CATALYST FOR THE PREPARATION OF POLYURETHANES

Abstract

Novel thermolatent bases and their use as catalysts for the preparation of polyurethanes or epoxy resins are disclosed herein. A process for the preparation of polyurethanes or epoxy resins in the presence of the catalyst is also disclosed.

Claims

1. Process for preparing a polyurethane comprising reacting at least one polyisocyanate with a polyol composition comprising at least one polyol in the presence of a catalyst composition comprising at least one compound (C) selected from the group consisting of compounds of the general formula (Ia) or (Ib) ##STR00078## wherein n is 0 or 1 when X is a carbon atom, n is 2 when X is a sulfur atom, n is 0 or 1, m is an integer from 1 to 6, R is selected from monovalent, or divalent, or trivalent or polyvalent residues, wherein when R is monovalent, R is H, OH, substituted or unsubstituted, linear or branched C.sub.1-C.sub.18 alkyl, C.sub.5-C.sub.7 cycloalkyl which can be substituted by OH, OR.sup.1 or NR.sup.2R.sup.3, and which may be interrupted by one or more O, S or NR.sup.4; when R is divalent, R is substituted or unsubstituted, linear or branched C.sub.3-C.sub.18 alkylene, C.sub.5-C.sub.7 cycloalkylene which can be substituted by OH, OR.sup.1 or NR.sup.2R.sup.3, and which may be interrupted by one or more O, S or NR.sup.4; when R is trivalent, R is selected from N(CH.sub.2CH.sub.2*).sub.3, ##STR00079## R is linear or branched C.sub.1-C.sub.5 alkyl substituted by NHR.sup.2, B is a nitrogen containing organic base, L is a C.sub.1-C.sub.8 substituted or unsubstituted alkylene chain, or a substituted or unsubstituted C.sub.6 cycloalkylene chain, or substituted or unsubstituted C.sub.9-C.sub.11 polycyclic chain, or a substituted or unsubstituted double bond, which can be interrupted by O, S, NR.sup.4, or a substituted or unsubstituted C.sub.3 to C.sub.4 alkenylene chain, or a substituted or unsubstituted benzene ring, or substituted or unsubstituted naphthalene ring, R.sup.1 is H, C.sub.1-C.sub.18 alkyl, R.sup.2 and R.sup.3, independently are hydrogen, unsubstituted or substituted C.sub.1-C.sub.18 alkyl or phenyl; or R.sup.2 and R.sup.3 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further heteroatom, R.sup.4 is H, unsubstituted or substituted C.sub.1-C.sub.18 alkyl, the ratio between A.sub.a and B.sub.a or between A.sub.b and B.sub.b ranges from 0.5:1 to 10:1.

2. The process according to claim 1, wherein the compound (C) is selected from the group consisting of compounds of the general formula (Ia) or (Ib) ##STR00080## wherein n is 1 when X is a carbon atom, n is 2 when X is a sulfur atom, n is 0 or 1, m is 1 or 2, R is a monovalent, divalent or trivalent rest, when R is monovalent, R is H, OH, linear or branched C.sub.1-C.sub.18 alkyl, C.sub.5-C.sub.7 cycloalkyl which may be interrupted by one or more O, S or NR.sup.4, when R is divalent, R is linear or branched C.sub.3-C.sub.18 alkylene, or C.sub.5-C.sub.7 cycloalkylene which may be interrupted by one or more O, S or NR.sup.4, when R is trivalent, R can be for example the following trivalent residues: N(CH.sub.2CH.sub.2*).sub.3, ##STR00081## R is linear or branched alkyl substituted by NHR.sup.2, B is substituted or unsubstituted 1,8-Diazabicyclo[5.4.0]undec-7-en (DBU), 1,5-Diazabicyclo[4.3.0]non-5-ene (DBN), Triazabycyclodecene (TBD), 1,4-Diazabicyclo[2.2.2]octan (DABCO), 1,1,3,3-tetramethylguanidine (TMG), or substituted or unsubstituted tertiary aliphatic amines, L is a C.sub.1 to C.sub.8 substituted or unsubstituted alkylene chain, or a substituted or unsubstituted double bond, or a substituted or unsubstituted C.sub.3 to C.sub.4 alkenylene chain, or has the formula: ##STR00082## when m is 1 or has the formula: ##STR00083## when m is 2 R.sup.5, R.sup.6, R.sup.7, R.sup.8 independently from each other are hydrogen, unsubstituted or substituted C.sub.1-C.sub.28alkyl, C.sub.2-C.sub.28alkenyl, C.sub.7-C.sub.9aralkyl, C.sub.3-C.sub.20 heteroalkyl, C.sub.5-C.sub.16heteroaralkyl, phenyl or naphthyl, OR.sup.1, NR.sup.2R.sup.3, or halogen, or R.sup.5 and R.sup.6, R.sup.6 and R.sup.7 or R.sup.7 and R.sup.8 are linked together to form 1, 2, 3 or 4 carbocyclic or heterocyclic rings, which may be uninterrupted or interrupted by one or more O, S or NR.sup.4; R.sup.1 is H, C.sub.1-C.sub.18 alkyl, R.sup.2, R.sup.3, independently are hydrogen, unsubstituted or substituted C.sub.1-C.sub.18alkyl or phenyl, or R.sup.2 and R.sup.3 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further heteroatom, R.sup.4 is H, unsubstituted or substituted C.sub.1-C.sub.18alkyl, the ratio between A.sub.a and B.sub.a or between A.sub.b and B.sub.b ranges from 1:1 to 4:1.

