPG) and/or monoethanolamine, in amounts of up to 95% by weight, preferably ≤ 70% by weight. %, in particular ≦30% by weight, preferably ≦10% by weight, particularly preferably ≦5% by weight, of a preferred embodiment of the invention. A lower limit can be 0.1% by weight, for example. Such a preferred product mixture of technical quality can be used with great advantage in the processes and uses according to the invention and makes it possible to solve the task at hand.

1. (a) zumindest eine stickstoffhaltige Verbindung der Formel (IVc), vorteilhafterweise in einer Gesamtmenge von ≥ 5 Gew.-%, bevorzugt 20-95 Gew.-%, insbesondere 30-70 Gew.-%,
2. (b) optional 1,4-Butandiol, vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
3. (c) optional Monoethylenglycol (MEG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
4. (d) optional Diethylenglycol (DEG) vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
5. (e) optional 1-2-Propylenglycol (PG) vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-% und/oder
6. (f) optional Dipropylenglycol (DPG) vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-% entspricht einer bevorzugten Ausführungsform dieser Erfindung.

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

1. (a) at least one nitrogen-containing compound of the formula (IVc), advantageously in a total amount of ≧5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
2. (b) optionally 1,4-butanediol, advantageously in an amount ≤ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
3. (c) optionally monoethylene glycol (MEG), advantageously in an amount ≤ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
4. (d) optionally diethylene glycol (DEG) advantageously in an amount ≤ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
5. (e) optionally 1-2-propylene glycol (PG) advantageously in an amount of ≦95% by weight, in particular 20-90% by weight, preferably 30-80% by weight and/or
6. (f) optionally dipropylene glycol (DPG), 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.

• mit a), mit b), mit c), mit d), mit e) oder mit f).

Within the meaning of the aforementioned preferred embodiment, particularly preferred technical product mixtures in the context of the present invention are those compositions in which at least at least one nitrogen-containing compound according to formula (IVc) and/or a corresponding quaternized and/or protonated compound is used in combination:

• with a), with b), with c), with d), with e) or with f).

The compound of the formula (IVc) described above and/or corresponding quaternized and/or protonated compounds are preferably used as catalysts in the production of rigid polyurethane foams according to the invention. The compounds of the formula (IVc) and/or the corresponding quaternized and/or protonated compounds can be used in addition to customary catalysts or as a substitute for customary catalysts. In particular, the compounds according to the invention can be used as a replacement for other nitrogen-containing catalysts, also referred to below as amine catalysts or amines, and depending on the application as a partial or complete replacement for customary metal-containing catalysts of the prior art.

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

It goes without saying that the person skilled in the art selects the substances required for the production of the various rigid polyurethane foams, such as isocyanates, polyols, stabilizers, surfactants, etc., in order to obtain the type of rigid polyurethane foam desired in each case.

In the production of rigid polyurethane foams according to the invention, preferably at least one compound according to the invention of formula (IVc), 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, reacts with each other.

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

The compounds of the formula (IVc) to be used according to the invention and/or a correspondingly quaternized and/or protonated compound, in total, are preferably used in a mass fraction 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) polyol component used.

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

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

Isocyanates suitable as isocyanate components for the purposes of this invention are all isocyanates which contain at least two isocyanate groups. In general, all aliphatic, cycloaliphatic, arylaliphatic and preferably aromatic polyfunctional isocyanates known per se 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 1,4-diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, tetramethylene 1,4-diisocyanate and preferably hexamethylene-1,6 diisocyanate (HMDI), cycloaliphatic diisocyanates such as cyclohexane-1,3- and 1-4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,35-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI for short), 2,4- and 2,6-hexahydrotoluylene diisocyanate and the corresponding isomer mixtures, and preferably aromatic di- and polyisocyanates, such as 2,4- and 2,6-toluene diisocyanate (TDI) and the corresponding isomer mixtures, mixtures of 2,4'- and 2,2'- '-diphenylmethane diisocyanates (MDI) and polyphenylpolymethylene polyisocyanates (crude MDI) and mixtures of crude MDI and toluene diisocyanates (TDI). The organic di- and polyisocyanates can be used individually or in the form of their mixtures.

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

Particularly suitable organic polyisocyanates and therefore particularly preferably used are various isomers of toluene diisocyanate (2,4- and 2,6-toluene diisocyanate (TDI), in pure form or as isomer mixtures of different composition), 4,4'-diphenylmethane diisocyanate (MDI), that so-called "crude MDI" or "polymeric MDI" (contains not only the 4,4'- but also the 2,4'- and 2,2'-isomers of MDI and polynuclear products) as well as the binuclear product referred to as "pure MDI". from predominantly 2,4'- and 4,4'-isomer mixtures or their prepolymers. Examples of particularly suitable isocyanates are, for example, in EP1712578 , EP1161474 , WO 00/58383 , US2007/0072951 , EP1678232 and the WO 2005/085310 listed, to which reference is made here in its entirety.

For the purposes of the present invention, polyols suitable as polyol components are all organic substances having a plurality of groups which are reactive toward isocyanates, preferably OH groups, and preparations thereof. Preferred polyols are all for the production of polyurethane systems, especially polyurethane foams; commonly used polyetherpolyols and/or polyesterpolyols and/or hydroxyl-containing aliphatic polycarbonates, in particular polyetherpolycarbonatepolyols and/or polyols of natural origin, so-called “natural oil-based polyols” (NOPs). The polyols usually have a functionality of 1.8 to 8 and number-average molecular weights in the range from 500 to 15,000. The polyols with hydroxyl numbers, also referred to below as OH numbers, in the range from 10 to 1200 mgKOH/g are usually used. The number-average molecular weights are usually determined by gel permeation chromatography (GPC), in particular using polypropylene glycol as the reference substance and tetrahydrofuran (THF) as the eluent. The OH numbers can be determined in particular according to the DIN standard DIN 53240:1971-12.

Polyether polyols can be prepared by known methods, 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 that preferably contains 2 or 3 reactive hydrogen atoms or by cationic polymerization of alkylene oxides in the presence of Lewis -Acids such as antimony pentachloride or boron trifluoride etherate or by double metal cyanide catalysis. Suitable alkylene oxides contain 2 to 4 carbon atoms in the alkylene radical. Examples are tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide; ethylene oxide and 1,2-propylene oxide are preferably used. The alkylene oxides can be used individually, cumulatively, in blocks, alternately one after the other, or as mixtures. In particular, compounds with at least 2, preferably 2 to 8, hydroxyl groups or with at least two primary amino groups in the molecule are used as starter molecules. Examples of starter molecules that can be used are water, di-, tri- or tetrahydric alcohols such as ethylene glycol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, castor oil, etc., higher polyfunctional polyols, in particular sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols 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 , particularly preferably TDA and PMDA. The selection of the suitable starter molecule depends on the respective field of application of the resulting polyether polyol in the production of polyurethane (e.g. different polyols are used for the production of flexible polyurethane foams than for 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 acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, maleic acid and fumaric acid. Examples of aromatic carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and the isomeric naphthalenedicarboxylic acids. The polyester polyols are obtained by condensing these polybasic carboxylic acids with polyhydric alcohols, preferably diols or triols having 2 to 12, particularly preferably 2 to 6, carbon atoms, preferably trimethylolpropane and glycerol.

Polyether polycarbonate polyols are polyols containing carbon dioxide bound as a carbonate. Since carbon dioxide is produced in large quantities as a by-product in many processes in the chemical industry, the use of carbon dioxide as a comonomer in alkylene oxide polymerizations is of particular commercial interest. Partial replacement of alkylene oxides in polyols with carbon dioxide has the potential to significantly reduce the cost of polyol production. In addition, the use of CO ₂ as a comonomer is ecologically very advantageous, since this reaction represents the conversion of a greenhouse gas into a polymer. The production of polyether polycarbonate polyols by addition of alkylene oxides and carbon dioxide onto H-functional starter substances using catalysts has been known for a long time. Various catalyst systems can be used here: The first generation represented heterogeneous zinc or aluminum salts, such as those found in US-A 3900424 or US-A 3953383 are described. Furthermore, mono- and binuclear metal complexes have been used successfully for the copolymerization of CO2 and alkylene oxides ( WO 2010/028362 , WO 2009/130470 , WO 2013/022932 or WO 2011/163133 ). The most important class of catalyst systems for the copolymerization of carbon dioxide and alkylene oxides are the double metal cyanide catalysts, also known as DMC catalysts ( US-A 4500704 , WO 2008/058913 ). Suitable alkylene oxides and H-functional starter substances are those which are also used for the 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 in view of the long-term limited availability of fossil resources, namely oil, coal and gas, and against the background of rising crude oil prices and are already often in such interest Applications described ( WO 2005/033167 ; US2006/0293400 , WO 2006/094227 , WO 2004/096882 , U.S. 2002/0103091 , WO 2006/116456 and EP1678232 ). A number of these polyols from various manufacturers are now available on the market ( WO2004/020497 , US2006/0229375 , WO2009/058367 ). Depending on the basic raw material (e.g. soybean oil, palm oil or castor oil) and the subsequent processing, polyols with different properties result. Two main groups can be distinguished here: a) Polyols based on renewable raw materials, which are modified to such an extent that they can be used 100% for the production of polyurethanes ( WO2004/020497 , US2006/0229375 ); b) Polyols based on renewable raw materials which, due to their processing and properties, can only replace the petrochemical-based polyol to a certain extent ( WO2009/058367 ).

The so-called packed polyols (polymer polyols) represent a further class of usable polyols. These are characterized in that they contain solid organic fillers up to a solids content of 40% or more in disperse distribution. Among others, SAN, PHD and PIPA polyols can be used. SAN polyols are highly reactive polyols containing a dispersed styrene/acrylonitrile (SAN)-based copolymer. PHD polyols are highly reactive polyols which also contain polyurea in dispersed form. PIPA polyols are highly reactive polyols containing a polyurethane in dispersed form, for example formed by the 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 improved cell opening, so that the polyol can be foamed in a controlled manner, especially with TDI, and the foams do not shrink. The solid thus acts as an essential process aid. Another function is to control the hardness through the proportion of solids, because higher proportions of solids result in greater hardness of the foam. The formulations with polyols containing solids are significantly less inherently stable and therefore require physical stabilization in addition to chemical stabilization through the crosslinking reaction. Depending on the solids content of the polyols, they can be used, for example, alone or, for example, in a mixture with the abovementioned unfilled polyols.

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

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

Depending on the required properties of the resulting foams, appropriate polyols can be used, as described, for example, in: U.S. 2007/0072951 A1 , WO 2007/111828 , US2007/0238800 , U.S.6359022 or WO 96/12759 . Other polyols are known to those skilled in the art and can, for example, EP-A-0380993 or US-A-3346557 be taken, to which reference is made in full.

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

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

According to a further preferred embodiment of the invention, autocatalytic polyols, as described above, are used.

According to a further preferred embodiment of the invention, 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 of 200-4000, preferably 400-3000, particularly preferably 600-2500 and usually OH numbers in the range of 10-1000, preferably 20 - 500, particularly preferably 30 - 300 mgKOH/g.

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

According to a further preferred embodiment of the invention, in particular for the production of rigid polyurethane foams, two- to eight-functional polyether alcohols are used which have secondary hydroxyl groups, preferably 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, particularly preferably 3 to 8, number-average molecular weights in the range from 500 to 2000, preferably 800 to 1200 and usually OH numbers in the range from 100 to 1200, preferably 120 to 700, particularly preferably 200 up to 600 mgKOH/g. Depending on the required properties of these inventively preferred foams, polyether alcohols, as described above with higher number-average molecular weights and lower OH numbers, and/or additional polyester polyols, as described above based on aromatic carboxylic acids, are used in addition to the polyols described here.

According to a further preferred embodiment of the invention, preference is given to using mixtures of different, preferably two or three, polyfunctional polyester alcohols and/or polyether alcohols. The polyol combinations used here usually consist of a low-molecular "crosslinker" polyol, for example a rigid foam polyol with high functionality (> 3) and/or a conventional high-molecular slabstock flexible foam or HR polyol and/or a "hypersoft" Polyether polyol with a high content of ethylene oxide blocks and with cell-opening properties.

A preferred ratio of isocyanate and polyol, expressed as the formulation index, i.e. as the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g. OH groups, NH groups) multiplied by 100, is in the range of 10 to 1000, preferred 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 inventive nitrogen-containing compound of the formula (IVc) and/or corresponding protonated and/or quaternized compounds, additional catalysts are used, specifically during foaming or with the inventive nitrogen-containing compounds afterwards of the formula (IVc) and/or corresponding protonated and/or quaternized compounds premixed catalyst combination.

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

The expression "premixed catalyst combination", also referred to below as catalyst combination, includes, in the context of this invention, in particular ready-made mixtures of nitrogen-containing compounds according to the invention of the formula (IVc), corresponding protonated and/or quaternized compounds, additional catalysts and optionally other 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 foaming and not as individual components during the foaming process have to be admitted.

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

Suitable additional catalysts for the purposes of the present invention are, for example, substances which catalyze one of the aforementioned reactions, in particular the gel reaction (isocyanate-polyol), the blowing reaction (isocyanate-water) and/or the dimerization 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 within the meaning of the present invention are all nitrogen-containing compounds according to the prior art, unlike the nitrogen-containing compound of the formula (IVc) according to the invention, which catalyze one of the abovementioned isocyanate reactions and/or for the production of polyurethanes, in particular polyurethane foams can be used.

