NITROGEN-CONTAINING COMPOUNDS SUITABLE FOR USE IN THE PRODUCTION OF POLYURETHANES

Abstract

The present invention provides for the use of nitrogen compounds of formula (I) and/or of corresponding quaternized and/or protonated compounds for production of polyurethanes, compositions containing these compounds and polyurethane systems, especially polyurethane foams, which have been obtained using the compounds.

Claims

1. A process for making a polyurethane comprising mixing at least one nitrogen compound and/or a corresponding quaternized and/or protonated compound, or mixtures of the nitrogen compound with corresponding quaternized and/or protonated compounds, wherein this nitrogen compound satisfies the formula (I) ##STR00054## with n=1-30, where R.sub.1 is H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated hydrocarbyl radical which is optionally substituted by one or more heteroatoms or interrupted by one or more heteroatoms and has 1 to 30 carbon atoms, where R.sub.2 is a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated hydrocarbyl radical which is optionally substituted by one or more heteroatoms or interrupted by one or more heteroatoms and has 1 to 30 carbon atoms.

2. The process according to claim 1, wherein at least one nitrogen compound of the formula (I) is employed, where R.sub.1 and R.sub.2 are bridged to form a pyrrolidine cycle, and so at least one nitrogen compound of the formula (I) which satisfies the formula (VI) is used, ##STR00055## with n=2-12 except for 4.

3. The process according to claim 1, wherein at least one nitrogen compound of the formula (I) is employed, with R.sub.1H and ##STR00056## and so at least one nitrogen compound of the formula (I) which satisfies the formula (II) is used ##STR00057## with n=2-12, where R.sub.3H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated hydrocarbyl radical which is optionally substituted by one or more heteroatoms or interrupted by one or more heteroatoms and has 1 to 30 carbon atoms.

4. The process according to claim 1, wherein at least one nitrogen compound of the formula (I) is employed, with R.sub.1H and ##STR00058## and so at least one nitrogen compound of the formula (I) which satisfies the formula (IV) is used ##STR00059## with n=2-12, where R.sub.5, R.sub.6 are the same or different and are each H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated hydrocarbyl radical which is optionally substituted by one or more heteroatoms or interrupted by one or more heteroatoms and has 1 to 30 carbon atoms.

5. The process according to claim 1, wherein at least one nitrogen compound of the formula (I) is employed, where R.sub.1 and R.sub.2 are bridged to form a piperazine cycle, and so at least one nitrogen compound of the formula (I) which satisfies the formula (VII) is used, ##STR00060## with n=2-12, and R.sub.8H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated hydrocarbyl radical which is optionally substituted by one or more heteroatoms or interrupted by one or more heteroatoms and has 1 to 30 carbon atoms.

6. The process according to claim 1, wherein at least one nitrogen compound of the formula (I) is employed, where R.sub.1 and R.sub.2 are bridged to form a triazine cycle, and so at least one nitrogen compound of the formula (I) which satisfies the formula (VIII) is used, ##STR00061## with identical or different n, q, r=2-12.

7. The process according to claim 1, wherein at least one nitrogen compound of the formula (I), is used as a technical product mixture, especially comprising impurities, intermediates and/or by-products as further constituents, especially comprising pyrrolidine, 1-(3-aminopropyl)pyrrolidine, 1-(2-aminoethyl)pyrrolidine, 1-(2-hydroxyethyl)pyrrolidine, 1-(3-hydroxypropyl)pyrrolidine, trimethylenediamine, ethylenediamine (EDA), butane-1,4-diol, monoethylene glycol (MEG), diethylene glycol (DEG) and/or monoethanolamine (MEA), in a total amount of up to 95% by weight, wherein the technical product mixture especially comprises (a) at least one nitrogen compound of the formula (I), advantageously in a total amount of 5% by weight, (b) optionally 1-(3-aminopropyl)pyrrolidine, advantageously in an amount of 5% by weight, (c) optionally 1-(2-aminoethyl)pyrrolidine, advantageously in an amount of 5% by weight, (d) optionally 1-(2-hydroxyethyl)pyrrolidine, advantageously in an amount of 5% by weight, (e) optionally 1-(3-hydroxypropyl)pyrrolidine, advantageously in an amount of 5% by weight, (f) optionally trimethylenediamine, advantageously in an amount of 5% by weight, (g) optionally ethylenediamine (EDA), advantageously in an amount of 95% by weight, (h) optionally butane-1,4-diol, advantageously in an amount of 95% by weight, (i) optionally monoethylene glycol (MEG), advantageously in an amount of 95% by weight, (j) optionally diethylene glycol (DEG), advantageously in an amount of 95% by weight, (k) optionally monoethanolamine (MEA), advantageously in an amount of 95% by weight.

8. The process according to claim 1, wherein the nitrogen compound of one of the formulae (I), a correspondingly quaternized and/or protonated compound, or mixtures of the nitrogen compounds of the formula (I) with corresponding quaternized and/or protonated compounds, is used as catalyst in the production of polyurethanes, especially polyurethane foams.

9. The process according to claim 1, wherein, in the production of the polyurethane, especially polyurethane foam, a composition including at least one nitrogen compound of the formula (I), and/or a corresponding quaternized and/or protonated compound, at least one polyol component, at least one isocyanate component and optionally one or more blowing agents is produced, and this composition is reacted.

10. The process according to claim 1, wherein the at least one nitrogen compound of the formula (I), is used in combination with at least one solvent, where the mass ratio of the total amount of catalyst used, comprising all the catalytically active compounds of the formula (I) and not of the formula (I), to solvent is from 100:1 to 1:4.

11. A composition comprising at least one polyol component, wherein the composition includes at least one nitrogen compound of the formula (I) as defined in claim 1, and/or the corresponding quaternized and/or protonated compounds, wherein the composition preferably includes at least one isocyanate component, and wherein the nitrogen compound of the formula (I), and wherein the composition comprises additional amine catalysts not of the formula (I).

12. The composition according to claim 11, wherein the molar ratio of the total amount of the nitrogen-containing catalysts, comprising the nitrogen compounds of the formula (I), relative to the total amount of the groups reactive with isocyanates in the polyol component is from 410.sup.4:1 to 0.2:1.

13. The compositions according to claim 11, wherein the nitrogen compounds of the formula (I), and corresponding quaternized and/or protonated compounds are used in an amount totalling a proportion by mass of 0.01 to 20.0 parts (pphp), of polyol component.