3. The process according to claim 1, wherein the compound (C) is selected from the group consisting of compounds of the general formula (Ia) or (Ib) ##STR00084## wherein n is 1 when X is a carbon atom, n is 2 when X is a sulfur atom, n is 0 or 1, R is monovalent, R is H, linear or branched alkyl, cycloalkyl, R is linear or branched alkyl substituted by NH.sub.2 or NH(alkyl), B is DBU, DBN, TBD, DABCO, TMG, tertiary aliphatic amines, L is a C.sub.1 to C.sub.8 substituted or unsubstituted alkylene chain, or a substituted or unsubstituted double bond, or a substituted or unsubstituted C.sub.3 to C.sub.4 alkenylene chain, or has the formula: ##STR00085## R.sup.5, R.sup.6, R.sup.7, R.sup.8 independently from each other are hydrogen, unsubstituted or substituted C.sub.1-C.sub.28alkyl, C.sub.2-C.sub.28alkenyl, C.sub.7-C.sub.9aralkyl, C.sub.3-C.sub.20heteroalkyl, C.sub.5-C.sub.16heteroaralkyl, phenyl or naphthyl, OR.sup.1, NR.sup.2R.sup.3, or halogen, or R.sup.5 and R.sup.6, R.sup.6 and R.sup.7 or R.sup.7 and R.sup.8 are linked together to form 1, 2, 3 or 4 carbocyclic or heterocyclic rings, which may be uninterrupted or interrupted by one or more O, S or NR.sup.4; R.sup.1 is H, C.sub.1-C.sub.18alkyl, R.sup.2, R.sup.3, independently are hydrogen, unsubstituted or substituted C.sub.1-C.sub.18alkyl or phenyl; or R.sup.2 and R.sup.3 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further heteroatom, R.sup.4 is H, unsubstituted or substituted C.sub.1-C.sub.18alkyl, the ratio between A.sub.a and B.sub.a or between A.sub.b and B.sub.b ranges from 1:1 to 4:1.

4. The process according to claim 1, wherein the compound (C) is selected from the group consisting of compounds of the general formula (Ia) or (Ib) ##STR00086## wherein R is monovalent, R is H, linear or branched alkyl, cycloalkyl, R is linear or branched alkyl substituted by NH.sub.2 or NH(alkyl), B is DBU, DBN, TBD, DABCO, TMG, tertiary aliphatic amines, L is a C.sub.1 to C.sub.8 substituted or unsubstituted alkylene chain, or has the formula: ##STR00087## R.sup.5, R.sup.6, R.sup.7, R.sup.8 independently from each other are hydrogen, unsubstituted or substituted C.sub.1-C.sub.28alkyl, C.sub.2-C.sub.28alkenyl, C.sub.7-C.sub.9aralkyl, C.sub.3-C.sub.20heteroalkyl, C.sub.5-C.sub.16heteroaralkyl, phenyl or naphthyl, OR.sup.1, NR.sup.2R.sup.3, or halogen, or R.sup.5 and R.sup.6, R.sup.6 and R.sup.7 or R.sup.7 and R.sup.8 are linked together to form 1, 2, 3 or 4 carbocyclic or heterocyclic rings, which may be uninterrupted or interrupted by one or more O, S or NR.sup.4; R.sup.1 is H, C.sub.1-C.sub.18 alkyl, R.sup.2, R.sup.3, independently are hydrogen, unsubstituted or substituted C.sub.1-C.sub.18alkyl or phenyl; or R.sup.2 and R.sup.3 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further heteroatom, R.sup.4 is H, unsubstituted or substituted C.sub.1-C.sub.18alkyl, the ratio between A.sub.a and B.sub.a or between A.sub.b and B.sub.b ranges from 1:1 to 4:1.

5. The process according to claim 1, wherein the compound (C) is selected from the group consisting of compounds of the general formula (Ia) or (Ib) ##STR00088## wherein R is monovalent, R is H, linear or branched alkyl, cycloalkyl, R is linear or branched alkyl substituted by NH.sub.2 or NH(alkyl), B is DBU, L is a C.sub.1 to C.sub.8 substituted or unsubstituted alkylene chain, or has the formula: ##STR00089## R.sup.5, R.sup.6, R.sup.7, R.sup.8 independently from each other are hydrogen, unsubstituted or substituted C.sub.1-C.sub.28alkyl, C.sub.2-C.sub.28alkenyl, C.sub.1-C.sub.9aralkyl, C.sub.3-C.sub.20heteroalkyl, C.sub.5-C.sub.16heteroaralkyl, phenyl or naphthyl, OR.sup.1, NR.sup.2R.sup.3, or halogen, or R.sup.5 and R.sup.6, R.sup.6 and R.sup.7 or R.sup.7 and R.sup.8 are linked together to form 1, 2, 3 or 4 carbocyclic or heterocyclic rings, which may be uninterrupted or interrupted by one or more O, S or NR.sup.4; R.sup.1 is H, C.sub.1-C.sub.16alkyl, R.sup.2, R.sup.3, independently are hydrogen, unsubstituted or substituted C.sub.1-C.sub.18alkyl or phenyl; or R.sup.2 and R.sup.3 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further heteroatom, R.sup.4 is H, unsubstituted or substituted C.sub.1-C.sub.18alkyl, the ratio between A.sub.a and B.sub.a or between A.sub.b and B.sub.b ranges from 1:1 to 4:1.

6. The process according to claim 1, wherein the catalyst composition comprises at least one further catalyst.

7. The process according to claim 1, wherein the at least one polyisocyanate is selected from the group consisting of MDI, polymeric MDI, and TDI, and derivatives thereof or prepolymers of these polyisocyanates.