For the purposes of this invention, the expression “nitrogen-containing compound of the formula (IVc)” includes in each case the corresponding protonated and/or quaternized compounds and mixtures of these compounds.

Examples of suitable additional nitrogen-containing compounds as catalysts in the context of the present invention are the amines triethylamine, N,N-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, N,N-dimethylaminoethylamine, N,N,N',N'-tetramethylethylene-1, 2-diamine, N,N,N',N'-Tetramethylpropylene-1,3-diamine, N,N,N',N'-Tetramethyl-1,4-butanediamine, N,N,N',N'- Tetramethyl-1,6-hexanediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N'-Trimethylaminoethylethanolamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-dimethylaminopropyl- N',N'-dipropan-2-olamine, 2-[[3-(dimethylamino)propyl]methylamino]ethanol, 3-(2-dimethylamino)ethoxy)propylamine, N,N-bis[3-(dimethylamino)propyl ]-amine, N,N,N',N",N"-pentamethyldipropylenetriamine, 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, N,N-bis[3-(dimethylamino)propyl ]-N',N'-dimethylpropane-1,3-diamine, triethylenediamine, 1,4-diazabicyclo[2.2.2]octane-2-methanol, N,N'-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'-dimorpholinodiethyl ether, N,N'-dimethylpiperazine, N-(2-hydroxyethyl)piperazine, N- (2-aminoethyl)piperazine, N,N-dimethylbenzylamine, N,N-dimethylaminoethanol, N,N-diethylaminoethanol, 3-dimethylamino-1-propanol, N,N-dimethylaminoethoxyethanol, N,N-diethylaminoethoxyethanol, bis(2-dimethylaminoethyl ether ), N,N,N'-Trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl)ether, N,N,N'-Trimethyl-N-3'-aminopropyl(bisaminoethyl)ether, tris(dimethylaminopropyl )hexahydro-1,3,5-triazine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,5,7- triazabicyclo[4.4.0]dec-5-ene, N-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,4,6-triazabicyclo[3.3.0]oct-4- en, 1,1,3,3-tetramethylguanidine, tert-butyl-1,1,3,3-tetramethylguanidine, guanidine, 3-dimethylaminopropyl urea, 1,3-bis[3-(dimethylamino)propyl]urea, bis-N,N-(dimethylaminoethoxyethyl)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 within the meaning of the present invention are all metal-containing compounds according to the prior art which catalyze one of the abovementioned isocyanate reactions and/or for the production of polyurethanes, in particular polyurethane foams, in addition to the nitrogen-containing compounds of the formula ( IVc) 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 metal chelate complexes.

For the purposes of this invention, the term “organometallic or organometallic compounds” includes, in particular, the use of metal-containing compounds that have a direct carbon-metal bond, here also as organometallic compounds (e.g. organotin) or organometallic or organometallic compounds (e.g. organotin compounds ) designated. For the purposes of this invention, the term “organometallic or organometallic salts” includes in particular the use of organometallic or organometallic compounds with a salt character, i.e. ionic compounds in which either the anion or cation is of an organometallic nature (e.g. organotin oxides, organotin chlorides or organotin -carboxylates). In the context of this invention, the expression “organic metal salts” includes in particular the use of metal-containing compounds that do not have a direct carbon-metal bond and are at the same time metal salts in which either the anion or the cation is an organic compound (e.g. tin(II )-carboxylates). In the context of this invention, the expression “inorganic metal salts” includes in particular the use of metal-containing compounds or metal salts in which neither anion nor cation is an organic compound, eg metal chlorides (eg tin(II) chloride), pure or mixed, ie containing several metals, metal oxides (eg tin oxides) and/or metal silicates or metal aluminosilicates. In the context of this invention, the expression "coordination compound" includes in particular the use of metal-containing compounds which are composed of one or more central particles and one or more ligands, the central particles being charged or uncharged metals (e.g. metal or tin-amine complexes ). For the purposes of this invention, the expression “metal chelate complexes” includes in particular the use of metal-containing coordination compounds which have ligands with at least two coordination or bonding sites to the metal center (e.g. metal or tin-polyamine or metal or tin- polyether complexes).

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

Suitable inorganic metal salts, in particular as defined above, as additional catalysts in the context of the present invention can be selected, for example, from the group of salts of inorganic acids such as hydrochloric acid, carbonic acid, sulfuric acid, nitric acid and phosphoric acid and/or of 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, can usually only be used in combination with in the production of polyurethane systems, in particular polyurethane foams other organometallic salts, organic metal salts or nitrogen-containing catalysts and not used as the only catalysts, in pure form or mixed in a solvent.

Suitable charged or uncharged metal-containing coordination compounds, in particular the metal chelate complexes, in particular as defined above, as additional catalysts for the purposes of the present invention can be selected, for example, from the group of mononuclear or polynuclear metal-amine, metal-polyamine , metal-polyether, metal-polyester and/or metal-polyamine-polyether complexes. Such complexes can either be formed in situ during foaming and/or prior to foaming, or they can be used as isolated complexes, in pure form or mixed in a solvent. Acetylacetone, benzoylacetone, trifluoroacetylacetone, ethylacetoacetate, salicylaldehyde, salicylaldehydedimine and other Schiff bases, cyclopentanone-2-carboxylate, pyrrolidones such as N-methyl-2-pyrrollidone, N- Ethyl-2-pyrrolidone and polyvinylpyrrolidone (of different 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.

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

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

For the purposes of this invention, the expression “organic acids” includes all organic-chemical, ie carbon-containing, compounds that have a functional group that can enter into an equilibrium reaction in the sense of an acid-base reaction with water and other protonatable solvents.

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

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

Examples of suitable monobasic, dibasic and polybasic, saturated and unsaturated, substituted and unsubstituted carboxylic acids, fatty acids and neoacids or cooking acids are carboxylic acids such as formic acid, acetic acid, propionic acid, propionic acids, acrylic acid, butyric acid, isobutyric acid, 2,2- dimethylbutyric acid, valeric acid, isovaleric acid, 2-methylvaleric acid, 2,2-dimethylvaleric acid (iso-heptanoic acid), pivalic acid, caproic acid, 2-ethylhexanoic acid (iso-octanoic acid), enoic acid, caprylic acid, pelargonic acid, iso-nonanoic acid, 3,5,5- Trimethylhexanoic acid, 2,5,5-trimethylhexanoic acid, 4,5,5-trimethylhexanoic acid, 2,2,4,4-tetramethylpentanoic acid, 6,6-dimethylheptanoic acid, capric acid, neodecanoic acid, 7,7-dimethyloctanoic acid, 2,2-dimethyloctanoic acid, 2,4-dimethyl-2-isopropylpentanoic acid, 2,2,3,5-tetramethylhexanoic acid, 2,2-diethylhexanoic acid, 2,5-dimethyl-2-ethylhexanoic acid, undecanoic acid, lauric acid, tridecanoic acid, neotridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, Margaric Acid, Ste aric acid, oleic acid, linoleic acid, alpha-linolenic acid, phytanic acid, icosenoic acid, erucic acid, ricinoleic acid, vernolic acid, arachidic acid, arachidonic acid, oxalic acid, glycolic acid, glyoxalic acid, malonic acid, lactic acid, citric acid, succinic acid, fumaric acid, maleic acid, malic acid, tartaric acid, glutaric acid, adipic acid, sorbic acid , cinnamic acid, salicylic acid, benzoic acid, terephthalic acid, phthalic acid, iso-phthalic acid, nicotinic acid, carbamic acid, pyrrolidine-2-carboxylic acid and cyclohexane carboxylic acid.

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

Suitable thiols, mercaptoacetic acid esters, sulfuric acid esters, sulfonic acids, phosphoric acid esters (alkyl phosphates), phosphonic acids and/or phosphoric acid esters are, for example, all linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted with one or more heteroatoms, or substituted by one or several heteroatoms interrupted chene 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, ethaneol and/or n-laurylmercaptide.

Particularly suitable organometallic salts and organic metal salts, as defined above, as additional catalysts for the purposes of the present invention are, for example, organotin, tin, zinc, bismuth and potassium salts, in particular corresponding metal carboxylates, alcoholates, thiolates and mercaptoacetates , such as dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate (DBTDL), dioctyltin dilaurate (DOTDL), dimethyltin dineodecanoate, dibutyltin dineodecanoate, dioctyltin dineodecanoate, dibutyltin dioleate, dibutyltin-bis-n-laurylmercaptide, dimethyltin-bis-n-laurylmercaptide, ethylhexmercaptide-ethylhexmercaptide, monomethylyl-trismethylyl-2-mercaptide dimethyltin bis-2-ethylhexylmercaptoacetate, dibutyltin bis-2-ethylhexylmercaptoacetate, dioctyltin bis-isooctylmercaptoacetate, tin(II) acetate, tin(II) 2-ethylhexanoate (tin(II) octoate), tin(II) -isononanoate (tin(II) 3,5,5-trimethylhexanoate), tin(II) neodecanoate, tin(II) ricinoleate, zinc(II) acetate, zinc(II) 2-ethylhexanoate (zinc(II) )-oct oate), zinc(II) isononanoate (zinc(II) 3,5,5-trimethylhexanoate), zinc(II) neodecanoate, zinc(II) ricinoleate, bismuth acetate, bismuth 2-ethylhexanoate, bismuth octoate, bismuth hisononanoate, Bismuth neodecanoate, potassium formate, potassium acetate, potassium 2-ethylhexanoate (potassium octoate), potassium isononanoate, potassium neodecanoate and/or potassium ricinoleate.

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

Suitable additional metal-containing catalysts are generally preferably selected such that they do not have any objectionable intrinsic odor, are essentially toxicologically harmless and that the resulting polyurethane systems, in particular polyurethane foams, have the lowest possible catalyst-related emissions.

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

Suitable additional catalysts are, for example, in UK 102007046860 , EP1985642 , EP1985644 , EP1977825 , U.S. 2008/0234402 , EP 0656382 B1 and U.S. 2007/0282026 A1 and the patents cited therein.

Suitable amounts of additional catalysts depend on the type of catalyst and are preferably in the range from 0.01 to 10.0 pphp, particularly preferably in the range from 0.02 to 5.00 pphp (= parts by weight based on 100 parts by weight 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 the use of additional catalysts and / or premixed catalyst combinations, as defined above, from the sum of all nitrogen-containing compounds used, i.e. the sum of the nitrogen-containing compounds according to the invention of formula (IVc) and the additional nitrogen-containing catalysts according to the prior art, compared to the sum of the metal-containing catalysts, in particular potassium, zinc and/or tin catalysts, a molar ratio of 1:0.05 to 0.05:1, preferably 1:0, 07 to 0.07:1 and more preferably 1:0.1 to 0.1:1.

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

In order to avoid a reaction of the components with one another, in particular reaction of the nitrogen-containing compound of formula (IVc) used according to the invention and/or additional nitrogen-containing catalysts with additional metal-containing catalysts, in particular potassium, zinc and/or tin catalysts, it may be preferred to store these components separately and then add them to the isocyanate and polyol reaction mixture simultaneously or sequentially.

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

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

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

is used, with advantageously before the production of the polyurethane foam, first a composition is prepared, for example in the sense of a pre-metering of the individual components in the mixing head or eg as a premixed catalyst combination, in particular as defined above, containing the aforementioned combination. In particular, the said nitrogenous compound of the formula (IVc) can also be used as a technical product mixture. Suitable technical product mixtures are explained in the description.

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

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

All substances suitable according to the prior art can be used as solvents. Depending on the application, aprotic non-polar, aprotic polar and protic solvents can be used. Suitable aprotic non-polar solvents can be selected, for example, from the following classes of substances, or classes of substances containing the following functional groups: aromatic hydrocarbons, aliphatic hydrocarbons (alkanes (paraffins) and olefins), carboxylic acid esters and polyesters, (Poly)ether and/or halogenated hydrocarbons of low polarity. Suitable aprotic-polar solvents can be selected, for example, from the following substance classes, or substance classes containing the following functional groups: ketones, lactones, lactams, nitriles, carboxamides, sulfoxides and/or sulfones. Suitable protic solvents can be selected, for example, from the following substance classes or substance classes containing the following functional groups: alcohols, polyols, (poly)alkylene glycols, amines, carboxylic acids, in particular fatty acids and/or primary and secondary amides.
Preferred solvents are, for example, mineral oils, hexane, pentane, heptane, decane or mixtures of saturated hydrocarbons, such as. B. Kaydol products from Sonneborn, glycol ethers such as ethylene glycol dimethyl ether (monoglyme), bis(2-methoxyethyl) ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), polyester and polyether polyols, polyols based on renewable raw materials ( NOPs), end-capped polyethers, preferably dialkyl polyethers which have butyl/methyl, methyl/methyl or butyl/butyl radicals as alkyl radicals, preferably those which are obtainable from diol-started polyethers, glycols, glycerol, Carboxylic acid esters, preferably fatty acid esters, for example ethyl acetate and isopropyl myristate, polycarbonates, phthalates, preferably dibutyl phthalate (DBP), dioctyl phthalate (DNOP), diethylhexyl phthalate (DEHP), diisononyl phthalate (DINP), dimethyl phthalate (DMP), diethyl phthalate (DEP), cyclohexanoates, preferably diisononyl cyclohexanoate ( DINCH).