14. A polyurethane foam wherein it is obtainable through the method according to claim 1, where the polyurethane foam is especially a rigid polyurethane foam, a flexible polyurethane foam, a viscoelastic foam, a cold-cure foam (also called high-resilience (HR) foam), a semirigid polyurethane foam, a thermoformable polyurethane foam or an integral foam, having a proportion by mass of nitrogen compounds of the formula (I) and/or the corresponding quaternized and/or protonated compounds, or the residues obtained by conversion thereof, in the finished polyurethane foam of 0.005% to 10% by weight.

15. The use of polyurethane foam according to claim 14 as refrigerator insulation, insulation panel, sandwich element, pipe insulation, spray foam, 1- and 1.5-pack canned foam, imitation wood, modelling foam, floral foam, packaging foam, mattress, furniture cushion, moldable foam for furniture, pillows, rebonded foam, sponge foam, automobile seat cushion, headrest, dashboard, automobile interior, automobile roof liner, sound absorption material, steering wheel, shoe sole, carpet backing foam, filter foam, sealing foam, sealant and adhesive, or for production of corresponding products.

16. The process according to claim 2, wherein the use of at least one nitrogenous compound of formula (VI), where n=2, 3, or 6.

17. The process according to claim 2, where this nitrogen compound (VI) is selected from the group consisting of ##STR00062##

18. The process according to claim 3, wherein where the nitrogen compound of formula (II) is selected from the group consisting of ##STR00063##

19. The process according to claim 4, wherein where the nitrogen compound of formula (IV) is selected from the group consisting of ##STR00064##

20. The process according to claim 5, wherein where the nitrogen compound of formula (VII) is selected from the group consisting of ##STR00065## ##STR00066##

Description

EXAMPLES

[0270] Preparation of Inventive Nitrogen Compounds

[0271] The 1-(3-aminopropyl)pyrrolidine (CAS 23159-07-1) required for the synthesis of the inventive compounds of the formula (II) to (VII) was, as known from the prior art, prepared by the Michael addition of acrylonitrile onto pyrrolidine and subsequent hydrogenation of the nitrile formed and final fine distillation.

Synthesis Example 1

Preparation of 1-pyrrolidinepropanenitrile

[0272]

TABLE-US-00002 [00031] Chemical CAS Supplier acrylonitrile, >99% 107-13-1 Sigma-Aldrich Chemie GmbH pyrrolidine, 99% 123-75-1 ABCR dichloromethane 75-09-2 Sigma-Aldrich Chemie GmbH sodium hydroxide, 99%, p.a. 1310-73-2 Karl Roth GmbH sodium chloride, 99.8%, 7647-14-5 Karl Roth extra fine GmbH methanol, 99.8% 67-56-1 Sigma-Aldrich Chemie GmbH

[0273] A 6 l five-neck flask equipped with dropping funnel, thermometer, precision glass stirrer and nitrogen feed is initially charged with 2224 ml of water at room temperature, and the reaction vessel is inertized. Then 861.2 ml (737.18 g, 10.37 mol) of pyrrolidine were added gradually, in the course of which the temperature rose to 35 C. The reaction apparatus was inertized again through the dropping funnel, and the latter was filled with 625 ml (500 g, 9.42 mol) of acrylonitrile. By means of a cooling bath, the amine solution was cooled down to 5 C., and then the addition of the acrylonitrile was commenced. Over the course of 5 hours, the rate of dropwise addition was adjusted in such a way that the reaction temperature did not exceed 5 C. The reaction mixture was allowed to warm up to room temperature and stirred for a further hour.

[0274] Then 2.1 1 of a 33% by weight aqueous sodium hydroxide solution were added, whereupon a milky suspension formed. After the mixture had been decanted off into a separating funnel, the phases separated, and the turbid upper organic phase, still containing water, was separated. For better phase separation, 200 ml of dichloromethane and 50 ml of a cold-saturated sodium chloride solution were added. The upper, slightly opaque organic phase was dried over magnesium sulphate and the solvent was concentrated on a rotary evaporator. The fine distillation that followed gave 1.25 kg of a clear, pale yellow oil, the NMR spectroscopy analysis of which was in accordance with expectation. A GC analysis confirmed a purity of >95%.

Synthesis Example 2

Preparation of 1-(3-aminopropyl)pyrrolidine

[0275] ##STR00032##

[0276] The subsequent hydrogenation of the above-prepared 1-pyrrolidinepropanenitrile was effected by means of Pd/Al.sub.2O.sub.3 (5% by weight), as described by Krupka and Jiri et al. inHydrogenation of 3-(dimethylamino)propionitrile over palladium catalysts (Czechoslovak Chemical Communications, 65 (11), 1805-1819; 2000). The resultant crude reaction mixture was admixed with Celite filtering aid, filtered and rinsed through with methanol. The solvent was concentrated and the crude product was subjected to a fine distillation, wherein the main fraction distilled over at a top temperature of 90 C. in a membrane pump vacuum at 24 mbar. An alternative electrochemical method is described in SU1421738 (A1).

Synthesis Example 3

Preparation of a compound of the formula (II), using the example of the compound of the formula (IIa)

[0277]

TABLE-US-00003 [00033] [00034] Chemical CAS Supplier urea, p.a. 57-13-6 Sigma-Aldrich Chemie GmbH 1-(3-aminopropyl)pyrrolidine 23159-07-1

[0278] A four-neck flask equipped with precision glass stirrer, reflux condenser, temperature measurement probe and inert gas feed was initially charged with 19.82 g (0.33 mol) of urea, and 84.62 g (0.66 mol) of 1-(3-aminopropyl)pyrrolidine were added. After inertization of the reaction apparatus by means of nitrogen, the mixture was heated to 130 C., in the course of which the urea went into solution. A gentle nitrogen stream assured a constant inert gas atmosphere, and the progress of the reaction was recognized by a continuous loss of ammonia, which was detectable by means of indicator paper at the gas outlet. After a total reaction time of 32 hours, an oil-pump vacuum of >1 mbar was applied to the pale yellowish product mixture which was viscous at 130 C., and excess reactant and other volatile constituents were thus distilled off. After cooling, it was possible to obtain the desired product of the formula (IIa) as a white to pale beige, crystalline product. The 13C NMR analyses corresponded to expectation and confirmed that the desired product had formed.