8. A catalyst for preparation of a polyurethane or epoxy resin, the catalyst comprising a compound (C) selected from the group consisting of compounds of the general formula (Ia) or (Ib) ##STR00090## wherein n is 0 or 1 when X is a carbon atom, n is 2 when X is a sulfur atom, n is 0 or 1, m is an integer from 1 to 6, R is selected from monovalent, or divalent, or trivalent or polyvalent residues, wherein when R is monovalent, R is H, OH, substituted or unsubstituted, linear or branched C.sub.1-C.sub.18 alkyl, C.sub.5-C.sub.7 cycloalkyl which can be substituted by OH, OR.sup.1 or NR.sup.2R.sup.3, and which may be interrupted by one or more O, S or NR.sup.4; when R is divalent, R is substituted or unsubstituted, linear or branched C.sub.3-C.sub.18 alkylene, C.sub.5-C.sub.7 cycloalkylene which can be substituted by OH, OR.sup.1 or NR.sup.2R.sup.3, and which may be interrupted by one or more O, S or NR.sup.4; when R is trivalent, R is selected from N(CH.sub.2CH.sub.2*).sub.3, ##STR00091## R is linear or branched C.sub.1-C.sub.5 alkyl substituted by NHR.sup.2, B is a nitrogen containing organic base, L is a C.sub.1-C.sub.8 substituted or unsubstituted alkylene chain, or a substituted or unsubstituted C.sub.6 cycloalkylene chain, or substituted or unsubstituted C.sub.9-C.sub.11 polycyclic chain, or a substituted or unsubstituted double bond, which can be interrupted by O, S, NR.sup.4, or a substituted or unsubstituted C.sub.3 to C.sub.4 alkenylene chain, or a substituted or unsubstituted benzene ring, or substituted or unsubstituted naphthalene ring, R.sup.1 is H, C.sub.1-C.sub.18 alkyl, R.sup.2 and R.sup.3, independently are hydrogen, unsubstituted or substituted C.sub.1-C.sub.18 alkyl or phenyl; or R.sup.2 and R.sup.3 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further heteroatom, R.sup.4 is H, unsubstituted or substituted C.sub.1-C.sub.18 alkyl, the ratio between A.sub.a and B.sub.a or between A.sub.b and B.sub.b ranges from 0.5:1 to 10:1.

Description

EXAMPLES

I. Preparation of Catalysts

[0316] Non limiting examples of the inventive compounds are given below. The respective structures obtained for compounds (1) to (30) are summarized in Table 1.

[0317] The starting acidic partners are commercially available or were synthesized by state of the art methods, for example for some of them by reaction between an amine and an anhydride, as exemplified in table 2.

1. Example 1: 2-(2-hydroxyethylcarbamoyl)benzoate;2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium

[0318] 307.5 g (1.47 mol) of 2-(2-hydroxyethylcarbamoyl)benzoic acid were mixed with 396.7 g ethyleneglycol to give a thick suspension to which were added 223.8 g (1.47 mol) DBU over 48 min while the temperature was maintained between 14 C. and 16 C. 134.6 g additional ethyleneglycol were then added to obtain a thin suspension. After stirring for 3 hours at room temperature, a colorless solution was obtained. .sup.13C-NMR (CDCl.sub.3, 400 MHz, ppm): 173.5, 171.5, 166, 137, 136, 129.5, 129, 128, 127, 63 (ethyleneglycol), 61, 54, 48, 42, 38, 32, 29, 26, 24, 19.

2. Example 2: 2-(2-hydroxyethylcarbamoyl)benzoate; 1-ethyl-4-methyl-piperazin-4-ium

[0319] 5.6 g (50 mmol) DABCO were mixed with 48.2 g of ethyleneglycol to give a white suspension. 10.5 g (50 mmol) of 2-(2-hydroxyethylcarbamoyl)benzoic acid were added under slight cooling to obtain a suspension. The mixture was stirred one hour at room temperature to give a yellowish solution. .sup.13C-NMR (D.sub.2O, 400 MHz, ppm): 175.5, 173, 137.5, 134.5, 130.5, 129.5, 129, 128, 62.5 (ethyleneglycol), 60, 44, 42.

3. Example 3: 2-(tert-butylcarbamoyl)benzoate; 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium

[0320] 11.1 g (50 mmol) of 2-(tert-butylcarbamoyl)benzoic acid were mixed with 18 g ethyleneglycol, which thick white suspension was cooled down to 15 C. at which temperature it could not be stirred anymore. 37.3 g ethyleneglycol were added. 7.6 g (50 mmol) DBU were added dropwise, followed by 1 g ethyleneglycol. The mixture was stirred for four hours at room temperature to give a clear solution. .sup.13C-NMR (CDCl.sub.3, 400 MHz, ppm): 175, 170, 166, 138.5, 135, 129.5, 128, 127.5, 63 (ethyleneglycol), 54, 51.5, 48.5, 38, 32.5, 29.5, 28.5, 26.5, 24, 19.

4. Example 4: 2-(tert-butylcarbamoyl)benzoate; 1-ethyl-4-methyl-piperazin-4-ium

[0321] 5.6 g (50 mmol) DABCO were mixed with 16.7 g of ethyleneglycol to give a white suspension. 11 g (50 mmol) of 2-(tert-butylcarbamoyl)benzoic acid were added in three portions under slight cooling to obtain a thin white suspension. The mixture was stirred over night at room temperature to give a colorless solution. .sup.13C-NMR (CDCl.sub.3, 400 MHz, ppm): 174.5, 170.5, 137, 136.5, 129.5, 129, 128, 127, 63.5 (ethyleneglycol), 51.5, 44.5, 28.5.