Particular preference is given to solvents which can be processed without problems in the foaming process and which do not adversely affect the properties of the foam. For example, isocyanate-reactive compounds are suitable because they react with the polymer matrix and do not generate any emissions in the foam. Examples are OH-functional compounds such as (poly)alkylene glycols, preferably monoethylene glycol (MEG or EG), diethylene glycol (DEG), triethylene glycol (TEG), 1-2-propylene glycol (PG), dipropylene glycol (DPG), trimethylene glycol (1,3 -propanediol PDO), tetramethylene glycol (butanediol BDO), butyl diglycol (BDG), neopentyl glycol, 2-methyl-1,3-propanediol (Ortegol CXT), 3-methyl-1,5-pentanediol and higher homologues thereof such as polyethylene glycol ( PEG) with average molecular weights between 200 and 3000. Further particularly preferred OH-functional compounds are polyethers with average molecular weights of 200 to 4500, in particular 400 to 2000, preferably water-, allyl-, butyl- or nonyl-started polyethers, in particular those based on propylene oxide (PO) and/or ethylene oxide (EO) blocks.
If the nitrogen-containing compound of the formula (IVc) according to the invention or premixed catalyst combinations of the compounds according to the invention are dissolved with additional catalysts, as defined above, or used in combination with a solvent, the mass ratio of catalyst or catalyst combination to solvent is preferably from 100 to 1 to 1 to 4, preferably from 50 to 1 to 1 to 3 and more preferably from 25 to 1 to 1 to 2.

All substances known from the prior art which are used in the production of polyurethanes, in particular polyurethane foams, can be used as additives, such as blowing agents, preferably water to form CO ₂ 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 ones catalytically active substances, in particular as defined above.

If polyurethane foams are to be produced as polyurethane systems, it can be advantageous to use water as a blowing agent. Preference is given to using enough water for the amount of water to be from 0.10 to 25.0 pphp (pphp=parts by weight based on 100 parts by weight of polyol).

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

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

Crosslinkers and chain extenders are low molecular weight, polyfunctional compounds that are reactive toward isocyanates. For example, hydroxyl or amine terminated substances such as glycerol, neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, triethanolamine (TEOA), diethanolamine (DEOA) and trimethylolpropane are suitable. The concentration used is usually between 0.1 and 5 parts per 100 parts of polyol, but can deviate from this depending on the formulation. When using crude MDI for foam molding, this also takes on a crosslinking function. The content of low-molecular crosslinkers can therefore be correspondingly reduced as the amount of crude MDI increases.

Suitable stabilizers against oxidative degradation, so-called antioxidants, are preferably all common free-radical scavengers, peroxide scavengers, UV absorbers, light stabilizers, complexing agents for metal ion impurities (metal deactivators). Preference can be given to compounds of the following substance classes or substance classes containing the following functional groups, particular preference being given to those which have isocyanate-reactive groups as substituents on the respective base bodies: 2-(2′-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, benzoic acids and Benzoates, phenols, in particular containing tert-butyl and/or methyl substituents on the aromatic, benzofuranones, diarylamines, triazines, 2,2,6,6-tetramethylpiperidines, hydroxylamines, alkyl and aryl phosphites, sulfides, zinc carboxylates, diketones. 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 methylenediphenols such as 4,4'-butylidene-bis-(6-tert-butyl-3-methylphenol) can be used. Preferred 2-(2'-hydroxyphenyl)benzotriazoles are, for example, 2-(2'hydroxy-5'-methylphenyl)benzotriazole or 2-(2'hydroxy-3',5'-di-tert-butylphenyl)benzotriazole. Preferred 2-hydroxybenzophenones are, for example, 2-hydroxy-4-n-octoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone or 2,4-dihydroxybenzophenone. Preferred benzoates are, for example, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate or tannins.

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

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

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

In order to influence the foam properties of polyurethane foams, siloxanes or organomodified siloxanes in particular can be used during their production, it being possible for the substances mentioned in the prior art to be used. Preference is given to using those compounds which are particularly suitable for the particular types of foam (rigid foams, hot flexible foams, viscoelastic foams, ester foams, cold flexible foams (HR foams), semi-rigid foams). Suitable (organomodified) siloxanes are described, for example, in the following publications: EP0839852 , EP1544235 , DE 102004001408 , EP0839852 , WO 2005/118668 , US20070072951 , DE 2533074 , EP1537159 EP 533202 , US3933695 , EP 0780414 , DE 4239054 , DE 4229402 , EP 867465 . These compounds can be prepared as described in the prior art. Suitable examples are e.g. Am US4147847 , EP0493836 and US4855379 described.

All stabilizers known from the prior art can be used as (foam) stabilizers. Foam stabilizers based on polydialkylsiloxane-polyoxyalkylene copolymers, such as are generally used in the production of urethane foams, are preferably used. These compounds are preferably constructed in such a way that, for example, a long-chain copolymer of ethylene oxide and propylene oxide is bonded to a polydimethylsiloxane radical. The linkage between the polydialkylsiloxane and the polyether part can take place via an SiC linkage or an Si—OC bond. Structurally, the different polyether(s) may be terminally or pendently attached to the polydialkylsiloxane. The alkyl radical or the various alkyl radicals can be aliphatic, cycloaliphatic or aromatic. Methyl groups are particularly advantageous here. The polydialkylsiloxane can be linear or contain branches. Suitable stabilizers, in particular foam stabilizers, are, inter alia, in US2834748 , US2917480 as in US3629308 described. Suitable stabilizers can be obtained from Evonik Industries AG under the trade name ^TEGOSTAB® .

Suitable siloxanes which can be used in the inventive use of the nitrogen-containing compound of the formula (IVc) and/or the corresponding quaternized and/or protonated compounds in the production of polyurethane foams have already been mentioned and preferred siloxanes have in particular those already mentioned above Structure (V).

The siloxanes of the formula (V) can be prepared by known methods, such as the noble metal-catalyzed hydrosilylation reaction of compounds containing a double bond with corresponding hydrosiloxanes, for example in EP1520870 , described. The font EP1520870 is hereby introduced as a reference and is considered part of the disclosure content of the present invention.

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

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

In a particularly preferred embodiment of the present invention (particularly within the scope of the use according to the invention), siloxanes of the formula (V) are used in which R ¹ is independently 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 be different independently of one another and are methyl, ethyl and/or phenyl represent leftovers. R'' is independently a hydrogen radical or an alkyl group with 1 to 4 carbon atoms, a -C(O)-R''' group with R''' = alkyl radical, a -CH ₂ -O-R' group, a alkylaryl group, such as e.g. a benzyl group, the group -C(O)NH-R', R ^IV is a linear, cyclic or branched, optionally substituted, e.g. B. substituted with halogens, hydrocarbon radical having 1 to 50, preferably 9 to 45, preferably 13 to 37 carbon atoms.

In a further preferred embodiment of the present invention (particularly within the scope of the use according to the invention), preferably for the production of rigid foams Siloxanes of the formula (V) are used, in which R ¹ is independently an organic radical selected from the group consisting of -CH ₂ -CH ₂ -CH ₂ -O-(CH ₂ -CH ₂ O-) _x -(CH ₂ -CH( R')O-) _y -R'' and/or
-CH ₂ -CH ₂ -O-(CH ₂ -CH ₂ O-) _x -(CH ₂ -CH(R')O-) _y -R'' and/or
-CH ₂ -R ^IV wherein x is 0 to 100, preferably >0, especially 1 to 50, y is 0 to 100, preferably >0, especially 1 to 50, R' is methyl and R'' is independently a hydrogen radical or an alkyl group with 1 to 4 carbon atoms, a group C(O)-R''' with R''' = alkyl radical, a group -CH2-O-R', an alkylaryl group, such as. B. a benzyl group, the group C(O)NH-R', where the molar proportion of oxyethylene units based on the total amount of oxyalkylene units makes up at least 70% of the oxyalkylene units, i.e. x/(x+y)>0 .7 is. With this premise, it is preferred that the polyoxyalkylene chain also carries a hydrogen at the end. Under these conditions, according to a further preferred embodiment of the invention (in particular within the scope of the use according to the invention), siloxanes of the formula (V) are used in which the oxyalkylene units contained in the radical R ¹ are exclusively oxyethylene units and the radical R'' is none is hydrogen.

In a further preferred embodiment of the present invention (in particular within the scope of the use according to the invention), preferably for the production of flexible slabstock foams, siloxanes of the formula (V) are used, in which R1 is independently an organic radical selected from the group consisting of -CH ₂ -CH ₂ -CH ₂ -O-(CH ₂ -CH ₂ O-) _x -(CH ₂ -CH(R')O-) _y -R'' and/or
-CH ₂ -CH ₂ -O-(CH ₂ -CH ₂ O-) _x -(CH ₂ -CH(R')O-) _y -R'' and/or
-CH ₂ -R ^IV wherein x is 0 to 100, preferably >0, especially 1 to 50, y is 0 to 100, preferably >0, especially 1 to 50, R' is methyl and R'' is independently a hydrogen radical or an alkyl group with 1 to 4 carbon atoms, a group C(O)-R''' with R''' = alkyl radical, a group -CH2-O-R', an alkylaryl group, such as. B. a benzyl group, the group C (O) NH-R ', wherein the molar proportion of oxyethylene units based on the total amount of oxyalkylene units makes up a maximum of 60% of the oxyalkylene units, i.e. x / (x + y) <0, 6 is.

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

In a further preferred embodiment of the present invention (particularly within the scope of the use according to the invention), siloxanes of the formula (V) are used in which the terminal, or else alpha and omega, positions on the siloxane are at least partially functionalized with R ¹ radicals. At least 10 mol %, preferably at least 30 mol %, particularly preferably at least 50 mol % of the terminal positions are functionalized with R ¹ radicals.

In a particularly preferred embodiment of the invention (particularly within the scope of the use according to the invention), siloxanes of the formula (V) are used in which, on average, a maximum of 50%, preferably a maximum of 45%, particularly preferably a maximum of 40% of the total average molecular weight of the siloxane on the total molar mass of all, possibly different, radicals R ¹ in the siloxane is 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 is greater than the number of structural elements with the Index b, such that the quotient a/b is at least seven, preferably greater than 10, particularly preferably greater than 12.

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

wobei der Anteil an Siloxanen mit N = (n + 2) > 9 höher als 10 Gew.-% und N > 12 gleich oder höher als 5 Gew.-% ist. Dabei kann es bevorzugt sein, dass auch Anteile an Siloxanen mit N > 22 enthalten sind, deren Anteil bis zu 5 Gew.-% beträgt. Dabei kann es weiter bevorzugt sein, dass als Polyole Polymerpolyole alleine oder in Abmischungen mit ungefüllten Polyolen eingesetzt werden, wobei die Polymerpolyole vorzugsweise feste organische Füllstoffe in disperser Verteilung enthalten, und die Polyole einen Gehalt an primären Hydroxylgruppen von mindestens 70 % aufweisen. Bevorzugt einsetzbare Polymethylsiloxane der Formel (1) werden insbesondere in EP1777252A1 beschrieben, auf deren Lehre hiermit vollumfänglich Bezug genommen wird.In a further preferred embodiment of the present invention, in the production of polyurethane foams, in particular cold polyurethane foams, it may be preferable to use polymethylsiloxanes of the following general formula (VI) as stabilizers

wherein the proportion of siloxanes with N = (n + 2) > 9 is higher than 10% by weight and N > 12 is equal to or higher than 5% by weight. It can be preferred here that proportions of siloxanes with N>22 are also present, the proportion of which is up to 5% by weight. It can further be preferred that the polyols used are polymer polyols alone or in mixtures with unfilled polyols, the polymer polyols preferably containing solid organic fillers in disperse distribution, and the polyols having a primary hydroxyl group content of at least 70%. Polymethylsiloxanes of the formula (1) which can be used with preference are used in particular in EP1777252A1 described, on the teaching of which reference is hereby made in full.

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

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

The nitrogen-containing compound of the formula (IVc) according to the invention, corresponding quaternized and/or protonated compounds, are used in the production of rigid polyurethane foams according to claim 1.

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

Disclosed is the use of the nitrogen-containing compound of the formula (IVc) described above, and/or a corresponding quaternized and/or protonated compound, for the production of low-emission polyurethanes, in particular low-emission polyurethane foams, namely advantageously low-emission with regard to emissions of nitrogen-containing compounds, such as amine before -Emissions called, advantageously low-emissions with regard 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 previous description and the explanations there, in particular test methods.

The use of the above-described nitrogen-containing compound of the formula (IVc) and/or a corresponding quaternized and/or protonated compound for producing low-odor polyurethanes, preferably low-odor polyurethane foams, in particular low-odor flexible polyurethane foams, is disclosed. With regard to the term “low odor”, reference is made to the preceding description and the explanations there.

The use of the above-described nitrogen-containing compound of the formula (IVc) and/or a corresponding quaternized and/or protonated compound for the production of age-resistant polyurethane systems, in particular polyurethane foams, is disclosed. With regard to the term “ageing-resistant”, reference is made to the preceding description and the explanations and test methods there.

The invention relates to the use of the above-described nitrogen-containing compound of the formula (IVc) and/or a corresponding quaternized and/or protonated compound for the production of rigid polyurethane foams which lead to less discoloration of plastics. With regard to preferred configurations of this subject, reference is made to the preceding description, in particular to the preferred embodiments mentioned. In particular, reference is made to the PVC discoloration test described above in accordance with Volkswagen test specification VW PV 3937.