Synthesis Example 4

Preparation of a Compound of the Formula (II), Using the Example of the Compound of the Formula (IIb)

[0279]

TABLE-US-00004 [00035] [00036] Chemical CAS Supplier 1-methylurea 598-50-5 TCI Deutschland GmbH 1-(3-aminopropyl)pyrrolidine 23159-07-1

[0280] A 250 ml four-neck flask equipped with precision glass stirrer, reflux condenser, temperature measurement probe and inert gas feed was initially charged with 40.75 g (0.55 mol) of 1-methylurea and 70.52 g (0.55 mol) of the previously prepared 1-(3-aminopropyl)pyrrolidine. Then the reaction apparatus was inertized with nitrogen and heated up to a reaction temperature of 110 C., in the course of which the methylurea melted in the temperature region of 90 C., and a clear and colorless solution formed. A continuous loss of ammonia was observed, which was detectable by means of an indicator paper at the gas outlet. After a reaction time of 17 hours, the reaction temperature was increased to 130 C., and this was maintained for a further 17 hours. Since no significant loss of ammonia was detectable any longer, the mixture was left to cool to room temperature. It was thus possible to obtain 101 g of a pale yellow, highly viscous product of the formula (IIb), and the 13C NMR analysis confirmed product formation.

Synthesis Example 5

Preparation of a Compound of the Formula (II), Using the Example of the Compound of the Formula (IIc)

[0281]

TABLE-US-00005 [00037] [00038] Chemical CAS Supplier 1-methylurea 598-50-5 TCI Deutschland GmbH 1-(2-aminoethyl)pyrrolidine 7154-73-6 ABCR

[0282] A 250 ml four-neck flask equipped with precision glass stirrer, reflux condenser, temperature measurement probe and inert gas feed was initially charged with 40.75 g (0.55 mol) of 1-methylurea and 62.80 g (0.55 mol) of 1-(2-aminoethyl)pyrrolidine. Then the reaction apparatus was inertized with nitrogen and heated up to a reaction temperature of 100 C., in the course of which the methylurea melted, and a clear and colorless solution formed. A continuous loss of ammonia was observed, which was detectable by means of an indicator paper at the gas outlet. After a reaction time of 32 hours, no significant loss of ammonia was detectable any longer and the reaction mixture was left to cool to room temperature. It was thus possible to obtain 92.2 g of a clear, pale brownish and highly viscous product of the formula (IIc), and the 13C NMR analysis confirmed product formation.

Synthesis Example 6

Preparation of a Compound of the Formula (III), Using the Example of the Compound of the Formula (IIIa)

[0283]

TABLE-US-00006 [00039] [00040] Chemical CAS Supplier ethylene carbonate, 98% 96-49-1 Sigma-Aldrich Chemie GmbH acetone, 99.6% 67-64-1 Acros Organics 1-(3-aminopropyl)pyrrolidine 23159-07-1

[0284] A 250 ml four-neck flask equipped with precision glass stirrer, reflux condenser, temperature measurement probe and inert gas feed was initially charged with 51.29 g (0.4 mol) of 1-(3-aminopropyl)pyrrolidine, and the reaction apparatus was inertized with nitrogen and cooled down to 0 C. with a cooling bath. A dropping funnel was charged with 35.22 g (0.4 mol) of ethylene carbonate dissolved in 35 ml of demineralized water, which were then added dropwise within 4 hours in such a way that a reaction temperature of 5-10 C. was not exceeded. Then the reaction mixture was allowed to warm up to room temperature and stirred for a further five hours. The next day, about 100 ml of acetone were added to the product and the reaction mixture was transferred into a one-neck round-bottom flask. On a rotary evaporator, the solvents and all the volatile constituents were finally removed successively up to a final bath temperature of 60 C. and an oil-pump vacuum of <1 mbar. It was thus possible to obtain 84.8 g of a clear viscous product of the formula (IIIa). The .sup.13C NMR spectroscopy analysis of the product was in accordance with expectation.

Synthesis Example 7

Preparation of a Compound of the Formula (III), Using the Example of the Compound of the Formula (IIIb)

[0285]

TABLE-US-00007 [00041] [00042] Chemical CAS Supplier ethylene carbonate, 98% 96-49-1 Sigma-Aldrich Chemie GmbH acetone, 99.6% 67-64-1 Acros Organics 1-(2-aminoethyl)pyrrolidine 7154-73-6 ABCR

[0286] A 250 ml four-neck flask equipped with precision glass stirrer, reflux condenser, temperature measurement probe and inert gas feed was initially charged with 45.08 g (0.4 mol) of 1-(2-aminoethyl)pyrrolidine, and the reaction apparatus was inertized with nitrogen and cooled down to 0 C. with a cooling bath. A dropping funnel was charged with 35.22 g (0.4 mol) of ethylene carbonate dissolved in 35 ml of demineralized water, which were then added dropwise within 4 hours in such a way that a reaction temperature of 5-10 C. was not exceeded. Then the reaction mixture was allowed to warm up to room temperature and stirred for a further five hours. The next day, about 100 ml of acetone were added to the product and the reaction mixture was transferred into a one-neck round-bottom flask. On a rotary evaporator, the solvents and all the volatile constituents were finally removed successively up to a final bath temperature of 60 C. and an oil-pump vacuum of <1 mbar. It was thus possible to obtain 84.8 g of a clear viscous product of the formula (IIIb). The .sup.13C NMR spectroscopy analysis of the product was in accordance with expectation.

Synthesis Example 8

Preparation of a Compound of the Formula (III), Using the Example of the Compound of the Formula (IIIc)

[0287]

TABLE-US-00008 [00043] [00044] Chemical CAS Supplier propylene carbonate, 99% 108-32-7 Sigma-Aldrich Chemie GmbH 1-(3-aminopropyl)pyrrolidine 23159-07-1

[0288] A 250 ml four-neck flask equipped with precision glass stirrer, reflux condenser, temperature measurement probe and inert gas feed was initially charged with 51.29 g (0.4 mol) of 1-(3-aminopropyl)pyrrolidine, and the reaction apparatus was inertized with nitrogen and cooled down to 0 C. with a cooling bath. By means of a dropping funnel, 40.84 g (0.4 mol) of propylene carbonate were then added dropwise within 4 hours in such a way that a reaction temperature of 5-10 C. was not exceeded. Then the reaction mixture was allowed to warm up to room temperature and stirred for a further five hours. The next day, the reaction mixture was transferred into a one-neck round-bottom flask, and all the volatile constituents were finally removed successively on a rotary evaporator up to a final bath temperature of 60 C. and an oil-pump vacuum of <1 mbar. It was thus possible to obtain 91 g of a clear viscous product of the formula (IIIc). The .sup.13C NMR spectroscopy analysis of the product was in accordance with expectation.