5. Example 5: 2-(isopropylcarbamoyl)benzoate; 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium

[0322] 10.4 g (50 mmol) of 2-(isopropylcarbamoyl)benzoic acid were mixed with 16 g ethyleneglycol, which white suspension was cooled down to 15 C. 7.6 g (50 mmol) DBU were added dropwise, followed by 2 g ethyleneglycol. The mixture was stirred for three hours to give a clear solution. .sup.13C-NMR (DMSO, 400 MHz, ppm): 173.5, 167.5, 165.5, 142, 132.5, 130, 129, 128.5, 127, 63 (ethyleneglycol), 54, 48, 41, 38, 32, 28.5, 26.5, 23.5, 22.5, 19.5.

6. Example 6: 2-(isopropylcarbamoyl)benzoate; 1-ethyl-4-methyl-piperazin-4-ium

[0323] 5.6 g (50 mmol) DABCO were mixed with 16.0 g of ethyleneglycol. 10.4 g (50 mmol) of 2-(isopropylcarbamoyl)benzoic acid were added in three portions under slight cooling to obtain a thin white suspension. The mixture was stirred over night at room temperature to give a colorless solution. .sup.13C-NMR (CDCl.sub.3, 400 MHz, ppm): 174.5, 170, 137.5, 135.5, 129.5, 129, 128, 127.5, 63.5 (ethyleneglycol), 44.5, 42, 22.

7. Example 7: 2-(propylcarbamoyl)benzoate; 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium

[0324] 10.4 g (50 mmol) of 2-(propylcarbamoyl)benzoic acid were mixed with 16 g ethyleneglycol, which white suspension was cooled down to 15 C. 7.6 g (50 mmol) DBU were added dropwise, followed by 2 g ethyleneglycol. The mixture was stirred for two hours to give a clear solution. .sup.13C-NMR (DMSO, 400 MHz, ppm): 173.5, 168.5, 166, 142, 133, 130, 129, 128.5, 127, 63 (ethyleneglycol), 53.5, 48, 41.5, 38, 32, 28.5, 26.5, 24, 22.5, 19.5, 12.

8. Example 8: 2-(propylcarbamoyl)benzoate; 1-ethyl-4-methyl-piperazin-4-ium

[0325] 5.6 g (50 mmol) DABCO were mixed with 16.0 g of ethyleneglycol. 10.4 g (50 mmol) of 2-(propylcarbamoyl)benzoic acid were added in four portions under slight cooling to obtain a thin white suspension. The mixture was stirred over night at room temperature to give a colorless solution. .sup.13C-NMR (CDCl.sub.3, 400 MHz, ppm): 174.5, 171, 138, 135.5, 129.5, 129, 128.5, 127.5, 63.5 (ethyleneglycol), 44.5, 41.5, 22.5, 11.5.

9. Example 9: 4-(tert-butylamino)-4-oxo-butanoate; 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium

[0326] 8.7 g (50 mmol) of 4-(tert-butylamino)-4-oxo-butanoic acid were mixed with 14.3 g of ethyleneglycol to give a which suspension to which were added 7.6 g (50 mmol) DBU maintaining the temperature between 14 and 18 C. to give a thin white suspension. 2 g additional ethyleneglycol were then added to obtain a thin suspension. After stirring for 2 hours at room temperature, a colorless solution was obtained. .sup.13C-NMR (DMSO, 400 MHz, ppm): 177, 173, 165, 63 (ethyleneglycol), 53.5, 50, 48, 38, 34.5, 34, 32, 29, 28, 26.5, 24, 19.5.

10. Example 10: 4-(tert-butylamino)-4-oxo-butanoate;1-ethyl-4-methyl-piperazin-4-ium

[0327] 5.6 g (50 mmol) DABCO were mixed with 35 g ethyleneglycol to give a white suspension. 6 g (50 mmol) of 4-(tert-butylamino)-4-oxo-butanoic acid were added in three portions under slight cooling to obtain a thin white suspension. 7 g ethyleneglycol were added and the mixture was stirred one hour at room temperature to give a colorless solution. .sup.13C-NMR (DMSO, 400 MHz, ppm): 176, 172, 63 (ethyleneglycol), 50, 46, 32, 31.5, 29.

11. Example 11: 4-(isopropylamino)-4-oxo-butanoate; 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium

[0328] 8.0 g (50 mmol) of 4-(isopropylamino)-4-oxo-butanoic acid were mixed with 13.6 g of ethyleneglycol to give a white suspension to which were added 7.6 g (50 mmol) DBU maintaining the temperature between 14 and 19 C. to give a thin white suspension. 2 g additional ethyleneglycol were then added to obtain a thin suspension. After stirring for 2 hours at room temperature, a colorless solution was obtained. .sup.13C-NMR (DMSO, 400 MHz, ppm): 177, 172.5, 165.5, 63 (ethyleneglycol), 53.5, 50, 48.5, 38, 34, 33.5, 32, 29, 26.5, 24, 23, 19.5.

12. Example 12: 4-(isopropylamino)-4-oxo-butanoate;1-ethyl-4-methyl-piperazin-4-ium

[0329] 4.26 g (38 mmol) DABCO were mixed with 8 g ethyleneglycol to give a colorless solution. 6 g (38 mmol) of 4-(isopropylamino)-4-oxo-butanoic acid were added in three portions under slight cooling to obtain a white suspension. 2.3 g ethyleneglycol were added and the mixture was stirred one hour at room temperature to give a colorless solution. .sup.13C-NMR (DMSO, 400 MHz, ppm): 175.5, 162, 63 (ethyleneglycol), 46, 40.5, 31.5, 31, 23.