Disclosed is the use of the nitrogen-containing compound of the formula (IVc) described above, and/or a corresponding quaternized and/or protonated compound, for the production of polyurethane systems with a wide processing range, in particular semi-rigid polyurethane foams (open-cell rigid foams, in particular for use as headliners in automobile interiors ). "Wide processing range" means that advantageously a greater range of variation in the use concentration of the nitrogen-containing compounds according to the invention without negatively affecting the desired material properties, for example the open-cell nature of the foam or the density distribution over the foam block, is possible compared to comparable amine catalysts or those commonly used for such applications the state of the art. Here, too, reference is made to the previous description and the explanations and test methods there.

Disclosed is a composition containing, in addition to at least one nitrogen-containing compound of the formula (IVc), as described above, at least one siloxane of the formula (V) as described above, the siloxane of the formula (V) preferably at least one radical R ₁ , this radical R ₁ preferably being a polyether radical, and/or containing a siloxane of the formula (VI), and preferably at least one polyol, preferably as described above.

A composition is disclosed containing at least one polyol component, the composition having at least one nitrogen-containing compound of the formula (IVc) and/or the corresponding quaternized and/or protonated compounds, the composition preferably having at least one isocyanate component, and the nitrogen-containing compound of Formula (IVc) is preferably contained as a technical product mixture as described above, and the composition preferably comprises additional amine catalysts other than formula (IVc).

The molar ratio of the total amount of the nitrogen-containing catalysts, comprising the nitrogen-containing compounds of the formula (IVc), 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 formula (IVc), corresponding quaternized and / or protonated compounds, in total in a mass fraction 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) polyol component are used.

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

The processing of the compositions according to the invention to give polyurethane systems, in particular polyurethane foams, can be carried out by any method familiar to the person skilled in the art, for example by hand mixing or preferably with the aid of foaming machines, in particular low-pressure or high-pressure foaming machines. Discontinuous processes, for example for the production of molded foams, refrigerators, automobile seats and panels, or continuous processes, for example for insulating boards, metal composite elements, block foams or spray processes can be used here.

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 systems. The compositions used according to the invention can also be used for CO ₂ technology. Use in Never derdruck and letterpress machines is possible, whereby the compositions can either be metered directly into the mixing chamber or else be mixed in before the mixing chamber with one of the components subsequently entering the mixing chamber. The admixing can also take place in the raw material tank.

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

1. (a) zumindest eine stickstoffhaltige Verbindung der Formel (IVc), vorteilhafterweise in einer Gesamtmenge von ≥ 5 Gew.-%, bevorzugt 20-95 Gew.-%, insbesondere 30-70 Gew.-%,
2. (b) optional 1,4-Butandiol, vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
3. (c) optional Monoethylenglycol (MEG), vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
4. (d) optional Diethylenglycol (DEG) vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
5. (e) optional 1-2-Propylenglycol (PG) vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%,
6. (f) optional Dipropylenglycol (DPG) vorteilhafterweise in einer Menge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%, und/oder
7. (g) optional Trimethylenglycol, Butyldiglycol, Neopentylglycol, 2-Methyl-1,3-propandiol, N,N-Dimethylcyclohexylamin, N,N-Dimethylaminopropylamin, Triethylendiamin, 2,2,4-Trimethyl-2-silamorpholin, N-Ethyl-2,2-dimethyl-2-silamorpholin, N-(2-Aminoethyl)morpholin, N-(2-Hydroxyethyl)morpholin, N,N-Dimethylaminoethanol, N,N-Dimethylaminopropyl-N',N'-dipropan-2-olamin, N,N-Diethylaminoethanol, Bis(2-Dimethylaminoethylether), N,N-Dimethyl-aminoethoxyethanol, N,N,N'-Trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl)ether, Tris-(dimethylaminopropyl)hexahydro-1,3,5-triazin, 1,8-Diazabicyclo[5.4.0]undec-7-en, 1,5-Diaza-bicyclo[4.3.0]non-5-en, 1,5,7-triazabicyclo[4.4.0]dec-5-en, N-Methyl-1,5,7-triazabicyclo-[4.4.0]dec-5-en, 1,4,6-triazabicyclo[3.3.0]oct-4-en, 1,1,3,3-Tetramethylguanidin und/oder 2,4,6-Tris(dimethylaminomethyl)phenol, vorteilhafterweise in einer Gesamtmenge ≤ 95 Gew.-%, insbesondere 20-90 Gew.-%, bevorzugt 30-80 Gew.-%.

A composition suitable for use in the production of polyurethanes, in particular polyurethane foams, is disclosed

1. (a) at least one nitrogen-containing compound of the formula (IVc), advantageously in a total amount of ≧5% by weight, preferably 20-95% by weight, in particular 30-70% by weight,
2. (b) optionally 1,4-butanediol, advantageously in an amount ≤ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
3. (c) optionally monoethylene glycol (MEG), advantageously in an amount ≤ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
4. (d) optionally diethylene glycol (DEG) advantageously in an amount ≤ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
5. (e) optionally 1-2-propylene glycol (PG), advantageously in an amount ≤ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
6. (f) optionally dipropylene glycol (DPG) advantageously in an amount ≦95% by weight, in particular 20-90% by weight, preferably 30-80% by weight, and/or
7. (g) optionally trimethylene glycol, butyl diglycol, neopentyl glycol, 2-methyl-1,3-propanediol, N,N-dimethylcyclohexylamine, N,N-dimethylaminopropylamine, triethylenediamine, 2,2,4-trimethyl-2-silamorpholine, N-ethyl- 2,2-dimethyl-2-silamorpholine, N-(2-aminoethyl)morpholine, N-(2-hydroxyethyl)morpholine, N,N-dimethylaminoethanol, N,N-dimethylaminopropyl-N',N'-dipropane-2- olamine, N,N-diethylaminoethanol, bis(2-dimethylaminoethyl ether), N,N-dimethylaminoethoxyethanol, N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether, tris- (dimethylaminopropyl)hexahydro-1,3,5-triazine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,5 ,7-triazabicyclo[4.4.0]dec-5-ene, N-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,4,6-triazabicyclo[3.3.0] oct-4-ene, 1,1,3,3-tetramethylguanidine and/or 2,4,6-tris(dimethylaminomethyl)phenol, advantageously in a total amount of ≤ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight.

• mit a), mit b), mit c), mit d), mit e), mit f), oder mit g).

In the context of the above disclosure, particularly preferred compositions are compositions in which at least one nitrogen-containing compound of the formula (IVc) 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), or with g).

A polyurethane system is disclosed which can be obtained by using it as described above.

Polyurethane systems according to the invention are rigid polyurethane foams. The term polyurethane is to be understood here as a generic term for a polymer made from di- or polyisocyanates and polyols or other species that are reactive towards isocyanate, such as amines, for example, where the urethane bond does not have to be the exclusive or predominant type of bond. Polyisocyanurates and polyureas are also expressly included.

The polyurethane system according to the invention is preferably characterized in that it is a rigid polyurethane foam, in which case it preferably contains a mass fraction of nitrogen-containing compounds of the formula (IVc) and/or the corresponding quaternized and/or protonated compounds or the residues obtained by reacting these Polyurethane foam from 0.005 to 10% by weight, preferably from 0.05 to 3% by weight, particularly preferably from 0.1 to 1% by weight.

A preferred composition for the production of polyurethane or polyisocyanurate foam for the purposes 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 Potassium Trimerization Catalyst 0 to 10 siloxane 0.1 to 15, preferably 0.2 to 7 water 0 to <25, preferably 0.1 to 15 propellant 0 to 130 flame retardants 0 to 70 fillers 0 to 150 other additives 0 to 20 Isocyanate Index: greater than 15

Disclosed is the use of polyurethane systems, in particular polyurethane foams, as described above, as refrigerator insulation, insulating board, sandwich element, pipe insulation, spray foam, 1- and 1.5-component canned foam, imitation wood, model foam, floral foam, packaging foam, mattress, furniture upholstery, molded furniture foam , pillow, rebonded foam, sponge foam, automotive seat pad, headrest, instrument panel, automotive interior panel, automotive headliner, sound absorbing material, steering wheel, shoe sole, carpet backing foam, filter foam, sealing foam, sealant and adhesive, or to manufacture related products.

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

Examples:

Production of nitrogenous compounds

Chemikalie CAS Lieferant Pyrrolidin, 99 % 123-75-1 ABCR Ethylenoxid, 3 M in THF 75-21-8 Sigma-Aldrich Chemie GmbH Synthesis Example 1 Preparation of Compounds of the Formula (IIIb) and (IIIc) Not According to the Invention

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

A quantity of 333.4 ml of a 3 molar solution of ethylene oxide in THF (equivalent to 1 mol Ethylene oxide) submitted and added a further 35.56 g (0.5 mol) of pyrrolidine. The autoclave, which had previously been purged with nitrogen, was then heated to 100° C. via the jacket with thermal oil, and a pressure increase could be observed. The reaction temperature was then maintained with stirring for 6 hours. After the end of the reaction time, the pressure vessel was allowed to cool to room temperature and flushed with nitrogen. The solvent was removed for several hours on a rotary evaporator at a bath temperature of 50° C. in a diaphragm pump vacuum. The crude reaction mixture was then examined by gas chromatography, in addition to 15.1% unreacted pyrrolidine, 42.9% of the desired mono-ethoxylated pyrrolidine and 26.7% of the di-ethoxylated pyrrolidine and 10.7% of tri-ethoxylated pyrrolidine and a total of 4.6% of other by-products or solvent residues were found. Precision distillation was then performed to isolate the desired mono- and di-ethoxylated pyrrolidine. It was thus possible at a pressure of 16 mbar and a top temperature of 75-78° C. in a clear fraction to obtain the mono-ethoxylated product of the formula (IIIb) with a GC purity of 96.9% and at a pressure of 3 mbar and a top temperature of 90-95° C., the di-ethoxylated target product of the formula (IIIc) can be obtained in a likewise clear fraction with a GC purity of 94.2%. The NMR spectroscopy as well as the GC or GC/MS analyzes confirmed the formation of the product.

Chemikalie CAS Lieferant Acrylnitril, >99% 107-13-1 Sigma-Aldrich Chemie GmbH Pyrrolidin, 99 % 123-75-1 ABCR Dichlormethan 75-09-2 Sigma-Aldrich Chemie GmbH Natriumhydroxid, ≥99 %, p.a. 1310-73-2 Karl Roth GmbH Natriumchlorid, ≥99,8 %, extra fein 7647-14-5 Karl Roth GmbH Methanol, ≥99.8% 67-56-1 Sigma-Aldrich Chemie GmbH Synthesis Example 2: Preparation of 1-pyrrolidinepropanenitrile

chemical CAS supplier Acrylonitrile, >99% 107-13-1 Sigma-Aldrich Chemie GmbH Pyrrolidine, 99% 123-75-1 ABCR dichloromethane 75-09-2 Sigma-Aldrich Chemie GmbH Sodium hydroxide, ≥99%, pa 1310-73-2 Karl Roth GmbH Sodium Chloride, ≥99.8%, extra fine 7647-14-5 Karl Roth GmbH methanol, ≥99.8% 67-56-1 Sigma-Aldrich Chemie GmbH

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

Synthesis Example 3 Preparation of the compound of the formula (IVb) not according to the invention

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

Chemikalie CAS Lieferant Verbindung hergestellt nach Synthesebeispiel 2 Pd/Al2O3 5% (Heraeus-Type K) 7440-05-3 Heraeus (Hanau) Methanol, ≥99.8% 67-56-1 Sigma-Aldrich Chemie GmbH Synthesis Example 4 Preparation of the compound of the formula (IVd) not according to the invention

chemical CAS supplier connected according to synthesis example 2 Pd/Al2O3 5% (Heraeus Type K) 7440-05-3 Heraeus methanol, ≥99.8% 67-56-1 Sigma-Aldrich Chemie GmbH

100 ml (94.55 g) of the nitrile prepared according to Synthesis Example 2 were placed in a 250 L high-pressure laboratory autoclave with heatable jacket, thermal sensor, inert gas supply line such as hydrogen and stirring device, and 2.02 g Pd/Al ₂ O ₃ (5% by weight) were added in portions. registered. The reaction vessel was closed, flushed with nitrogen and the hydrogen supply line was connected. A pressure test of the apparatus was carried out for 20 minutes using nitrogen at a low stirring speed, the apparatus was then flushed with hydrogen (50 bar) and finally the hydrogen pressure was adjusted to 90 bar. The stirring speed was increased to 1300 rpm and heated to 90° C. by means of the heating device. After the hydrogen pressure had dropped to 20 bar after one hour, it was increased again to 90 bar and stirring was continued over a period of 5 hours at a constant reaction temperature of 90° C. until a significant drop in pressure could no longer be observed. After the end of the reaction time, the reaction vessel was allowed to cool to room temperature, and the pressure vessel was vented and purged with nitrogen. The reaction mixture was transferred from the reactor with 100 ml of methanol, fitted with Celite ^Ⓒ filter aid and filtered through a pleated filter. The filter cake was rinsed with 50 ml of methanol and the filtrate was analyzed by GC-MS. The analysis gave a proportion of 8.12% unreacted starting material, 18.65% of the dimeric by-product, 58.46% of the trimeric target product of the formula (IVd) and other by-products. To separate dimeric by-product and trimeric target product, the solvent was removed on a rotary evaporator and the residue subjected to precision distillation. For this, the residue was placed in a one-necked round bottom flask and distilled through a 20 cm Vigreux column in a strong oil pump vacuum. At a pressure of 1.1×10 ^-1 mbar, at a bath temperature of 150° C. and a head temperature of 95-110° C., the clear dimeric by-product could be obtained in a fraction with a GC purity of 98.6%. A further reduction of the pressure to 2.7×10 ^-2 mbar at a bath temperature of 252° C. and a top temperature of 140° C. gave the trimeric target product of the formula (IVd), which is viscous at room temperature, in a GC purity of 98.2 %. The recorded 1H and 13C NMR spectra were in agreement with expectations and also confirmed the product formation and its purity.