Synthesis Example 9

Preparation of a Compound of the Formula (III), Using the Example of the Compound of the Formula (IIId)

[0289]

TABLE-US-00009 [00045] [00046] Chemical CAS Supplier propylene carbonate, 99% 108-32-7 Sigma-Aldrich Chemie GmbH 1-(2-aminoethyl)pyrrolidine 7154-73-6 ABCR

[0290] A 250 ml four-neck flask equipped with precision glass stirrer, reflux condenser, temperature measurement probe and inert gas feed was initially charged with 45.68 g (0.4 mol) of 1-(2-aminoethyl)pyrrolidine, and the reaction apparatus was inertized with nitrogen and cooled down to 0 C. with a cooling bath. By means of a dropping funnel, 40.84 g (0.4 mol) of propylene carbonate were then added dropwise within 4 hours in such a way that a reaction temperature of 5-10 C. was not exceeded. Then the reaction mixture was allowed to warm up to room temperature and stirred for a further five hours. The next day, the reaction mixture was transferred into a one-neck round-bottom flask, and all the volatile constituents were finally removed successively on a rotary evaporator up to a final bath temperature of 60 C. and an oil-pump vacuum of <1 mbar. It was thus possible to obtain 85.6 g of a clear, pale yellowish and viscous product of the formula (IIId). The .sup.13C NMR spectroscopy analysis of the product was in accordance with expectation.

Synthesis Example 10

Preparation of a Compound of the Formula (IV), Using the Example of the Compound of the Formula (IVa)

[0291]

TABLE-US-00010 [00047] [00048] Chemical CAS Supplier guanidine hydrochloride, 50-01-1 Sigma-Aldrich >99% Chemie GmbH 1-(3-aminopropyl)pyrrolidine 23159-07-1 sodium methoxide 124-41-4 ABCR methanol 67-56-1 Sigma-Aldrich Chemie GmbH

[0292] A 250 ml four-neck flask equipped with reflux condenser, precision glass stirrer, internal thermometer and argon inlet was initially charged with 114.19 g (1 mol) of 1-(3-aminopropyl)pyrrolidine under inert conditions, and 31.84 g (0.33 mol) of guanidine hydrochloride were added. The reaction mixture thus produced was heated up to 110 C., and a gentle vacuum was applied by means of a membrane pump in order to facilitate the departure of ammonia. The color of the product changed to red-brown within a few minutes. After a total reaction time of 35 hours, all the volatile constituents were removed at 95-100 C. in an oil-pump vacuum (<1 mbar). In the course of cooling to room temperature, the red-brown product crystallized, but exhibited good solubility in standard laboratory solvents. The 1H/13C NMR spectra confirmed product formation and corresponded to expectation.

[0293] In order to obtain the analogous free guanidine base, an aliquot of the above product was dissolved in 40% by weight solution in methanol, and a stoichiometric amount of sodium methoxide was added. After stirring at room temperature overnight, turbidity was observed, and the solvent was removed on a rotary evaporator at 80 C. and a pressure of 1 mbar, resulting in precipitation of sodium chloride. After filtration by means of a pressurized filter press, it was possible to obtain the free guanidine base of the formula (IVa) as a brown oil.

Synthesis Example 11

Preparation of a Compound of the Formula (IV), Using the Example of the Compound of the Formula (IVb)

[0294]

TABLE-US-00011 [00049] [00050] Chemical CAS Supplier guanidine hydrochloride, 50-01-1 Sigma-Aldrich >99% Chemie GmbH 1-(2-aminoethyl)pyrrolidine 7154-73-6 ABCR sodium methoxide 124-41-4 ABCR methanol 67-56-1 Sigma-Aldrich Chemie GmbH

[0295] A 250 ml four-neck flask equipped with reflux condenser, precision glass stirrer, internal thermometer and argon inlet was initially charged with 76.0 g (0.66 mol) of 1-(2-aminoethyl)pyrrolidine under inert conditions, and 15.92 g (0.166 mol) of guanidine hydrochloride were added. The reaction mixture thus produced was heated up to 110 C., and a gentle vacuum was applied by means of a membrane pump in order to facilitate the departure of ammonia. The color of the product changed to red-brown within a few minutes. After a total reaction time of 35 hours, the excess equivalent of 1-(2-aminoethyl)pyrrolidine and all the other volatile constituents were removed at 95-100 C. in an oil-pump vacuum (<1 mbar). In the course of cooling to room temperature, the red-brown product crystallized, but exhibited good solubility in standard laboratory solvents. The 1H/13C NMR spectra confirmed product formation and corresponded to expectation.

[0296] In order to obtain the analogous free guanidine base, an aliquot of the above product was dissolved in 40% by weight solution in methanol, and a stoichiometric amount of sodium methoxide was added. After stirring at room temperature overnight, turbidity was observed, and the solvent was removed on a rotary evaporator at 80 C. and a pressure of 1 mbar, resulting in precipitation of sodium chloride. After filtration by means of a pressurized filter press, it was possible to obtain the free guanidine base of the formula (IVb) as a brown oil.

Synthesis Example 12

Preparation of a Compound of the Formula (V), Using the Example of the Compound of the Formula (Va)

[0297]

TABLE-US-00012 [00051] [00052] Chemical CAS Supplier caprolactone, 97% 502-44-3 Sigma-Aldrich Chemie GmbH 1-(3-aminopropyl)pyrrolidine 23159-07-1

[0298] A 1000 ml four-neck flask equipped with reflux condenser, precision glass stirrer, internal thermometer and argon inlet is initially charged under inert conditions with 256.43 g (2 mol) of 1-(3-aminopropyl)pyrrolidine and 228.28 g (2 mol) of -caprolactone. The reaction mixture thus produced was heated to 150 C. for four hours. After the reaction had ended, the mixture was fractionated using a short cold finger in an oil-pump vacuum (5.Math.10.sup.2 mbar), and it was possible to obtain a main fraction of 241 g of the product with 50% yield. The 1H/13C NMR spectra of the main fraction confirmed that the product of the formula (Va) had been formed and corresponded to expectation.