13. Example 13: 2-(2-hydroxyethylcarbamoyl)benzoate; 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidin-1-ium

[0330] 5.0 g (36 mmol) TBD were mixed with 37.6 g ethyleneglycol to give a solution. 7.5 g (36 mmol) of 2-(2-hydroxyethylcarbamoyl)benzoic acid were added in four portions at a temperature maintained between 14 and 19 C. Stirring was continued for 3 hours to give a colorless solution. .sup.13C-NMR (MeOD, 400 MHz, ppm): 174.5, 172, 151, 138.5, 135.5, 129, 128.5, 128, 127, 63 (ethyleneglycol), 60, 46.5, 42.5, 38, 20.5.

14. Example 14: 2-(hydroxycarbamoyl)benzoate;2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium

[0331] 4.5 g (25 mmol) of 2-(hydroxycarbamoyl)benzoic acid were mixed with 6.34 g of ethyleneglycol to give a yellow suspension to which were added 3.8 g (25 mmol) DBU maintaining the temperature between 14 and 18 C. to give a thin orange suspension. 2 g additional ethyleneglycol were then added to obtain a thin suspension. After stirring for 2 hours at room temperature, the thin suspension was filtered to give a clear orange solution. .sup.13C-NMR (DMSO, 400 MHz, ppm): 177.5, 166, 165, 140.5, 132, 129.5, 129, 128, 63 (ethyleneglycol), 53.5, 48.5, 33, 29, 28, 24.5, 20.

15. Example 15: 2-(hydroxycarbamoyl)benzoate;1-ethyl-4-methyl-piperazin-4-ium

[0332] 5.1 g (28 mmol) of 2-(hydroxycarbamoyl)benzoic acid were mixed with 8.2 g of ethyleneglycol to give a suspension to which were added 3.1 g (28 mmol) DABCO maintaining the temperature below 22 C. to give a yellow suspension. 8.2 g additional ethyleneglycol were then added to obtain a thin suspension. After stirring for 2 hours at room temperature, the thin suspension was filtered to give a clear yellow solution.

16. Example 16: 4-aminobutanoate; 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium

[0333] 5.2 g (50 mmol) of 4-aminobutanoic acid were mixed with 10.8 g of ethyleneglycol to give a white suspension which was cooled down to 13 C. 7.6 g (50 mmol) DBU were added dropwise and 2 g additional ethyleneglycol were then added to give a suspension. 25.5 g additional ethyleneglycol were added and stirring was continued over night to give a colorless solution. .sup.13C-NMR (DMSO, 400 MHz, ppm): 178.5, 165, 63.5 (ethyleneglycol), 53.5, 0.48, 42, 38.5, 36, 32.5, 30, 29, 26.5, 24, 20.

17. Example 17: 4-aminobutanoate;1-ethyl-4-methyl-piperazin-4-ium

[0334] 4.1 g (40 mmol) of 4-aminobutanoic acid were mixed with 6.6 g of ethyleneglycol to give a white suspension to which were added 4.5 g (40 mmol) DABCO maintaining the temperature below 15 C. 70 g additional ethyleneglycol were then added to obtain a clear solution. .sup.13C-NMR (D2O, 400 MHz, ppm): 181.5, 62.5 (ethyleneglycol), 45, 40, 34.5, 24.

18. Example 18: (Z)-4-(tert-butylamino)-2,3-dimethyl-4-oxo-but-2-enoate; 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium; 2-methylpropan-2-amine

[0335] DBU was neutralized by the t-butylammonium salt of the acid.

[0336] 6.8 g (25 mmol) of (Z)-4-(tert-butylamino)-2,3-dimethyl-4-oxo-but-2-enoate; tert-butylammonium were mixed with 8.6 g of ethyleneglycol to give a white suspension which was cooled down to 17 C. 3.8 g (25 mmol) DBU were added dropwise and 2 g additional ethyleneglycol were then added. Stirring was continued for two hours to give a colorless solution. .sup.13C-NMR (DMSO, 400 MHz, ppm): 176, 170, 165.5, 140.5, 123, 63.5 (ethyleneglycol), 53.5, 50, 48.5, 47.5, 38.5, 32.5, 29, 28.5, 26.5, 24, 19.5, 18.5, 15.

19. Example 19: (Z)-4-(tert-butylamino)-2,3-dimethyl-4-oxo-but-2-enoate; 1-ethyl-4-methyl-piperazin-4-ium; 2-methylpropan-2-amine

[0337] DABCO was neutralized by the t-butylammonium salt of the acid.

[0338] 6.1 g (22 mmol) of (Z)-4-(tert-butylamino)-2,3-dimethyl-4-oxo-but-2-enoate; tert-butylammonium were mixed with 6.6 g of ethyleneglycol to give a white suspension which was cooled down to 15 C. 2.5 g (22 mmol) DABCO were added dropwise and 19.1 g additional ethyleneglycol were then added. Stirring was continued for two hours to give a colorless solution. .sup.13C-NMR (DMSO, 400 MHz, ppm): 176.5, 170, 139, 124.5, 63 (ethyleneglycol), 51, 50.5, 47, 39, 38.5, 18, 15.