Rigid foam - foaming examples

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

The foam formulation given in Table 1 was used to test the performance of the nitrogen-containing compounds according to the invention. Table 1: Formulation 1 for rigid foam applications. Formulation 1 Bulk parts (pphp) Polyol 1 ¹⁾ 100 parts water 2.60 parts cyclopentane 13.1 parts amine 1.50 parts TEGOSTAB ^® B 8460 ²⁾ 1.50 parts Desmodur® ^{44V20L 3)} 198.5 parts
¹⁾ Polyol 1: Sorbitol/glycerin-based polyether polyol with an OH number of 471 mgKOH/g.
²⁾ Polyether modified polysiloxane.
³⁾ polymeric MDI from Bayer, 200 m Pa·s, 31.5% NCO, functionality 2.7.

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

The results of the assessment of the catalytic properties of the nitrogen-containing compounds of the formulas (III) and (IV) are summarized in Table 2. N,N-dimethylcyclohexylamine (DMCHA) and N,N-dimethylaminoethoxyethanol (DMEE) were used as comparative catalysts according to the prior art. Table 2: Results of the foaming according to formulation 1 (Table 1). amine cream time gel time rise time Tack-free [s] ³⁾ [s] ³⁾ [s] ³⁾ [s] ³⁾ DMCHA 41 141 297 315 DMEE 29 154 276 304 FORMULA (IIIb)** 45 190 235 376 FORMULA (IIIc)** 34 176 289 323 FORMULA (IVb)** 30 140 198 300 FORMULA (IVc)* 50 165 260 350 FORMULA (IVd)** 35 125 187 201
¹⁾ Time specifications in seconds [s].
*according to the invention
** not according to the invention

As can be seen from Table 2, the compounds of the formula (IIIb), (IIIc), (IVb) and (IVc) exhibit moderate to very good catalytic activity in rigid foam. The compound of the formula (IVb) is particularly active here. The compound of the formula (IVd) shows an even greater activity, even greater than that of DMCHA when used in the same amount, and is also very similar to DMCHA in terms of selectivity.

Example 2 Production of open-cell rigid polyurethane foams, for example for use as headliners in automobiles

The foam formulation given in Table 3 was used to test the performance of the nitrogen-containing compounds according to the invention. Table 3: Formulation 2 for open-cell rigid foam applications. Formulation 2 Polyol 1 ¹⁾ 35.0 parts polyol 2 ²⁾ 35.0 parts Polyol 3 ³⁾ 25.0 parts Dipropylene Glycol (DPG) 5.00 parts amine -variable- water 4.00 parts Tego rod B 8523 0.50 parts Tego rod B 8871 1.00 parts Desmodur 44V20L ⁴⁾ 134 parts
¹⁾ Polyol 1: glycerol-based polyether polyol, with a functionality of 3 and OH number of 250 mgKOH/g.
²⁾ Polyol 2: Sugar/glycerol based polyether polyol, with a functionality of 4.3 and an OH number of 490 mgKOH/g.
³⁾ Polyol 3: Glycerol-based polyether polyol, with a functionality of 3 and an OH number of 28 mgKOH/g.
⁴⁾ polymeric MDI from Bayer, 200 m Pa·s, 31.5% NCO, functionality 2.7.

The foaming was carried out using the hand mixing method. The formulations as given in Table 3 were used with various nitrogen-containing catalysts (amines). For this purpose, a mixture containing the nitrogen-containing compounds according to the invention was prepared and weighed into a beaker. The MDI was then added, the reaction mixture stirred with a 6 cm diameter plate stirrer at 3000 rpm for 5 seconds and immediately transferred to a box (27 cm x 14 cm base and 14 cm height) lined with paper.
The foams were analyzed one day after foaming. After the foams had been cut open, the interior defects were rated subjectively on a scale from 1 to 10, with 10 representing undisturbed foam and 1 representing extremely severely disrupted foam. To determine the open-cell content, cylindrical specimens (3.4 cm in diameter and 4 cm in height) were cut from the foams and measured using an Accupyc 1330 pycnometer from Micromeritics.

The results are compiled in Table 4. The nitrogen-containing compounds used according to the formulas (III) and (IV) and the visual assessment and the open-cell nature of the foams are summarized.

N,N-dimethylaminoethoxyethanol (DMEE) and N,N-dimethylaminopropylamine (DMAPA) were used as a reference. The nitrogen-containing compounds according to the invention and DMAPA were used in equimolar amounts, based on the amount of DMEE used in each case. Table 4: Results of the foaming according to formulation 2 (Table 3). amine dosage [pphp] Rating / Inside Open cells [%] ¹⁾ DMEE 1.50 8th 25 DMEE 2.00 9 45 DMEE 2.50 8th 75 Formula (IIIc)** 2.00 8th 57 Formula (IIIc)** 2.60 9 72 Formula (IIIc)** 3.30 9 79 DMAPA 1.20 6 80 DMAPA 1.50 6 88 DMAPA 1.90 6 91 Formula (IVb)** 1.50 8th 96 Formula (IVb)** 2.00 9 95 Formula (IVb)** 2.50 8th 95 Formula (IVc)* 1.50 8th 91 Formula (IVc)* 2.00 8th 96 Formula (IVc)* 2.50 8th 97
¹⁾ Percentages of open cells: 100% = fully open, 0% = closed cells.
* according to the invention
** not according to the invention

It is found that the nitrogen-containing compound (IVc) according to the invention can be used in a broader concentration range without the open-cell content falling sharply. Thus, the open cell content changes from 25 to 75% with DMEE, while more constant values in a range from 57 to 79% are obtained with the nitrogen-containing compound of the formula (IIIc). The non-inventive formulations with DMAPA all gave foams with significantly more internal defects. With the nitrogen-containing compound of the formula (IVc) according to the invention, it was possible—over the same concentration range—to obtain foams of good quality and with open cells of more than 80%.

Flexible foam - Application tests

Physical properties of flexible polyurethane foams:

1. a) Rücksacken des Schaumstoffes nach dem Ende der Steigphase (=Rückfall): Der Rückfall, bzw. das Nachsteigen ergibt sich aus der Differenz der Schaumhöhe nach direktem Abblasen und nach 3 Minuten. nach Abblasen des Schaums. Die Schaumhöhe wird dabei durch eine an einem Zentimetermaß befestigte Nadel auf dem Maximum in der Mitte der Schaumkuppe gemessen. Ein negativer Wert beschreibt hierbei das Rücksacken des Schaumes nach dem Abblasen, ein positiver Wert beschreibt entsprechend das Nachsteigen des Schaumes.

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

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

1. a) Sagging of the foam after the end of the climbing phase (= relapse): The relapse or the subsequent ascent results from the difference in the foam height after direct blowing off and after 3 minutes. after blowing off the foam. The foam height is measured using a needle attached to a centimeter ruler at the maximum in the center of the foam dome. A negative value describes the sagging of the foam after blowing off, a positive value describes the subsequent rise of the foam.

1. b) Foam height: The final height of the foam is determined by subtracting or adding the fallback or subsequent ascent from or to the foam height after blowing off. Foam height is reported in centimeters (cm).
2. c) Density (RG): The determination is made, as described in ASTM D 3574-11 under Test A, by measuring the core density. The density is given in kg/m ³ .
3. d) Porosity: The air permeability of the foam was determined by measuring the dynamic pressure on the foam. The measured dynamic pressure is given in mm of water column, with lower dynamic pressure values characterizing a more open foam. The values were measured in the range from 0 to 300 mm. The dynamic pressure was measured using an apparatus comprising a nitrogen source, reducing valve with manometer, flow control screw, washing bottle, flow meter, T-piece, support nozzle and a scaled glass tube filled with water. The support nozzle has an edge length of 100×100 mm, a weight of 800 g, a clear width of the outlet opening of 5 mm, a clear width of the lower support ring of 20 mm and an outer diameter of the lower support ring of 30 mm. The measurement is carried out by setting the nitrogen pre-pressure to 1 bar using the reducing valve and adjusting the flow rate to 480 l/h. The amount of water is set in the graduated glass tube in such a way that no pressure difference can be built up and read. For the measurement of the test specimen with dimensions of 250 x 250 x 50 mm, the contact nozzle is placed at the corners of the test specimen with the edges congruent and placed once at the (estimated) center of the test specimen (each on the side with the largest surface). It is read when a constant back pressure has been established. The evaluation is carried out by averaging over the five measured values obtained.
4. e) Compression hardness CLD, 40% according to DIN EN ISO 3386. The measured values are given in kilopascals (kPa).

• Das Verfahren dient zur Ermittlung von Emissionen aus nichtmetallischen Materialein, die für Formteile in Kraftfahrzeugen zum Einsatz kommen. Die Emission von leichtflüchtigen organischen Verbindungen (VOC-Wert, 30 Minuten bei 90 °C) sowie dem Anteil kondensierbarer Substanzen (Fog-Wert, 60 Minuten bei 120 °C), insbesondere der Katalyse-bedingten Emissionen, die Emissionen der einzelnen Bestandteile erfindungsgemäßer Katalysatorkombinationen oder ihrer Zer- oder Umsetzungsprodukte, wurde in Anlehnung an die Prüfvorschrift VDA 278 in der Version vom Oktober 2011 bestimmt. Im Folgenden wird die Durchführung der entsprechenden Thermodesorption mit anschließender Gaschromatographie/Massenspektrometrie-Kopplung (GC/MS) beschrieben.

1. a) Messtechnik: Die Thermodesorption wurde mit einem Thermodesorber „TDS2“ mit Probenwechsler der Fa. Gerstel, Mülheim, in Verbindung mit einem Agilent 7890/5975 GC/MSD-System durchgeführt.
2. b) Die Messbedingungen für VOC-Messungen sind in Tabellen 5 und 6 angegeben.

Tabelle 5: Messparameter Thermodesorption für den VOC-Analysenlauf. Thermodesorption Gerstel TDS2 Desorptionstemperatur 90 °C Desorptionsdauer 30 min Fluss 65 ml/min Transferline 280°C Kryofokussierung KAS 4 Liner Glasverdampferrohr mit silanisierter Glaswolle Temperatur -150°C Tabelle 6: Messparameter Gaschromatographie/Massenspektrometrie für den VOC-Analysenlauf. GC Kapillar-GC Agilent 7890 Injektor PTV Split 1:50 Temperaturprogramm -150°C; 1 min; ⇗10°C/s; 280°C Säule Agilent 19091B-115, Ultra 2, 50 m * 0,32 mm dF 0,5µm Fluss 1,3 ml/min const. Flow Temperaturprogramm 50°C; 2 min; ⇗3°C/min; 92°C; ⇗5°C/min; 160°C; ⇗10°C/min; 280°C, 20 min Detektor Agilent MSD 5975 Modus Scan 29-350 amu 2,3 scans/sec Auswertung Auswertung des Totalionenstrom-Chromatrogramms durch Berechnung als Toluoläquivalent

1. c) Kalibrierung: Zur Kalibrierung wurde 2 µl eines Gemisches aus Toluol und Hexadekan in Methanol (je 0,125 mg/ml) auf ein gereinigtes, mit Tenax^® TA (mesh 35/60) gefülltes Adsorptionsröhrchen gegeben und vermessen (Desorption 5 min; 280 °C).
2. d) Bei Tenax^® TA handelt es sich um ein poröses Polymerharz basierend auf 2.6-Diphenylen oxid, erhältlich beispielsweise bei der Firma Scientific Instrument Services, 1027 Old York Rd., Ringoes, NJ 08551.
3. e) Probenvorbereitung für die VOC-Messung: 15 mg Schaumstoff wurden in drei Teilproben in einem Thermodesorptionsröhrchen platziert. Dabei wurde darauf geachtet, dass der Schaum nicht komprimiert wird.
4. f) Probenvorbereitung für die Fog-Messung: Es wurde die gleiche Schaumprobe verwendet, wie für die VOC-Messung. Hinsichtlich der Messanordnung wurde immer zuerst die VOC-Messung und im Anschluss die Fog-Messung durchgeführt, wobei mittels eines Autosampler-Systems ein jeweils konstanter Abstand zwischen den entsprechenden VOC- und Fog-Messungen gewährleistet wurde.
5. g) Die Messbedingungen für Fog-Messungen sind in Tabelle 7 und 8 wiedergegeben.