Synthesis Example 13

Preparation of a Compound of the Formula (VI), Using the Example of the Compound of the Formula (VIa)

[0299]

TABLE-US-00013 (VIa) [00053] Chemical CAS Supplier 1,6-dichlorohexane, 98% 2163-00-0 Sigma-Aldrich Chemie GmbH triethylamine, 99% 121-44-8 ABCR toluene, 99.5%, ACS 108-88-3 Acros Organics sodium hydroxide, 99%, p.a. 1310-73-2 Karl Roth GmbH diethyl ether, 99% 60-29-7 Sigma-Aldrich Chemie GmbH

[0300] A 1 l four-neck flask equipped with precision glass stirrer, reflux condenser, temperature measurement probe and inert gas feed was initially charged with 242.9 g (2.4 mol) of triethylamine and 50 g of toluene. Then the reaction apparatus was inertized with nitrogen, and 170.7 g (2.4 mol) of pyrrolidine were added at room temperature, whereupon the temperature rose to 35 C. Subsequently, the mixture was heated to pyrrolidine reflux at 77 C. and an amount of 93.4 g (0.6 mol) of 1,6-dichlorohexane was added by means of a dropping funnel within 10 minutes. The mixture was stirred at 86 C. for a further 16 hours and then a solution of 48.2 g of sodium hydroxide in 250 ml of water was added. The now biphasic reaction mixture was transferred into a separating funnel, the organic phase was removed and the aqueous phase was extracted 2 with 100 ml each time of diethyl ether. The combined organic phases were concentrated on a rotary evaporator at 80 C. and 30 mbar, and the crude product was subjected to a fractional distillation. At a top temperature of 125 C. and oil-pump vacuum 3 mbar, it was possible to obtain 44.1 g of a clear colorless fraction of the product of the formula (VIa), which had a purity of 97.3% by GC analysis.

[0301] Rigid FoamFoaming Examples

Example 1

Production of Rigid Polyurethane Foams, for Example for Use in the Insulation of Cooling Units

[0302] For the performance testing of the inventive nitrogen compounds, the foam formulation specified in Table 1 was used.

TABLE-US-00014 TABLE 1 Formulation 1 for rigid foam applications Formulation 1 Parts by mass (pphp) Polyol 1 .sup.1) 100 parts Water 2.60 parts Cyclopentane 13.1 parts Amine 0.80 or 1.50 parts (see Table 2) TEGOSTAB B 8460.sup.2) 1.50 parts Desmodur 44V20L.sup.3) 198.5 parts .sup.1) Polyol 1: sorbitol/glycerol-based polyether polyol having an OH number of 471 mg KOH/g. .sup.2)Polyether-modified polysiloxane. .sup.3)Polymeric MDI from Bayer, 200 mPa .Math. s, 31.5% NCO, functionality 2.7.

[0303] The foams were produced by manual mixing. The formulations as specified in Table 1 were used with various nitrogen-containing catalysts (amines). For this purpose, polyol 1, conventional or inventive nitrogen-containing catalyst (amine), water, foam stabilizer and blowing agent were weighed into a cup and mixed with a disc stirrer of diameter 6 cm at 1000 rpm for 30 seconds. The blowing agent quantity which had evaporated during the mixing operation was determined by reweighing and replenished. Now the isocyanate (MDI) was added, and the reaction mixture was stirred with the stirrer described at 3000 rpm for 5 s and transferred immediately into a paper-lined box (base area 27 cm14 cm and height 14 cm). To assess the catalytic properties, the following characteristic parameters were determined: cream time, gel time (fiber time), rise time and tack-free time.

[0304] The results of the assessment of the catalytic properties of the inventive nitrogen compounds of the formulae (II), (III), (IV), (V) and (VI) are compiled in Table 2. Comparative catalysts according to the prior art used were N,N-dimethylcyclohexylamine (DMCHA), dimethylaminoethoxyethanol (DMEE) and pentamethyldiethylenetriamine (PMDETA).

TABLE-US-00015 TABLE 2 Results of the foaming operations on formulation 1 (Table 1) Cream Gel Rise Tack-free time time time time Amine [s].sup.3) [s].sup.3) [s].sup.3) [s].sup.3) DMCHA.sup.1) 38 137 298 310 DMEE.sup.1) 30 150 272 308 PMDETA.sup.2) 15 128 199 224 FORMULA (IIa).sup.1) 100 375 440 478 FORMULA (IIb).sup.1) 55 225 315 408 FORMULA (IIc).sup.1) 50 210 315 405 FORMULA (IIIa).sup.1) 65 275 350 431 FORMULA (IIIb).sup.1) 90 325 417 444 FORMULA (IIIc).sup.1) 80 280 345 428 FORMULA (IIId).sup.1) 85 315 405 445 FORMULA (IVa).sup.1) 103 390 435 475 FORMULA (IVb).sup.1) 105 397 438 460 FORMULA (Va).sup.1) 79 277 347 431 FORMULA (VIa).sup.1) 35 120 155 205 .sup.1)1.50 parts catalyst used. .sup.2)1.50 parts catalyst used. .sup.3)Times reported in seconds [s].

[0305] As can be inferred from Table 2, the inventive nitrogen compounds of the formulae (II), (III), (IV), (V) and (VI) show a moderate to very good catalytic activity and selectivity in the rigid foam, in some cases comparable to DMCHA and in some cases even better than DMEE. The compound of the formula (VIa) is even a very selective blowing catalyst which is very much more vigorous in terms of activity than DMEE and has a similar selectivity profile to PMDETA.

[0306] Flexible FoamPerformance Tests

[0307] Physical properties of the flexible polyurethane foams:

[0308] The flexible polyurethane foams produced were assessed using the following physical properties: [0309] a) Foam settling after the end of the rise phase (=fall-back): The fall-back, or the further rise, is found from the difference in the foam height after direct blow-off and after 3 minutes after foam blow-off. The foam height is measured at the maximum in the middle of the foam crest by means of a needle secured to a centimeter scale. A negative value here describes the settling of the foam after blow-off; a positive value correspondingly describes the further rise of the foam. [0310] b) Foam height: The final height of the foam is determined by subtracting the fall-back from or adding the further rise to the foam height after blow-off. Foam height is reported in centimeters (cm). [0311] c) Density: The determination is effected, as described in ASTM D 3574-11 under Test A, by measuring the core density. Density is reported in kg/m.sup.3. [0312] d) Porosity: The air permeability of the foam was determined by dynamic pressure measurement on the foam. The dynamic pressure measured is reported in mm water column, and lower dynamic pressure values characterize a more open foam. The values were measured in the range from 0 to 300 mm. [0313] The dynamic pressure was measured by means of an apparatus comprising a nitrogen source, a reducing valve with manometer, a screw-thread flow regulator, a wash bottle, a flow meter, a T-piece, a nozzle head and a scaled glass tube filled with water. The nozzle head has an edge length of 100100 mm, a weight of 800 g, a clear width of the exit orifice of 5 mm, a clear width of the lower applicator ring of 20 mm and an external diameter of the lower applicator ring of 30 mm. [0314] The measurement is effected by adjusting the nitrogen supply pressure to 1 bar with the reducing valve and adjusting the flow rate to 480 l/h. The amount of water in the scaled glass tube is adjusted such that no pressure differential is built up and none can be read off. For the analysis of the test specimen having dimensions of 25025050 mm, the nozzle head is placed onto the corners of the test specimen, flush with the edges, and once onto the (estimated) middle of the test specimen (in each case on the side with the greatest surface area). The result is read off when a constant dynamic pressure has been established. [0315] Evaluation is effected by forming the average of the five measurements obtained. [0316] e) Indentation hardness CLD, 40% to DIN EN ISO 3386. The measurements are reported in kilopascal (kPa).