20. Example 20:2-sulfamoylbenzoate; 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium

[0339] 5 g (25 mmol) of 2-sulfamoylbenzoic acid were mixed with 5.6 g of ethyleneglycol to give a white suspension which was cooled down to 13 C. 3.8 g (25 mmol) DBU were added dropwise and 19.7 g additional ethyleneglycol were then added to give a white suspension. 53 g additional ethyleneglycol were then added to give a colorless solution. .sup.13C-NMR (DMSO, 400 MHz, ppm): 171.5, 166, 141, 140.5, 132, 131, 128, 126, 63 (ethyleneglycol), 54, 48.5, 38.5, 32.5, 29.5, 26.5, 24, 19.5.

21. Example 21: 2-sulfamoylbenzoate; 1-ethyl-4-methyl-piperazin-4-ium

[0340] 6 g (30 mmol) of 2-sulfamoylbenzoic acid were mixed with 7.4 g of ethyleneglycol to give a white suspension which was cooled down to 17 C. 3.4 g (30 mmol) DABCO were added dropwise to give a white suspension. 2 g additional ethyleneglycol were then added. Stirring was continued over night to give a colorless solution. .sup.13C-NMR (DMSO, 400 MHz, ppm): 172, 140.5, 140, 132, 130, 128.5, 126, 63.5 (ethyleneglycol), 44.5.

22. Example 22: 2-(2-amino-2-methyl-propoxy)carbonylbenzoate;2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium

[0341] 5.9 g (25 mmol) of 2-(2-amino-2-methyl-propoxy)carbonylbenzoic acid were mixed with 8.6 g of ethyleneglycol to give a white suspension which was cooled down to 14 C. 3.8 g (25 mmol) DBU were added dropwise and 2 g additional ethyleneglycol were then added to give a thin white suspension. 21.1 g additional ethyleneglycol were then added and stirring was continued over night to give a colorless solution. .sup.13C-NMR (DMSO, 400 MHz, ppm): 171.5, 166, 141, 140.5, 132, 131, 128, 126, 63 (ethyleneglycol), 54, 48.5, 38.5, 32.5, 29.5, 26.5, 24, 19.5.

23. Example 23: 2-(hydroxymethyl)benzoate; 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium

[0342] 3.8 g (25 mmol) of 2-(hydroxymethyl)benzoic acid were mixed with 5.6 g of ethyleneglycol to give a white suspension which was cooled down to 13 C. 3.8 g (25 mmol) DBU were added dropwise and 2 g additional ethyleneglycol were then added to give a thin white suspension. 15.2 g additional ethyleneglycol were then added and stirring was continued for three hours to give a colorless solution. .sup.13C-NMR (DMSO, 400 MHz, ppm): 173, 165.5, 141, 139.5, 130.5, 129, 128.5, 127, 64.5, 63 (ethyleneglycol), 54, 48, 38, 32, 28.5, 26.5, 24, 19.

24. Example 24: 2-(hydroxymethyl)benzoate;1-ethyl-4-methyl-piperazin-4-ium

[0343] 4.9 g (32 mmol) of 2-(hydroxymethyl)benzoic acid were mixed with 6.5 g of ethyleneglycol to give a thick white suspension to which were added 3.6 g (32 mmol) DABCO maintaining the temperature between 15 C. and 17 C. 2 g additional ethyleneglycol. Stirring was continued for 4 hours to obtain a clear solution. .sup.13C-NMR (DMSO, 400 MHz, ppm): 172.5, 142.5, 136.5, 130.5, 130, 128, 127, 64, 63 (ethyleneglycol), 45.

25. Example 25: 4-(propylamino)-4-oxo-butanoate; 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium

[0344] 8.0 g (50 mmol) of 4-(propylamino)-4-oxo-butanoic acid were mixed with 13.6 g of ethyleneglycol to give a thick white suspension. 7.6 g (50 mmol) DBU were added dropwise maintaining the temperature between 16 and 17 C. 2 g additional ethyleneglycol were then added to give a thin suspension. Stirring was continued for three hours to give a colorless solution. .sup.13C-NMR (DMSO, 400 MHz, ppm): 177, 173, 165.5, 63.5 (ethyleneglycol), 53.5, 48.5, 40.5, 38, 34, 33.5, 32, 29, 26.5, 24, 23, 19.5, 12.

26. Example 26: 4-(propylamino)-4-oxo-butanoate;1-ethyl-4-methyl-piperazin-4-ium

[0345] 5.6 g (50 mmol) DABCO were mixed with 10 g ethyleneglycol to give a colorless solution. 7.96 g (50 mmol) of 4-(propylamino)-4-oxo-butanoic acid were added in three portions under slight cooling to obtain a white suspension. 3.6 g ethyleneglycol were added and the mixture was stirred one hour at room temperature to give a colorless solution. .sup.13C-NMR (DMSO, 400 MHz, ppm): 176, 172, 63 (ethyleneglycol), 45.5, 41, 32, 31.5, 23, 12.

27. Examples 27-30 were Synthesized Using the Same General Method by Adjusting the Ration Between the Starting Acid and the Amine Base

[0346]