Tabelle 7: Messparameter Thermodesorption für den Fog-Analysenlauf. Thermodesorption Gerstel TDS2 Desorptionstemperatur 120 °C Desorptionsdauer 60 min Fluss 65 ml/min Transferline 280°C Kryofokussierung KAS 4 Liner Glasverdampferrohr mit silanisierter Glaswolle Temperatur -150°C Tabelle 8: Messparameter Gaschromatographie/Massenspektrometrie für den Fog-Analysenlauf. GC Kapillar-GC Agilent 7890 Injektor PTV Split 1:50 Temperaturprogramm -150°C; 1 min; ⇗10°C/s; 280°C Säule Agilent 19091B-115, Ultra 2, 50 m * 0,32 mm dF 0,5µm Fluss 1,3 ml/min const. Flow Temperaturprogramm 50°C; 2 min; ⇗25°C/min; 160°C; ⇗10°C/min; 280°C; 20 min Detektor Agilent MSD 5975 Modus Scan 29-450 amu 2,3 scans/sec Auswertung Auswertung des Totalionenstrom-Chromatrogramms durch Berechnung als Hexadekanäquivalent

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

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

• The method is used to determine emissions from non-metallic materials used for molded parts in motor vehicles. The emission of volatile organic compounds (VOC value, 30 minutes at 90 ° C) and the proportion of condensable substances (fog value, 60 minutes at 120 ° C), in particular the catalysis-related emissions, the emissions of the individual components of catalyst combinations according to the invention or their decomposition or conversion products, was determined based on the test specification VDA 278 in the October 2011 version. The implementation of the corresponding thermal desorption with subsequent gas chromatography/mass spectrometry coupling (GC/MS) is described below.

1. a) Measurement technology: The thermal desorption was carried out with a thermal desorber "TDS2" with sample changer from the company Gerstel, Mülheim, in connection with an Agilent 7890/5975 GC/MSD system.
2. b) The measurement conditions for VOC measurements are given in Tables 5 and 6.

Table 5: Thermal desorption measurement parameters for the VOC analysis run. thermal desorption Gerstel TDS2 desorption temperature 90°C desorption time 30 min Flow 65mL/min transfer line 280°C cryofocusing CAS 4 liners Glass evaporator tube with silanized glass wool temperature -150°C Table 6: Gas chromatography/mass spectrometry measurement parameters for the VOC analysis run. G.C Capillary GC Agilent 7890 injector PTV Split 1:50 temperature program -150°C; 1 min; ⇗10°C/s; 280°C pillar Agilent 19091B-115, Ultra 2, 50m * 0.32mm dF 0.5µm Flow 1.3 ml/min const. Flow temperature program 50°C; 2 minutes; ⇗3°C/min; 92°C; ⇗5°C/min; 160°C; ⇗10°C/min; 280°C, 20 min detector Agilent MSD 5975 mode Scan 29-350 amu 2.3 scans/sec Evaluation Evaluation of the total ion current chromatogram by calculation as a toluene equivalent

1. c) Calibration: For calibration, 2 µl of a mixture of toluene and hexadecane in methanol (0.125 mg/ml each) was placed in a cleaned adsorption tube filled with Tenax ^® TA (mesh 35/60) and measured (desorption 5 min; 280° C).
2. d) Tenax ^® TA is a porous polymer resin based on 2.6-diphenylene oxide, available for example from Scientific Instrument Services, 1027 Old York Rd., Ringoes, NJ 08551.
3. e) Sample preparation for the VOC measurement: 15 mg of foam were placed in three sub-samples in a thermal desorption tube. Care was taken not to compress the foam.
4. f) Sample preparation for the fog measurement: The same foam sample was used as for the VOC measurement. With regard to the measurement arrangement, the VOC measurement was always carried out first, followed by the fog measurement, with an autosampler system ensuring a constant interval between the corresponding VOC and fog measurements.
5. g) The measurement conditions for fog measurements are given in Tables 7 and 8.

Table 7: Thermal desorption measurement parameters for the fog analysis run. thermal desorption Gerstel TDS2 desorption temperature 120℃ desorption time 60 mins Flow 65mL/min transfer line 280°C cryofocusing CAS 4 liners Glass evaporator tube with silanized glass wool temperature -150°C Table 8: Gas chromatography/mass spectrometry measurement parameters for the fog analysis run. G.C Capillary GC Agilent 7890 injector PTV Split 1:50 temperature program -150°C; 1 min; ⇗10°C/s; 280°C pillar Agilent 19091B-115, Ultra 2, 50m * 0.32mm dF 0.5µm Flow 1.3 ml/min const. Flow temperature program 50°C; 2 minutes; ⇗25°C/min; 160°C; ⇗10°C/min; 280°C; 20 min detector Agilent MSD 5975 mode Scan 29-450 amu 2.3 scans/sec Evaluation Evaluation of the total ion current chromatogram by calculation as a hexadecane equivalent

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

1. a) Messtechnik: Die Thermodesorption wurde mit einem Thermodesorber „TDS2“ mit Probenwechsler der Fa. Gerstel, Mülheim, in Verbindung mit einem Agilent 7890/5975 GC/MSD-System durchgeführt.
2. b) Die Messbedingungen sind in Tabelle 9 und 10 angegeben.

Tabelle 9: Messparameter Thermodesorption für PK-Messung. Thermodesorption Gerstel TDS2 Desorptionstemperatur 280°C Desorptionsdauer 5 min Fluss 65 ml/min Transferline 280°C Kryofokussierung KAS 4 Liner Glasverdampferrohr mit silanisierter Glaswolle Temperatur -150°C Tabelle 10: Messparameter Gaschromatographie/Massenspektrometrie für PK-Messung. GC Kapillar-GC Agilent 7890 Temperaturprogramm -150°C; 1 min; ⇗10°C/s; 280°C Säule Agilent 19091B-115, Ultra 2, 50 m * 0,32 mm dF 0,5µm Fluss 1,3 ml/min const. Flow Temperaturprogramm 50°C; 2 min; ⇗3°C/min; 92°C; ⇗5°C/min; 160°C; ⇗10°C/min; 280°C, 20 min Detektor Agilent MSD 5975 Auswertung Auswertung des Totalionenstrom-Chromatrogramms durch Berechnung als Toluoläquivalent

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

Determination of the room temperature emission according to the so-called test chamber test (PK): From the foams obtained, the emission, in particular the catalysis-related emissions, the emissions of the individual components of catalyst combinations according to the invention or their decomposition or reaction products, at room temperature based on the DIN -Regulation DIN EN ISO 16000-9:2008-04. The sampling took place after 24 hours. For this purpose, 2 liters of the test chamber atmosphere were poured through an adsorption tube filled with Tenax ^® TA (mesh35/60) at a flow rate of 100 ml/min. In the following, the implementation of thermal desorption with subsequent gas chromatography/mass spectrometry coupling (GC/MS) is described.

1. a) Measurement technology: The thermal desorption was carried out with a thermal desorber “TDS2” with a sample changer from Gerstel, Mülheim, in connection with an Agilent 7890/5975 GC/MSD system.
2. b) The measurement conditions are given in Tables 9 and 10.

Table 9: Thermal desorption measurement parameters for PK measurement. thermal desorption Gerstel TDS2 desorption temperature 280°C desorption time 5 mins Flow 65mL/min transfer line 280°C cryofocusing CAS 4 liners Glass evaporator tube with silanized glass wool temperature -150°C Table 10: Gas chromatography/mass spectrometry measurement parameters for PK measurement. G.C Capillary GC Agilent 7890 temperature program -150°C; 1 min; ⇗10°C/s; 280°C pillar Agilent 19091B-115, Ultra 2, 50m * 0.32mm dF 0.5µm Flow 1.3 ml/min const. Flow temperature program 50°C; 2 minutes; ⇗3°C/min; 92°C; ⇗5°C/min; 160°C; ⇗10°C/min; 280°C, 20 min detector Agilent MSD 5975 Evaluation Evaluation of the total ion current chromatogram by calculation as a toluene equivalent

1. c) For calibration, 2 µl of a mixture of toluene and hexadecane in methanol (each 0.125 mg/ml) was placed in a cleaned adsorption tube filled with Tenax ^® TA (mesh35/60) and measured (desorption 5 min; 280°C).

1. a) Vorbereitung: Für die Testmethode werden 1000 ml Weithalsgläser mit Deckel verwendet. Die Weithalsgläser müssen sauber und trocken sein. Um dies zu gewährleisten werden die Gläser vor der Benutzung gereinigt, mit destilliertem Wasser gespült und bis kurz vor der Messung zur Trocknung (temperieren auf 100 °C) im Trockenschrank gelagert. Die PVC-Folie (ursprüngliche Farbe hellgrau) muss ausgeschnitten werden und glatt mit der Strukturseite Richtung Glas/Probenkörper in den Deckel eingebracht werden, so dass das 1000 ml Weithalsglas luftdicht verschlossen werden kann.
2. b) Durchführung: Ca. 24 Stunden nach der Reaktion/Verschäumung (+- 1 Stunde) wird ein genau 5 × 52 cm³ großer Probenkörper aus dem Kern geschnitten, auf den Boden des auf 100 °C temperierten 1000 ml Weithalsglases gelegt, mit dem Deckel, beinhaltend die PVC-Folie, luftdicht verschlossen und 72 Stunden bei einer Temperatur von 100 °C gelagert. Um Messschwankungen zu vermeiden, sollte der Probenkörper aus dem Kern, mindestens ≥ 3 cm von der Außenseite entfernt und bei jedem Test aus dem gleichen Bereich geschnitten werden. Nach 72 Stunden werden die Gläser für 30 Minuten auf Raumtemperatur abgekühlt. Die PVC-Folie wird im Folgenden entnommen und einer optischen Kontrolle hinsichtlich Verfärbung unterzogen. Zu jeder Messung ist ein BLANK durchzuführen, also eine Messung ohne Schaum. Nach der BLANK-Messung sollte sich keine Farbveränderung zeigen und die PVC-Folie weiterhin grau sein.

PVC discoloration test according to the Volkswagen test specification VW PV 3937:

1. a) Preparation: 1000 ml wide-necked jars with lids are used for the test method. The wide-mouth jars must be clean and dry. To ensure this, the glasses are cleaned before use, rinsed with distilled water and stored in the drying cabinet until just before the measurement to dry (temperature to 100 °C). The PVC film (original color light grey) must be cut out and inserted into the lid with the structure side facing the glass/test specimen so that the 1000 ml wide-necked glass can be sealed airtight.
2. b) Execution: About 24 hours after the reaction/foaming (+- 1 hour), a specimen measuring exactly 5×52 cm ³ is cut out of the core, placed on the bottom of the 1000 ml wide-necked glass heated to 100° C., with the Lid containing the PVC film, hermetically sealed and stored at a temperature of 100 °C for 72 hours. To avoid measurement fluctuations, the specimen should be cut from the core, at least ≥ 3 cm from the outside, and from the same area for each test. After 72 hours, the jars are cooled to room temperature for 30 minutes. The PVC film is then removed and subjected to a visual check for discoloration. A BLANK must be carried out for each measurement, i.e. a measurement without foam. After the BLANK measurement, there should be no change in color and the PVC film should still be gray.

• Die Aldehyd-Emissionswerte der erhaltenen Schäume wurden in Anlehnung an die VDA 275 (VDA 275 „Formteile für den Fahrzeuginnenraum - Bestimmung der Formaldehydabgabe“. Messverfahren nach der modifizierten Flaschen-Methode; Quelle: VDA 275, 07/1994, www.vda.de) auf ihren Formaldehyd-, den Acetaldehyd- und den Propionaldehyd-Gehalt analysiert.

1. a) Messprinzip: Bei der Methode wurden Probekörper einer bestimmten Masse und Abmessung über destilliertem Wasser in einer geschlossenen 1 L-Glasflasche befestigt und bei konstanter Temperatur über eine definierte Zeit gelagert. Danach wurden die Flaschen abgekühlt und der im destillierten Wasser den absorbierte Formaldehyd, Acetaldehyd und Propionaldehyd bestimmt. Die ermittelte Formaldehyd-, Acetaldehyd- und Propionaldehydmenge wurde auf trockenes Formteilgewicht bezogen (mg/kg).
2. b) Analytik: Prüfkörper: Probenvorbereitung, Probenahme und Probekörperabmessungen: Nach dem Entformen der Schäume wurden diese 24 Stunden bei 21 °C und ca. 50 % relativer Luftfeuchte gelagert. Es wurden dann Probekörper gleichmäßig verteilt über die Breite des (abgekühlten) Schaumstoffs an geeigneten und repräsentativen Stellen entnommen. Danach wurden die Schäume in eine Aluminium-Folie eingeschlagen und in einem Polyethylenbeutel versiegelt. Die Größe der Probekörper betrug jeweils 100 x 40 x 40 mm Dicke (ca. 9g). Pro Formteil wurden 3 Probekörper für die Aldehyd-Bestimmung entnommen.
3. c) Durchführung der Prüfung: Formaldehyd-/Acetaldehyd-/Propionaldehyd-Abgabe: Direkt nach Erhalt der versiegelten Probekörper wurden diese der Direktbestimmung zugeführt. Die Proben wurden vor Beginn der Analyse auf der Analysenwaage auf 0,001 g genau ausgewogen. In die verwendeten Glasflaschen wurden jeweils 50 ml destilliertes Wasser pipettiert. Nach Anbringung der Probekörper in der Glasflasche wurde das Gefäß geschlossen und über 3 Stunden im Wärmeschrank bei einer konstanten Temperatur von 60 °C verwahrt. Nach Ablauf der Prüfzeit wurden die Gefäße aus dem Wärmeschrank genommen. Nach 60 Minuten Standzeit bei Raumtemperatur wurden die Probekörper aus der Prüfflasche entfernt. Anschließend erfolgte die Derivatisierung nach der DNPH-Methode (Dinitrophenylhydrazin). Dazu werden 900 µl der Wasserphase mit 100 µl einer DNPH Lösung versetzt. Die DNPH-Lösung ist wie folgt hergestellt: 50 mg DNPH in 40 mL MeCN (Acetonitril) werden mit 250 µL HCl (1:10 verd.) angesäuert und auf 50 mL mit MeCN aufgefüllt. Nach der erfolgten Derivatisierung wird eine Probe mittels HPLC analysiert. Es erfolgt eine Auftrennung in die einzelnen Aldehyd-Homologen.
4. d) Geräteparameter HPLC Es wurde das folgende Gerät für die Analyse verwendet:
   • Agilent Technologies 1260
   • Chromatographiesäule: Phenomenex Luna 250*4,6 mm C18, 5 µ Teilchengröße Laufmittel: Wasser Acetonitril Gradient
   • Detektion: UV 365 nm

Measurement of the aldehyde emissions based on the test specification VDA 275 in the July 1994 version:

• The aldehyde emission values of the foams obtained were based on VDA 275 (VDA 275 "Mouldings for vehicle interiors - Determination of formaldehyde emission". Measurement method using the modified bottle method; Source: VDA 275, 07/1994, www.vda.de ) analyzed for their formaldehyde, acetaldehyde and propionaldehyde content.