[0317] Measurement of foam emissions (VOC and fog value) based on test method VDA 278 in the version dated October 2011:

[0318] The method serves 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.), especially of the catalysis-related emissions, the emissions of the individual constituents of inventive catalyst combinations or the breakdown or conversion products thereof, were determined based on test method VDA 278 in the version dated October 2011. There follows a description of the procedure for the corresponding thermal desorption with subsequent gas chromatography-mass spectrometry coupling (GC-MS). [0319] a) Equipment: The thermal desorption was conducted with a TDS2 thermal desorber with autosampler from Gerstel, Mlheim, in conjunction with an Agilent 7890/5975 GC/MSD system. [0320] b) The measurement conditions for VOC analyses are stated in Tables 3 and 4.

TABLE-US-00016 TABLE 3 Thermal desorption analysis parameters for the VOC analysis run Thermal desorption Gerstel TDS2 Desorption temperature 90 C. Desorption time 30 min Flow rate 65 ml/min Transfer line 280 C. Cryofocusing KAS 4 Liner glass evaporator tube with silanized glass wool Temperature 150 C.

TABLE-US-00017 TABLE 4 Gas chromatography-mass spectrometry analysis parameters for the VOC analysis run GC capillary - GC Agilent 7890 Injector PTV split 1:50 Temperature programme 150 C.; 1 min; 10 C./s; 280 C. Column Agilent 19091B-115, Ultra 2, 50 m * 0.32 mm FT 0.5 m Flow rate 1.3 ml/min const. Flow Temperature programme 50 C.; 2 min; 3 C./min; 92 C.; 5 C./min; 160 C.; 10 C./min; 280 C., 20 min Detector Agilent MSD 5975 Mode Scan 29-350 amu 2.3 scans/sec Evaluation Evaluation of the total ion current chromatogram by calculation as toluene equivalent [0321] c) Calibration: For calibration, 2 l of a mixture of toluene and hexadecane in methanol (0.125 mg/ml of each) were introduced into a cleaned adsorption tube filled with Tenax TA (mesh 35/60) and analyzed (desorption 5 min; 280 C.). [0322] d) Tenax TA is a porous polymer resin based on 2,6-diphenylene oxide, obtainable, for example, from Scientific Instrument Services, 1027 Old York Rd., Ringoes, N.J. 08551. [0323] e) Sample preparation for the VOC analysis: 15 mg of foam were positioned in three sample portions in a thermal desorption tube. In doing so, it was ensured that the foam was not compressed. [0324] f) Sample preparation for the fog analysis: The same foam sample was used as for the VOC analysis. With regard to the measurement arrangement, the VOC analysis was always conducted first and the fog analysis thereafter, ensuring a constant separation between each of the corresponding VOC and fog analyses by means of an autosampler system. [0325] g) The measurement conditions for fog analyses are stated in Tables 5 and 6.

TABLE-US-00018 TABLE 5 Thermal desorption analysis parameters for the fog analysis run Thermal desorption Gerstel TDS2 Desorption temperature 120 C. Desorption time 60 min Flow rate 65 ml/min Transfer line 280 C. Cryofocusing KAS 4 Liner glass evaporator tube with silanized glass wool Temperature 150 C.

TABLE-US-00019 TABLE 6 Gas chromatography-mass spectrometry analysis parameters for the fog analysis run GC capillary - GC Agilent 7890 Injector PTV split 1:50 Temperature programme 150 C.; 1 min; 10 C./s; 280 C. Column Agilent 19091B-115, Ultra 2, 50 m * 0.32 mm FT 0.5 m Flow rate 1.3 ml/min const. Flow Temperature programme 50 C.; 2 min; 25 C./min; 160 C.; 10 C./min; 280 C.; 20 min Detector Agilent MSD 5975 Mode Scan 29-450 amu 2.3 scans/sec Evaluation Evaluation of the total ion current chromatogram by calculation as hexadecane equivalent [0326] h) Calibration: For calibration, 2 l of a mixture of toluene and hexadecane in methanol (0.125 mg/ml of each) were introduced into a cleaned adsorption tube filled with Tenax TA (mesh 35/60) and analyzed (desorption 5 min; 280 C.).

[0327] Determination of room temperature emissions by the test chamber test:

[0328] The emission, especially the catalysis-related emissions, the emissions of the individual constituents of inventive catalyst combinations or the breakdown or conversion products thereof were determined at room temperature based on DIN method DIN EN ISO 16000-9:2008-04. Sampling was affected after 24 hours. For this purpose, 2 1 of the test chamber atmosphere were passed through an adsorption tube filled with Tenax TA (mesh35/60) at a flow rate of 100 ml/min. There follows a description of the procedure for the thermal desorption with subsequent gas chromatography-mass spectrometry coupling (GC-MS). [0329] a) Equipment: The thermal desorption was conducted with a TDS2 thermal desorber with autosampler from Gerstel, Mlheim, in conjunction with an Agilent 7890/5975 GC/MSD system. [0330] b) The measurement conditions are stated in Tables 7 and 8.

TABLE-US-00020 TABLE 7 Analysis parameters for thermal desorption for test chamber analysis Thermal desorption Gerstel TDS2 Desorption temperature 280 C. Desorption time 5 min Flow rate 65 ml/min Transfer line 280 C. Cryofocusing KAS 4 Liner glass evaporator tube with silanized glass wool Temperature 150 C.

TABLE-US-00021 TABLE 8 Gas chromatography-mass spectrometry analysis parameters for test chamber analysis GC capillary - GC Agilent 7890 Temperature programme 150 C.; 1 min; 10 C./s; 280 C. Column Agilent 19091B-115, Ultra 2, 50 m * 0.32 mm FT 0.5 m Flow rate 1.3 ml/min const. Flow Temperature programme 50 C.; 2 min; 3 C./min; 92 C.; 5 C./min; 160 C.; 10 C./min; 280 C., 20 min Detector Agilent MSD 5975 Evaluation Evaluation of the total ion current chromatogram by calculation as toluene equivalent [0331] c) For calibration, 2 l of a mixture of toluene and hexadecane in methanol (0.125 mg/ml of each) were introduced into a cleaned adsorption tube filled with Tenax TA (mesh35/60) and analyzed (desorption 5 min; 280 C.).