TABLE-US-00001 TABLE 1 Structure of compounds (1) to (30) No. Structure 1 [00039] Molar ratio DBU:Acid 1:1 2 [00040] Molar ratio DABCO:Acid 1:1 3 [00041] Molar ratio DBU:Acid 1:1 4 [00042] Molar ratio DABCO:Acid 1:1 5 [00043] Molar ratio DBU:Acid 1:1 6 [00044] Molar ratio DABCO:Acid 1:1 7 [00045] Molar ratio DBU:Acid 1:1 8 [00046] Molar ratio DABCO:Acid 1:1 9 [00047] Molar ratio DBU:Acid 1:1 10 [00048] Molar ratio DABCO:Acid 1:1 11 [00049] Molar ratio DBU:Acid 1:1 12 [00050] Molar ratio DABCO:Acid 1:1 13 [00051] Molar ratio TBD:Acid 1:1 14 [00052] Molar ratio DBU:Acid 1:1 15 [00053] Molar ratio DABCO:Acid 1:1 16 [00054] Molar ratio DBU:Acid 1:1 17 [00055] Molar ratio DABCO:Acid 1:1 18 [00056] Molar ratio DBU:Acid 1:1 19 [00057] Molar ratio DABCO:Acid 1:1 20 [00058] Molar ratio DBU:Acid 1:1 21 [00059] Molar ratio DABCO:Acid 1:1 22 [00060] Molar ratio DBU:Acid 1:1 23 [00061] Molar ratio DBU:Acid 1:1 24 [00062] Molar ratio DABCO:Acid 1:1 25 [00063] Molar ratio DBU:Acid 1:1 26 [00064] Molar ratio DABCO:Acid 1:1 27 [00065] Molar ratio DBU:Acid 1:1.25 28 [00066] Molar ratio DBU:Acid 1:1.5 29 [00067] Molar ratio DABCO:Acid 1:1.25 30 [00068] Molar ratio DABCO:Acid 1:1.5 31 [00069] Molar ratio DABCO:Acid 1:1

TABLE-US-00002 TABLE 2 starting acidic partners Number of the corre- Acidic partner sponding salt(s) reference [00070] 3,4 Kaicharla, Trinadh; Thangaraj, Manikandan; Biju, Akkattu T. Organic Letters 2014, 16, 1728- 1731. 2-(tert-butylcarbamoyl)benzoic acid [00071] 5,6 Verbicky, John W., Jr.; Williams, Louella Journal of Organic Chemistry 1981, 46, 175-7. 2-(isopropylcarbamoyl)benzoic acid [00072] 7,8 Yasuda, Naohiko; Naka- mura, Asao; Tsuboi, Masamichi Journal of Heterocyclic Chemistry 1987, 24, 303-7 2-(propylcarbamoyl)benzoic acid [00073] 9,10 Zhang, Fu-chen; Gong, Sheng-chen; Chen, Qi-fan Liaodong Xueyuan Xuebao, Ziran Kexueban 2010, 17, 1-4. 4-(tert-butylamino)-4-oxo-butanoic acid [00074] 11,12 Valla, Alain; Cartier, Dominique; Zentz, Frederic; Labia, Roger Synthetic Communica- tions 2006, 36, 3591- 3597. 4-(isopropylamino)-4-oxo-butanoic acid [00075] 14,15 Wang, Wen-Hua; Liu, Wei-Sheng; Wang, Ya- Wen; Li, Yang; Zheng, Li- Fang; Wang, Da-Qi Journal of Inorganic Bio- chemistry 2007, 101, 297- 304. 2-(hydroxycarbamoyl)benzoic acid [00076] 25,26 Tanaka, Kazuo; Ishiguro, Fumiyasu; Chujo, Yoshiki Journal of the American Chemical Society 2010, 132, 17649-17651. 4-oxo-4-(propylamino)butanoic acid [00077] 31 Commercially available 4-amino-4-oxo-butanoic acid

II. Preparation of Polyurethanes

1. Formulation

[0347]

TABLE-US-00003 Polyol wt. % Polyol A 32 Polyol B 30 Polyol C 35 Additive 1 2.9 Additive 2 0.1 Catalyst (active species) 0.05 Isocyanate wt. % Iso A 40 Iso B 60 MV 100:98 [0348] Polyol A: Polyetherpolyol with an average OH value of 248 mg KOH/g, a functionality of 2.0 and a propylene oxide content, respect to the polymer weight, of approx. 83 wt. % [0349] Polyol B: Isopol 1200-3600 of the company ISO-ELEKTRA Elektrochemische Fabrik GmbH [0350] Polyol C: Polyetherpolyol with an average OH value of 490 mg KOH/g, a functionality of 4.3 and a propylene oxide content, respect to the polymer weight, of approx. 67 wt. % [0351] Additive 1: Zeolite-Paste 3A from the company ISO-ELEKTRA Elektrochemische Fabrik GmbH [0352] Additive 2: Xiameter ACP-1000 Antifoam compound from the company Dow Corning Corporation [0353] Iso A: Poly(methylen-diphenyl-diisocyanate) with a NCO content of 31.5 wt. % and an average functionality of 2.7 [0354] Iso B: Methylene-diphenyl-diisocyanat with a NCO content of 33.5 Gew.-% and an average functionality of 2, with an isomeric 4,4 content of 49 wt. %

2. Preparation of the Novel Catalyst.

[0355] In a typical experiment, 50 wt. % ethylene glycol solution of the different salts were prepared. The corresponding amounts of acid, base and solvent were added and shortly heated in a microwave oven (900 Watts) for 20 sec. After that the mixture was vigorously stirred for 10 sec to obtain a homogeneous solution.

3. Catalyst

[0356] The amount specified in the formulation corresponds to the concentration of catalytic species. [0357] Cat. Ref. 1:1,8-diazabicyclo-5,4,0-undecen-7 (DBU) from BASF AG [0358] Cat. Ref. 2: Polycat SA1-10 from Air Products [0359] Cat. Ref. 3: 50 wt. % ethylene glycol solution of 1 eq. of phthalamic acid (Aldrich) and DBU from BASF AG [0360] Cat. Ref. 4: structure from JP2014055114A 20140327 [0361] 3.1 For the preparation of Cat. Ref. 4, the acidic component was prepared according to Jha, Amitabh; Chou, Ting-Yi; Al Jaroudi, Zainab; Ellis, Bobby D.; Cameron, T. Stanley, Beilstein Journal of Organic Chemistry, 2014, 10, 848-857.