1. a) Measuring principle: In the method, test specimens of a certain mass and dimensions were fixed over distilled water in a closed 1 L glass bottle and stored at a constant temperature for a defined period of time. The bottles were then cooled and the formaldehyde, acetaldehyde and propionaldehyde absorbed in the distilled water were determined. The amount of formaldehyde, acetaldehyde and propionaldehyde determined was based on the dry weight of the molded part (mg/kg).
2. b) Analysis: Test specimens: Sample preparation, sampling and specimen dimensions: After the foams had been demoulded, they were stored for 24 hours at 21° C. and approx. 50% relative humidity. Specimens were then taken from suitable and representative locations evenly distributed across the width of the (cooled) foam. Thereafter, the foams were wrapped in aluminum foil and sealed in a polyethylene bag. The size of the specimens was 100 x 40 x 40 mm thickness (approx. 9g). 3 specimens were taken from each molded part for the aldehyde determination.
3. c) Carrying out the test: Release of formaldehyde/acetaldehyde/propionaldehyde: Immediately after receipt of the sealed test specimens, they were used for direct determination. The samples were weighed on the analytical balance to within 0.001 g before the start of the analysis. 50 ml of distilled water were pipetted into each of the glass bottles used. After placing the test specimens in the glass bottle, the vessel was closed and kept in a heating cabinet at a constant temperature of 60 °C for 3 hours. After the test time had elapsed, the vessels were removed from the heating cabinet. After standing for 60 minutes at room temperature, the test specimens were removed from the test bottle. The derivatization was then carried out using the DNPH method (dinitrophenylhydrazine). For this purpose, 100 μl of a DNPH solution are added to 900 μl of the water phase. The DNPH solution is prepared as follows: 50 mg DNPH in 40 mL MeCN (acetonitrile) are acidified with 250 µL HCl (1:10 dilution) and made up to 50 mL with MeCN. After the derivatization has taken place, a sample is analyzed by HPLC. A separation into the individual aldehyde homologues takes place.
4. d) Device parameters HPLC The following device was used for the analysis:
   • Agilent Technologies 1260
   • Chromatography column: Phenomenex Luna 250*4.6 mm C18, 5 μ particle size Mobile phase: water acetonitrile gradient
   • Detection: UV 365 nm

Flexible foam not according to the invention - examples of foaming

Example 3 Production of flexible polyurethane foams (flexible block foam) not according to the invention

The foam formulations given in Table 11 were used to test the performance of the nitrogen-containing compounds. Table 11: Formulation 3 for flexible slabstock applications. Formulation 3 Bulk parts (pphp) Polyol 1 ¹⁾ 100 parts water 3.00 parts tin catalyst ²⁾ 0.20 parts amine 0.20 parts TEGOSTAB ^® BF 2370 ³⁾ 0.80 parts ^Desmodur® T 80 ⁴⁾ 38.1 parts
¹⁾ Polyol 1: glycerin-based polyether polyol with an OH number of 48 mgKOH/g.
^{2) KOSMOS®} 29, available from Evonik Industries: tin(II) salt of 2-ethylhexanoic acid.
³⁾ Polyether modified polysiloxane.
⁴⁾ Tolylene diisocyanate T 80 (80% 2,4-isomer, 20% 2,6-isomer) from Bayer, 3 m Pa·s, 48% NCO, functionality 2.

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

The foaming was carried out using the hand mixing method. Those used in formulations as given in Table 11 with various nitrogen-containing catalysts (amines). de. For this purpose, polyol, conventional or inventive nitrogen-containing catalyst (amine), tin catalyst, water and foam stabilizer were weighed into a beaker and mixed at 1000 rpm for 60 seconds. After addition of the isocyanate (TDI), the reaction mixture was stirred at 2500 rpm for 7 s and immediately transferred to a paper-lined box (27 cm x 27 cm base and 27 cm height). To assess the catalytic properties, the following characteristic parameters were determined: cream time, rise time, height of rise, intensity of blowing off (=blow off) and sagging of the foam after the end of the rise phase (=fall back).

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

Table 12 summarizes the results of the assessment of the catalytic properties of the nitrogen-containing compounds of the formulas (III) and (IV) and of the physical properties of the resulting flexible slabstock foams. Triethylenediamine, a 33% by weight solution in dipropylene glycol ( ^TEGOAMIN® 33, available from Evonik Industries), N,N-dimethylethanolamine (TEGOAMIN® ^DMEA , available from Evonik Industries), N'-(3-dimethylaminopropyl)-N,N-diisopropylamine (TEGOAMIN ^® ZE 1, available from Evonik Industries) and bis(2-dimethylaminoethyl ether), 70% by weight solution in dipropylene glycol (TEGOAMIN ^® BDE, available at Evonik Industries). In each case 0.20 pphp (=parts by weight based on 100 parts by weight of polyol) of amine were used. Table 12: Results of the foaming according to formulation 3 (Table 11). amine rise time [s] relapse [cm] Height [cm] RG [kg/m ³ ] porosity [mm] ¹⁾ CLD 40% [kPa] TEGOAMIN ^® 33 123 0.1 28.6 31:8 24 4.4 TEGOAMIN ^® ZE 1 138 0.2 28.4 31:6 20 4.0 TEGOAMIN® ^DMEA 136 0.2 28.3 31.2 18 3.7 TEGOAMIN ^® BDE 92 0.5 28.2 30.9 14 3.5 FORMULA (IIIb) 139 0.2 28.1 31.0 17 3.8 FORMULA (IIIc) 129 0.2 28.6 30.9 13 3.6 FORMULA (IVb) 120 0.3 28.7 31.7 18 3.9 FORMULA (IVc) 131 0.2 28.3 31:1 13 3.5 FORMULA (IVd) 99 0.9 29.1 31:1 12 3.9
¹⁾ = (dynamic pressure in mm water column).

As can be seen from Table 12, the nitrogen-containing compounds of the formula (IIIb), (IIIc), (IVb), (IVc) and (IVd) exhibit good to excellent catalytic activity in flexible foam. The compounds of the formula (IIIb), (IIIc) and (IVc) are similar to TEGOAMIN ^® DMEA and TEGOAMIN ^® ZE 1, with all three compounds being somewhat more balanced in terms of selectivity and catalytic profile and in this respect between TEGOAMIN ^® DMEA and TEGOAMIN ^® ZE 1. The nitrogen-containing compound of the formula (IVb) is comparable to TEGOAMIN ^® 33 in terms of activity and selectivity.

Example 4 Emissions from flexible polyurethane slabstock foams not according to the invention

In order to investigate the influence of the nitrogen-containing compounds on the foam emissions, the foam formulation given in Table 13, which contains a low-emission polyol and a low-emission tin catalyst, was used for the performance testing of flexible slabstock foams. Table 13: Formulation 4, Foam emissions in flexible slabstock applications. Formulation 4 Bulk parts (pphp) Polyol 1 ¹⁾ 100 parts water 3.00 parts tin catalyst ²⁾ 0.60 parts amine 0.15 parts TEGOSTAB ^® BF 2370 ³⁾ 0.80 parts ^Desmodur® T 80 ⁴⁾ 41.6 parts
¹⁾ Polyol 1: Low-emission glycerol-based polyether polyol with an OH number of 56 mgKOH/g.
^{2) KOSMOS®} EF, available from Evonik Industries: tin(II) salt of ricinoleic acid.
³⁾ Polyether modified polysiloxane.
⁴⁾ Tolylene diisocyanate T 80 (80% 2,4-isomer, 20% 2,6-isomer) from Bayer, 3 m Pa·s, 48% NCO, functionality 2.

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

The foaming was carried out using the hand mixing method. The formulation as given in Table 13 was used with various nitrogen-containing catalysts (amines). For this purpose, low-emission polyol, conventional or inventive nitrogen-containing catalyst (amine), low-emission tin catalyst, water and foam stabilizer were weighed into a beaker and mixed at 1000 rpm for 60 seconds. After addition of the isocyanate (TDI), the reaction mixture was stirred at 2500 rpm for 7 s and immediately transferred to a paper-lined box (27 cm x 27 cm base and 27 cm height) and the resulting foam, after blowing off, covered with polyethylene film hermetically sealed. After a hardening phase of 24 hours, a defined foam cube (7 cm×7 cm×7 cm) was cut out of the resulting block of foam, which was completely enclosed with aluminum foil and further sealed with polyethylene foil.

The emission behavior of the foams described above was then examined at room temperature using the test chamber test based on the DIN specification DIN EN ISO 16000-9:2008-04, as described above. The results are shown in Table 14. Table 14: Emissions of flexible slabstock foams according to formulation 4 (Table 13). Content of volatile organic compounds according to the test chamber test (PK) amine PK _total ¹⁾ [µg/m ³ ] PK _amine ¹⁾ [µg/m ³ ] TEGOAMIN ^® 33 96 67 TEGOAMIN ^® ZE 1 < 20 < 10 TEGOAMIN® ^DMEA 29 < 10 TEGOAMIN ^® BDE 293 276 FORMULA (IIIb) < 20 < 10 FORMULA (IIIc) < 20 < 10 FORMULA (IVb) < 20 < 10 FORMULA (IVc) < 20 < 10 FORMULA (IVd) < 20 < 10
¹⁾ PK _tot = total emissions; PK _Amin = amine emissions of all volatile organic compounds in the test chamber test.

Table 14 shows that the compounds of formula (III) and (IV) are low in amine emissions after the chamber test as described above.

Example 6 Aging Resistance of Flexible Polyurethane Slabstock Foams Not According to the Invention

The thermal aging resistance of these foams was investigated for performance testing of the nitrogen-containing compounds with regard to the aging behavior of the flexible polyurethane slabstock foams produced with these catalysts. The foam formulation given in Table 15 was used for this. Table 15: Formulation 5 for determining the heat aging resistance of flexible block foams. Formulation 5 Polyol 1 ¹⁾ 100 parts water 3.00 parts tin catalyst ²⁾ 0.20 parts amine -variable- ^TEGOSTAB® B 8244 0.70 parts ^Desmodur® T 80 ³⁾ 37.6 parts
¹⁾ Polyol 1: glycerol-based polyether polyol, with a functionality of 3 and an OH number of 48 mgKOH/g.
²⁾ KOSMOS ^Ⓡ 29, available from Evonik Industries: tin(II) salt of 2-ethylhexanoic acid.
³⁾ Toluylene diisocyanate T 80 (80% 2,4-isomer, 20% 2,6-isomer) from Bayer, 3 m Pa·s, 48% NCO, functionality 2.

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

The foaming was carried out using the hand mixing method. Those in formulations as given in Table 15 with various nitrogen-containing catalysts (amines) were used. For this purpose, low-emission polyol, conventional or inventive nitrogen-containing catalyst (amine), low-emission tin catalyst, water and foam stabilizer were weighed into a beaker and mixed at 1000 rpm for 60 seconds. After addition of the isocyanate (TDI), the reaction mixture was stirred at 2500 rpm for 7 s and immediately transferred to a paper-lined box (27 cm x 27 cm base and 27 cm height). To assess the catalytic properties, the following characteristic parameters were determined: cream time, rise time, height of rise, intensity of blowing off (=blow off) and sagging of the foam after the end of the rise phase (=fall back).

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

Table 16 summarizes the results of the assessment of the catalytic properties of the nitrogen-containing compounds of the formula (IIIb), (IIIc) and (IVb) and of the physical properties of the resulting flexible slabstock foams. In addition to triethylenediamine, a 33% by weight solution in dipropylene glycol ( ^TEGOAMIN® 33, available from Evonik Industries), N,N-dimethylethanolamine (TEGOAMIN® ^DMEA , available from Evonik Industries), N,N -dimethylaminoethoxyethanol (DMEE) and N,N-dimethylaminopropylamine (DMAPA). The results are shown in Table 16.