[0332] Flexible FoamFoaming Examples

Example 2

Production of Flexible Polyurethane Foams (Flexible Slabstock Foam)

[0333] For the performance testing of the inventive nitrogen compounds, the foam formulation specified in Table 9 was used.

TABLE-US-00022 TABLE 9 Formulation 2 for flexible slabstock foam applications Formulation 2 Parts by mass (pphp) Polyol 1 .sup.1) 100 parts Water 3.00 parts Tin catalyst.sup.2) 0.20 parts Amine 0.20 parts TEGOSTAB BF 2370.sup.3) 0.80 parts Desmodur T 80.sup.4) 38.1 parts .sup.1) Polyol 1: glycerol-based polyether polyol having an OH number of 48 mg KOH/g. .sup.2)KOSMOS 29, available from Evonik Industries: tin(II) salt of 2-ethylhexanoic acid. .sup.3)Polyether-modified polysiloxane. .sup.4)Tolylene diisocyanate T 80 (80% 2,4 isomer, 20% 2,6 isomer) from Bayer, 3 mPa .Math. s, 48% NCO, functionality 2.

[0334] In the foaming operation, 500 g of polyol were used; the other formulation constituents were adjusted correspondingly. In this context, for example, 1.00 part of a component meant 1.00 g of a substance per 100 g of polyol.

[0335] The foams were produced by manual mixing. The formulations as specified in Table 9 were used with various nitrogen-containing catalysts (amines). For this purpose, polyol, conventional or inventive nitrogen-containing catalyst (amine), tin catalyst, water and foam stabilizer were weighed into a cup and mixed at 1000 rpm for 60 seconds. After the isocyanate (TDI) had been added, the reaction mixture was stirred at 2500 rpm for 7 s and transferred immediately into a paper-lined box (base area 27 cm27 cm and height 27 cm). To assess the catalytic properties, the following characteristic parameters were determined: cream time, rise time, rise height, blow-off intensity and settling of the foam after the end of the rise phase (=fall-back).

[0336] Defined foam pieces were cut out of the resulting foam blocks and were analyzed further. The following physical properties were determined using the specimens: density, porosity (=air permeability) and indentation hardness CLD (40%).

[0337] The results of the assessment of the catalytic properties of the inventive nitrogen compounds of the formulae (II), (III), (IV), (V) and (VI) and the physical properties of the resulting flexible slabstock foams are compiled in Table 10. Comparative catalysts used according to the prior art were triethylenediamine, 33% by weight solution in dipropylene glycol (TEGOAMIN 33, available from Evonik Industries), N,N-dimethylethanolamine (TEGOAMIN DMEA, available from Evonik Industries), 1,1-{[3-(dimethylamino)propyl]imino}bis-2-propanol (TEGOAMIN ZE 1, available from Evonik Industries), bis(2-dimethylaminoethyl ether), 70% by weight solution in dipropylene glycol (TEGOAMIN BDE, available from Evonik Industries) and N,N,N-trimethyl-N-(2-hydroxyethyl)bis(2-aminoethyl) ether (Jeffcat ZF-10, available from Huntsman). 0.20 pphp (=parts by weight based on 100 parts by weight of polyol) of amine was used in each case.

TABLE-US-00023 TABLE 10 Results of the foaming operations on formulation 2 (Table 9) Rise Fall- CLD time back Height Density Porosity 40% Amine [s] [cm] [cm] [kg/m.sup.3] [mm].sup.1) [kPa] TEGOAMIN 33 118 0.1 28.7 31.8 24 4.4 TEGOAMIN ZE 1 143 0.2 28.2 31.9 24 4.3 TEGOAMIN DMEA 140 0.1 28.0 31.2 14 3.7 TEGOAMIN BDE 91 0.8 28.8 30.8 8 3.3 Jeffcat ZF-10 108 0.7 28.9 30.7 9 3.4 FORMULA (IIa) 124 0.1 28.5 31.5 22 4.1 FORMULA (IIb) 127 0.2 28.6 31.3 23 4.0 FORMULA (IIc) 131 0.1 28.4 31.0 27 3.9 FORMULA (IIIa) 140 0.2 28.4 31.7 23 3.9 FORMULA (IIIb) 140 0.1 28.7 31.5 21 4.0 FORMULA (IVa) 138 0.2 28.5 31.2 28 4.3 FORMULA (Va) 143 0.1 27.6 31.3 26 3.9 FORMULA (VIa) 118 0.5 28.8 30.9 12 3.6 .sup.1) = (dynamic pressure in mm water column).

[0338] As can be inferred from Table 10, the inventive nitrogen compounds of the formulae (II), (III), (IV), (V) and (VI) exhibit moderate to good catalytic activity in a flexible foam. In terms of their catalytic profile and their selectivity, all the compounds of the formulae (II), (III), (IV) and (V) examined can be classified as slightly gel-selective catalysts and, in this regard, are all within a range similar to TEGOAMIN ZE 1 or TEGOAMIN DMEA. The compounds of the formulae (IIa), (IIb), (IIc) and (VIa) are actually within the range of TEGOAMIN 33 in terms of their rise profile. The compound of the formula (VIa) in particular has excellent catalytic activity, but the comparatively large fall-back and the somewhat lower CLD value are an indication that structure (VIa) is a more blowing-selective catalyst than TEGOAMIN 33.

Example 3

Emissions from Flexible Slabstock Polyurethane Foams

[0339] In order to study the influence of the inventive nitrogen compounds on foam emissions, the foam formulation specified in Table 11 containing a low-emission polyol and a low-emission tin catalyst was used for the performance testing of flexible slabstock foams.

TABLE-US-00024 TABLE 11 Formulation 3, foam emissions in flexible slabstock foam applications Formulation 3 Parts by mass (pphp) Polyol 1 .sup.1) 100 parts Water 3.00 parts Tin catalyst.sup.2) 0.60 parts Amine 0.15 parts TEGOSTAB BF 2370.sup.3) 0.80 parts Desmodur T 80.sup.4) 41.6 parts .sup.1) Polyol 1: low-emission glycerol-based polyether polyol having an OH number of 56 mg KOH/g. .sup.2)KOSMOS EF, available from Evonik Industries: tin(II) salt of ricinoleic acid. .sup.3)Polyether-modified polysiloxane. .sup.4)Tolylene diisocyanate T 80 (80% 2,4 isomer, 20% 2,6 isomer) from Bayer, 3 mPa .Math. s, 48% NCO, functionality 2.