[0362] The acid was mixed with ethyleneglycol to give a thick suspension to which DBU was added while the temperature was maintained between 14 C. and 16 C. After stirring for 3 hours at room temperature, a colorless solution was obtained.

4. Curing with the DSC

[0363] The polyol component was mixed using a speed mixer for 5 min under vacuum conditions. Then, the isocyanates component was added and the components were mixed again with a speed mixer under vacuum for additional 2 min. Approximately 10 mg was weighted into a DSC Al-pan. The reactive mixture was then heated from 30 C. to 250 C. at 20 K/min. An example can be appreciated in FIG. 1. The curing reaction was recorded. The onset, peak and offset temperatures were extracted from the curve, the results can be appreciated in Table 3. They were calculated by estimating the area under the curve. The temperatures at 10%, 50% and 95% area were considered as the onset, peak and offset temperatures, respectively.

[0364] The cured resin was cooled down (30 C.) and re-heated (150 C.). The glass transition of the cured resin was approx. 80 C. in all the cases.

[0365] The latency of the DBU-carboxylate can be measured as the shift of the temperature peak during the curing reaction. A good thermolatent catalyst would be one that shift the onset of the temperature of the curing reaction by keeping, at least, the same offset temperature as the reference (DBU).

[0366] From the results can be observed that the DBU carboxylate prepared with succinamic acid has the better latency (shift of temperature at 10% curing) and lower end-curing temperature (temperature at 95% degree of curing). By using the DBU carboxylate prepared with 4-oxo-4-(propylamino)butanoic acid, a minimum shift in the 10% temperature is observed by comparable end-curing temperature to polycat SA1-10.

[0367] The thermolatency of the different DBU carboxylates can be also evaluated by varying the ratio DBU:acid ratio. Table 4 summarizes the results. Surprisingly, in the case of the 4-oxo-4-(propylamino)butanoic acid the increase in its concentrations, related to DBU, shifted the onset of the curing reaction and shortens the offset temperature.

TABLE-US-00004 TABLE 3 Comparison uncatalyzed with catalyzed system. Molar ratio DBU to acid 1:1 From the area 10% 50% 95% ID Catalyst ( C.) ( C.) ( C.) 1 93 138 207 2 Cat. Ref. 1 78 102 132 3 Cat. Ref. 2 77 101 130 4 Cat. Ref. 3 82 107 137 5 Cat. Ref. 4 78 103 134 4-methoxyphthalanilic acid:DBU 1:1 6 Succinamic acid:DBU 1:1 80 104 130 7 4-oxo-4-(propylamino)butanoic 79 103 132 acid:DBU 1:1 (25) 8 2-(propyl carbomoyl)benzoic 80 104 134 acid:DBU 1:1 (1) 9 2-(hydroxymethyl)benzoic 81 104 132 acid:DBU 1:1 (23) 10 7 80 111 143 11 4-methoxysuccinanilic acid:DBU 79 101 127 1:1

TABLE-US-00005 TABLE 4 Comparison different DBU molar ratio. Variation of Molar ratio between DBU and acid From the area 10% 50% 95% ID Catalyst ( C.) ( C.) ( C.) 1 4-oxo-4-(propylamino)butanoic 79 103 132 acid:DBU 1:1 (25) 3 4-oxo-4-(propylamino)butanoic 80 102 129 acid:DBU 1.5:1 4 4-oxo-4-(propylamino)butanoic 81 102 129 acid:DBU 2:1 5 4-oxo-4-(propylamino)butanoic 80 105 132 acid:DBU 3:1 6 4-oxo-4-(propylamino)butanoic 81 104 128 acid:DBU 4:1 7 4-oxo-4-(propylamino)butanoic 81 117 157 acid:DBU 10:1 8 2-(propylcarbomoyl)benzoic 80 104 134 acid:DBU 1:1 (1) 9 2-(propylcarbomoyl)benzoic 81 107 138 acid:DBU 1.5:1 10 Cat. Ref. 3 82 107 137 11 Phthalamic acid:DBU 1.5:1 81 107 140 12 2-(hydroxymethyl)benzoic 81 104 131 acid:DBU 1:1 (23) 13 2-(hydroxymethyl)benzoic 81 112 139 acid:DBU 2:1 14 2-(hydroxymethyl)benzoic 81 115 141 acid:DBU 3:1 15 Succinamic acid:DBU 1:1 80 101 125 16 Succinamic acid:DBU 1:1 81 105 135 17 Succinamic acid:DBU 2:1 80 106 136 18 Succinamic acid:DBU 4:1 79 105 134 19 Succinamic acid:DBU 10:1 74 112 142

5. Production of Plates Via Reaction Transfer Molding

[0368] Plates were produced via reaction transfer molding.

[0369] A commercial RTM formulation, named BASF Ellastolit R8819/104 LT was tested. 14 cm12 cm2 mm plates were prepared with/without Toray T700 carbon fiber fabrics at 90 C. and 110 C. (mold temperature). Without carbon fibers it can be appreciated that the plates catalyzed with ID1 (Table 4) are more transparent than the original Ellastolit formulation. In the case of the fiber reinforced plates, the addition of the catalyst ID 1 (Table 4) reduced the de-molding time at 90 C. from 3 to 2 min and at 110 C. from higher than to 2 to 2 min. The use of catalyst ID 1 (Table 4) reduces the de-molding time of an approx. 30%. Most translucent PU composite parts are an advantage for the monitoring of defect (e.g. fiber orientation, hot spots, enclosed air, etc.) during production.