The compounds of the formula (IIIb), (IIIc) and (IVb) were carried out using an equimolar amount, based on 0.30 pphp of the respective reference substance, with TEGOAMIN ^® DMEA being the reference substance for the compound of the formula (IIIb), TEGOAMIN ^® DMEE is the reference to the compound of formula (IIIc) and DMAPA is the reference to the compound of formula (IVb). Table 16: Results of the foaming according to formulation 2 (Table 9). amine pphp ¹⁾ rise time [s] relapse [cm] Height [cm] RG [kg/m ³ ] porosity [mm] ²⁾ CLD 40% [kPa] TEGOAMIN ^® 33 0.20 125 0.1 27.4 32.5 23 3.8 TEGOAMIN® ^DMEA 0.30 135 0.3 27.3 32.0 10 3.5 FORMULA (IIIb) 0.388 130 0.7 27.2 32.8 12 3.5 DMEE 0.30 121 0.6 26.5 31:8 11 3.3 FORMULA (IIIc) 0.358 116 0.3 27.1 31:6 13 3.3 DMAPA 0.30 112 0.4 26.4 31:3 12 3.3 FORMULA (IVb) 0.376 111 0.4 27.6 30.8 12 3.5
¹⁾ pphp = parts per hundred percent.
²⁾ = (dynamic pressure in mm water column).

The specimens for determining the compressive strength were used for heat aging experiments. Two heat aging processes based on the DIN standard DIN EN ISO 2440/A1:2009-01 were considered here. Once a dry thermal aging at 130 °C for 2 h and once a long-term study for 7 d at 100 °C was carried out. The results of the compression hardness measurements and a qualitative assessment of the foams are shown in Table 17. Table 17: Results of the heat aging tests. Compression hardness CLD 40% [kPa] amine pphp after foaming after aging (100 °C / 7 d) after aging (130 °C/ 2 h) TEGOAMIN ^® 33 0.20 3.8 3.8 3.8 TEGOAMIN® ^DMEA 0.30 3.5 3.0 3.3 FORMULA (IIIb) 0.388 3.5 3.3 3.5 DMEE 0.30 3.3 2.3 2.6 FORMULA (IIIc) 0.358 3.3 3.0 3.0 DMAPA 0.30 3.3 3.0 3.2 FORMULA (IVb) 0.376 3.5 3.4 3.5

It can be seen from Table 17 that heat aging of foams obtained using TEGOAMIN ^® 33 does not have a negative effect on compressive strength. In comparison, the use of the reactive and installable catalysts DMEE, TEGOAMIN ^® DMEA and DMAPA leads to a significantly lower compressive strength value after heat aging. The use of the nitrogen-containing compounds of the formula (IIIb), (IIIc) and (IVb), which are also reactive, in each case shows a significant improvement in the aging resistance of the resulting foams, which can be read from the respectively better values for the compression hardness after heat treatment.

Example 7 Production of HR Foams (Block/Molded) Not According to the Invention

The foam formulation given in Table 18 was used to test the performance of the nitrogen-containing compounds. Table 18: Formulation 6 for cold flexible foam applications (HR block/moulded). Formulation 6 Bulk parts (pphp) Polyol 1 ¹⁾ 70.0 parts polyol 2 ²⁾ 30.0 parts water 3.70 parts glycerin 0.50 parts Diethanolamine (DEOA) 1.00 parts amine 0.25 parts TEGOSTAB ^® B 8716 LF2 ³⁾ 1.00 parts ^Desmodur® T 80 ⁴⁾ 44.0 parts
¹ ) Polyol 1: Sorbitol/glycerin-based polyether polyol, with an OH number of 32 mgKOH/g.
²⁾ Polyol 2: Glycerol-based polyether polyol containing 43% solids (SAN) with an OH number of 20 mgKOH/g.
³⁾ Preparation of organomodified polysiloxanes.
⁴⁾ Toluylene diisocyanate T 80 (80% 2,4-isomer, 20% 2,6-isomer) from Bayer, 3 mPa s, 48% NCO, functionality 2.

The same foaming methods as in the case of the classic flexible polyurethane foam in Examples 3 and 4 were used here.

500 g of polyol were used in the foaming; the other formulation components were converted accordingly. For example, 1.00 part of a component means 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, a stirrer was used for 4 s at 3000 rpm. stirred and the mixture poured into a paper-lined wooden box (27 cm x 27 cm base and 27 cm height). A foam was formed which was subjected to the performance tests described below.

Table 19 summarizes the results of evaluating the catalytic properties of the nitrogen-containing compounds of the formulas (III) and (IV) and the physical properties of the resulting foams. Bis(2-dimethylaminoethyl ether), 70% by weight solution in dipropylene glycol ( ^TEGOAMIN® BDE, available from Evonik Industries), N,N-dimethylethanolamine (TEGOAMIN® ^DMEA , available from Evonik Industries), N,N-dimethylaminoethoxyethanol (DMEE), triethylenediamine, 33% weight solution in dipropylene glycol ( ^TEGOAMIN® 33, available from Evonik Industries), N,N-dimethylaminopropylamine (DMAPA) and N,N -dimethylaminoethylamine (DMEN) used. The comparative catalysts were each used with 0.25 pphp (=parts by weight based on 100 parts by weight polyol) of amine. The nitrogen-containing compounds of formula (III) and (IV) were also each used with 0.25 pphp of amine. In addition, however, foaming was carried out here with an equimolar amount of the nitrogen-containing compound of the formula (IIIb), (IIIc), (IVb) and (IVc), based on 0.25 pphp of the respective reference substance, with TEGOAMIN ^® DMEA being the reference substance the compound of formula (IIIb), N,N-dimethylaminoethoxyethanol (DMEE) the reference to the compound of formula (IIIc), DMAPA the reference to the compound of formula (IVb) and DMEN the reference to the compound of formula (IVc) represents. Table 19: Results of the foaming according to formulation 6 (table 18). amine pphp ¹⁾ gel time [s] rise time [s] Height [cm] relapse [cm] Number of cells ²⁾ [cm ^-1 ] TEGOAMIN ^® BDE 0.25 58 85 33.0 1.8 10.5 TEGOAMIN® ^DMEA 0.25 169 235 25.1 collapse collapse FORMULA (IIIb) 0.25 175 237 26.9 0.1 9.5 FORMULA (IIIb) ³⁾ 0.32 153 229 28.3 0.2 9.5 DMEE 0.25 112 219 30.8 0.2 10.0 FORMULA (IIIc) 0.25 113 204 31:6 0.2 10.0 FORMULA (III _C ) ³⁾ 0.30 106 192 31:9 0.2 10.0 TEGOAMIN ^® 33 0.25 94 175 30.5 0.0 11.0 DMAPA 0.25 98 165 28.6 0.6 10.5 FORMULA (IVb) 0.25 88 162 29.6 0.7 10.5 FORMULA (IVb) ³⁾ 0.31 77 128 30.1 0.6 11.0 DMEN 0.25 134 217 28.2 0.7 10.5 FORMULA (IVc) 0.25 116 180 29.1 0.4 10.5-11.0 FORMULA (IVc) ³⁾ 0.32 91 179 29.2 0.5 11.0 Formula (IIId) 0.25 69 126 32.2 0.7 10.5
¹⁾ pphp = parts per hundred percent.
²⁾ Number of cells = number of cells per cm [cm ^-1 ].
³⁾ Equimolar amount used based on the respective reference substance.

As can be seen from Table 19, the nitrogen-containing compounds of the formula (IIIb), IIIc), (IVb), (IVc) and (IVd) are excellent catalysts for this cold foam application, even when used in small quantities. Even when used as little as 0.25 pphp, the compounds are of comparable activity to the corresponding reference substances. This effect increases when the amount used is equimolar, so that all compounds have a higher activity than the corresponding references. In terms of selectivity, all compounds have slightly more balanced catalysis and slightly prefer the gel reaction compared to the references. This effect can be seen most clearly in the comparison of TEGOAMIN ^® DMEA and the compound of the formula (IIIb), where the higher activity when used in small amounts, in contrast to TEGOAMIN ^® DMEA, is sufficient to prevent the foam from collapsing. The compound of formula (IVb), for example, is also a highly gel-selective catalyst and is in the range of ^TEGOAMIN® 33 in terms of activity and selectivity. The compound of formula (IVd) is already at an input level of 0.25 pphp even more active and of similar selectivity as TEGOAMIN ^® 33 and the compound of formula (IVb).

The emission behavior of the foams described above was then examined based on the test specification VDA 278 in the October 2011 version, as described above. The results are shown in Table 20. Table 20: Emissions from flexible cold foams according to VDA 278. Content of volatile organic compounds (VOC) amine pphp VOC _total ¹⁾ [µg/g] VOC _amine ¹⁾ [µg/g] Fog _total ²⁾ [µg/g] Fog _amine ²⁾ [µg/g] TEGOAMIN ^® BDE 0.25 645 325 314 < 10 TEGOAMIN® ^DMEA 0.25 365 < 10 302 < 10 FORMULA (IIIb) 0.32 350 < 10 296 < 10 DMEE 0.25 332 < 10 278 < 10 FORMULA (IIIc) 0.30 340 < 10 298 < 10 TEGOAMIN ^® 33 0.25 532 188 260 < 10 DMAPA 0.25 330 < 10 200 < 10 FORMULA (IVb) 0.31 340 < 10 210 < 10 DMEN 0.25 330 < 10 208 < 10 FORMULA (IVc) 0.32 320 < 10 202 < 10
¹⁾ VOC _tot = total emissions; VOC _Amine = Amine emissions of all volatile organic compounds at 90°C (30 minutes).
²⁾ Fog _tot = total emissions; Fog _amine = amine emissions of all volatile organic compounds at 120 °C (60 minutes).

As can be seen from Table 20, the polyurethane foams, which using the nitrogen-containing compounds of the formula (IIIb), IIIc), (IVb) and (IVc), as well as the Foams used using the appropriate references have no amine emissions. This is an advantage of these compounds compared to TEGOAMIN ^® BDE and TEGOAMIN ^® 33. With regard to the good fog values, the compounds described here also represent an advantageous alternative to other reactive amine catalysts, especially for use in foams for automotive interior applications.

In addition, the foams described above were examined with regard to their influence on the discoloration of plastics. For this purpose, a PVC discoloration test was carried out in accordance with Volkswagen test specification VW PV 3937, as described above. After the examination, the PVC film was subjected to a visual inspection. The results are shown in Table 21. Table 21: Results of the PVC discoloration test according to VW test specification VW PV 3937. amine pphp visual assessment BLANK grey, no coloring TEGOAMIN ^® BDE 0.25 strong red coloration TEGOAMIN® ^DMEA 0.25 slight yellowing FORMULA (IIIb) 0.32 at most faint yellowing DMEE 0.25 slight yellowing FORMULA (IIIc) 0.30 very faint yellowish tinge TEGOAMIN ^® 33 0.25 strong red coloration DMAPA 0.25 slight yellowing FORMULA (IVb) 0.31 no to weak yellowing DMEN 0.25 slight yellowing FORMULA (IVc) 0.32 no to weak yellowing

As can be seen from Table 21, the polyurethane foams made using the nitrogen-containing compounds of formula (IIIb), IIIc), (IVb) and (IVc), like the foams made using the corresponding references, in each case to a weaker discoloration of the PVC film than those foams that were produced with TEGOAMIN ^® BDE and TEGOAMIN ^® 33, moreover, is with the nitrogen-containing compounds of the formula (IIIb), IIIc), (IVb) and (IVc ) again a visually clearly recognizable improvement in the discoloration than with the corresponding references.

The foams described above were finally tested for emissions of aldehydes based on the test specification VDA 275, the July 1994 version, as described above. The results are shown in Table 22. Table 21: Results of the determination of aldehyde emissions according to VDA 275. amine pphp Formaldehyde [ppm] ¹⁾ Acetaldehyde [ppm] ¹⁾ Propionaldehyde [ppm] ¹⁾ TEGOAMIN® ^DMEA 0.25 0.80 0.41 0.08 FORMULA (IIIb) 0.32 0.21 0.22 0.10 DMEE 0.25 0.58 0.12 0.07 FORMULA (IIIc) 0.30 0.19 0.10 0.08 DMAPA 0.25 0.32 0.19 0.08 FORMULA (IVb) 0.31 0.13 0.08 0.09 DMEN 0.25 0.56 0.12 0.04 FORMULA (IVc) 0.32 0.16 0.08 0.06
¹⁾ ppm = parts per million.

Table 21 shows that when the nitrogen-containing compounds of the formula (IIIb), IIIc), (IVb) and (IVc) are used in equimolar amounts instead of the corresponding references, a measurable reduction in aldehyde emissions, in particular formaldehyde emissions, of the resulting polyurethane foams can be seen. Especially in the case of open-cell foams, it is of particular interest to avoid emissions of such toxic aldehydes as far as possible, which can be helped by using the compounds of the formula (III) or (IV).

Claims (3)

Use of at least one nitrogen-containing compound and/or a corresponding quaternized and/or protonated compound for the production of rigid polyurethane foams which lead to less discoloration of plastics, characterized in that the nitrogen-containing compound satisfies the formula (IVc).

use after claim 1 , characterized in that at least one nitrogen-containing compound of the formula (IVc) is used as a technical product mixture containing impurities, intermediates and/or by-products as further ingredients, comprising pyrrolidine, 1-(2-chloroethyl)pyrrolidine, 1,4- Butanediol, monoethylene glycol (MEG), diethylene glycol (DEG), 1-2-propylene glycol (PG), dipropylene glycol (DPG) and/or monoethanolamine, in amounts of ≤ 30% by weight. Use according to one of the preceding claims, characterized in that the nitrogen-containing compound according to formula (IVc) is used as a catalyst in the production of rigid polyurethane foams, the said nitrogen-containing compound being used as a technical product mixture in accordance with claim 2 is used.