[0340] In the foaming operation, 500 g of polyol were used; the other formulation constituents were adjusted correspondingly. In this context, for example, 1.00 part of a component meant 1.00 g of a substance per 100 g of polyol.

[0341] The foams were produced by manual mixing. The formulations as specified in Table 11 were used with various nitrogen-containing catalysts (amines). For this purpose, low-emission polyol, conventional or inventive nitrogen-containing catalyst (amine), low-emission tin catalyst, water and foam stabilizer were weighed into a cup and mixed at 1000 rpm for 60 seconds. After the isocyanate (TDI) had been added, the reaction mixture was stirred at 2500 rpm for 7 s and transferred immediately into a paper-lined box (base area 27 cm27 cm and height 27 cm) and the resulting foam, after blow-off, was sealed airtight with polyethylene film. After a curing phase of 24 hours, a defined foam cube (7 cm7 cm7 cm) was cut out of the resulting foam block, which was fully encased with aluminum foil and additionally sealed with polyethylene film.

[0342] The emission characteristics of the above-described foams were subsequently examined at room temperature by the test chamber test based on the DIN method DIN EN ISO 16000-9:2008-04 as described above. The results are given in Table 12.

TABLE-US-00025 TABLE 12 Emissions from the flexible slabstock foams according to formulation 3 (Table 11) Content of volatile organic compounds by the test chamber test (TCT) TCT.sub.tot .sup.1) TCT.sub.amine .sup.1) Amine [g/m.sup.3] [g/m.sup.3] TEGOAMIN 33 92 64 TEGOAMIN ZE 1 <20 <10 TEGOAMIN DMEA 28 <10 TEGOAMIN BDE 340 293 Jeffcat ZF-10 <20 <10 FORMULA (IIa) <20 <10 FORMULA (IIb) <20 <10 FORMULA (IIc) <20 <10 FORMULA (IIIa) <20 <10 FORMULA (IIIb) <20 <10 FORMULA (IVa) <20 <10 FORMULA (Va) <20 <10 FORMULA (VIa) <20 <10 .sup.1) TCT.sub.tot = total emissions; TCT.sub.amine = amine emissions of all volatile organic compounds in the test chamber test.

[0343] Table 12 shows that it is possible to distinctly reduce amine emissions in the test chamber test when using the inventive nitrogen compounds of the formulae (II), (III), (IV), (V) and (VI) compared to conventional catalysts such as TEGOAMIN 33, which may be a prerequisite in the application for production of flexible slabstock foams.

Example 4

Production of HR Foams (Block/Molded)

[0344] For the performance testing of the inventive nitrogen compounds, the foam formulation specified in Table 13 was used.

TABLE-US-00026 TABLE 13 Formulation 4 for cold-cure flexible foam applications (HR block/molded) Formulation 4 Parts by mass (pphp) Polyol 1 .sup.1) 70.0 parts Polyol 2.sup.2) 30.0 parts Water 3.70 parts Glycerol 0.50 parts Diethanolamine (DEOA) 1.00 parts Amine 0.25 parts TEGOSTAB B 8716 LF2.sup.3) 1.00 parts Desmodur T 80.sup.4) 44.0 parts .sup.1) Polyol 1: sorbitol/glycerol-based polyether polyol having an OH number of 32 mg KOH/g. .sup.2)Polyol 2: glycerol-based polyether polyol, containing 43% solids (SAN), having an OH number of 20 mg KOH/g. .sup.3)Formulation of organomodified polysiloxanes. .sup.4)Tolylene diisocyanate T 80 (80% 2,4 isomer, 20% 2,6 isomer) from Bayer, 3 mPa .Math. s, 48% NCO, functionality 2.

[0345] The same foaming methods were employed here as for the conventional flexible polyurethane foam in Examples 2 and 3.

[0346] In the foaming operation, 500 g of polyol were used; the other formulation constituents were adjusted correspondingly. In this context, for example, 1.00 part of a component means 1.00 g of a substance per 100 g of polyol.

[0347] For the foaming operation, polyol, water, amine and silicone stabilizer were mixed well with stirring. After the isocyanate had been added, the mixture was stirred with a stirrer at 3000 rpm for 4 s and the mixture was cast in a paper-lined wooden box (base area 27 cm27 cm and height 27 cm). The result was a foam, which was subjected to the performance tests described hereinafter.

[0348] The results of the assessment of the catalytic properties of the inventive nitrogen compounds of the formulae (III), (IV) and (V) and the physical properties of the resulting foams are compiled in Table 14. Comparative catalysts used according to the prior art were triethylenediamine, 33% by weight solution in dipropylene glycol (TEGOAMIN 33, available from Evonik Industries), 1,1-{[3-(dimethylamino)propyl]imino}bis-2-propanol (TEGOAMIN ZE 1, available from Evonik Industries), N,N-dimethylethanolamine (TEGOAMIN DMEA, available from Evonik Industries). 0.25 pphp (=parts by weight based on 100 parts by weight of polyol) of amine was used in each case.

TABLE-US-00027 TABLE 14 Results of the foaming operations on formulation 4 (Table 13) Gel Rise Fall- Cell time time Height back count.sup.1) Amine [s] [s] [cm] [cm] [cm.sup.1] TEGOAMIN 33 85 151 31.2 0.4 10.5 TEGOAMIN ZE 1 131 215 30.4 0.1 9.0 TEGOAMIN DMEA 148 265 26.6 0.0 collapse FORMULA (IIa) 137 235 29.4 0.5 9.0 FORMULA (IIIa) 141 243 29.0 0.0 9.0 FORMULA (IIIb) 155 273 26.5 0.0 9.0 FORMULA (IVa) 153 263 26.8 0.1 9.0 FORMULA (Va) 151 275 27.1 0.1 9.0 FORMULA (VIa) 78 157 32.1 0.6 10.0 .sup.1)Cell count = number of cells per cm [cm.sup.1].

[0349] As can be inferred from Table 14, the inventive nitrogen compounds of the formulae (II), (III), (IV), (V) and (VI) in this cold-cure foam formulation show a moderate catalytic activity and selectivity, in some cases comparable to TEGOAMIN ZE 1 and TEGOAMIN DMEA. The compound of the formula (VIa) again has a high activity in the range of TEGOAMIN 33, but slight selectivity for the blowing reaction can again be observed.