Metal complex compounds as catalysts for polyurethane compositions

Abstract

The invention relates to metal complex compounds of the formula M.sub.k(L).sub.x(Y).sub.kz-nx, where the ligand L has the formula (I), and to metal complex compounds which include the reaction product of at least one salt or a complex of a transition metal or a main group metal element of the groups 13 to 15 and at least one 1,3-ketoamide. Such complex compounds are suitable in particular as catalysts for polyurethane compositions. The invention also relates to two-component polyurethane compositions including at least one polyisocyanate as the first component, at least one polyol as the second component, and at least one such metal complex compound as the catalyst. The invention additionally relates to different uses of the two-component polyurethane compositions.

Claims

1. A metal complex compound of formula M.sub.k(L).sub.x(Y).sub.kz-nx, where: M stands for a z-valent metal cation chosen from metal cations and oxometal cations of transitional metals, zinc, or main metal group elements of periodic table groups 13 to 15, k stands for a whole number in a range of from 1 to 20, x stands for 1, 2, 3 or 4, z stands for 2, 3 or 4, n stands for 2 or 3, Y stands for a single negatively charged ligand, L stands for a ligand of formula (I), and kz-nx may be 0, ##STR00006## where: each of R.sup.1 and R.sup.2 independently stands for a hydrogen residue, a monovalent saturated or unsaturated hydrocarbon residue with 1 to 10 carbon atoms, or together stand for a divalent alkylene residue with 3 to 6 carbon atoms, R.sup.3 stands for a hydrogen residue or a monovalent saturated hydrocarbon residue with 1 to 12 carbon atoms that optionally contains heteroatoms, and A stands for a polyoxyalkylene-containing residue with a mean molecular weight M.sub.n of 200 to 5000 g/mol, optionally with one or two terminal 1,3-ketoamide groups of formula ##STR00007##

2. The metal complex compound according to claim 1, wherein the metal cation is a metal cation or oxometal cation of scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, aluminum, gallium, indium, germanium, tin, lead, antimony, or bismuth.

3. The metal complex compound according to claim 1, wherein the metal cation or oxometal cation is a dioxomolybdenum (VI), iron (III), zinc (II), bismuth (III), or zirconium (IV) cation.

4. The metal complex compound according to claim 1, wherein R.sup.1 stands for an alkyl residue with 1 to 4 carbon atoms.

5. The metal complex compound according to claim 1, wherein R.sup.2 stands for a hydrogen residue.

6. The metal complex compound according to claim 1, wherein R.sup.3 stands for a hydrogen residue or an alkyl residue with 1 to 8 carbon atoms.

7. The metal complex compound according to claim 1, wherein n is 2.

8. A method for producing the metal complex compound according to claim 1, comprising reacting a 1,3-ketoamide with a metal salt or metal complex chosen from a salt or a complex of a transitional metal, zinc, or an element of main metal group elements of periodic table groups 13 to 15, wherein the 1,3-ketoamide has a formula: ##STR00008## where: each of R.sup.1 and R.sup.2 independently stands for a hydrogen residue, a monovalent saturated or unsaturated hydrocarbon residue with 1 to 10 carbon atoms, or together stand for a divalent alkylene residue with 3 to 6 carbon atoms, R.sup.3 stands for a hydrogen residue or a monovalent saturated hydrocarbon residue with 1 to 12 carbon atoms that optionally contains heteroatoms, and A stands for a polyoxyalkylene-containing residue, optionally with one or two terminal 1,3-ketoamide groups of formula ##STR00009##

9. The method according to claim 8, wherein the metal salt or metal complex are chlorides, carbonates, carboxylates, or 1,3 diketonates.

10. The metal complex compound according to claim 1, wherein the polyoxyalkylene-containing residue is a polyoxypropylene amine, which optionally contains moieties of oxybutylene and/or oxyethylene units.

11. A metal complex compound, obtained by reacting a 1,3-ketoamide with a metal salt or a metal complex chosen from a salt or a complex of a transitional metal, zinc, or an element of main metal group elements of periodic table groups 13 to 15; wherein the 1,3-ketoamide has a formula: ##STR00010## where: each of R.sup.1 and R.sup.2 independently stands for a hydrogen residue, a monovalent saturated or unsaturated hydrocarbon residue with 1 to 10 carbon atoms, or together stand for a divalent alkylene residue with 3 to 6 carbon atoms, R.sup.3 stands for a hydrogen residue or a monovalent saturated hydrocarbon residue with 1 to 12 carbon atoms that optionally contains heteroatoms, A stands for a polyoxyalkylene-containing residue with a mean molecular weight M.sub.n of 200 to 5000 g/mol, optionally with one or two terminal 1,3-ketoamide groups of formula ##STR00011##  and n stands for 2 or 3.

12. A metal complex compound of formula M.sub.k(L).sub.x(Y).sub.kz-nx, where: M stands for a z-valent metal cation chosen from metal cations and oxometal cations of scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, cobalt, nickel, copper, zinc, aluminum, gallium, indium, germainium, tin, lead, antimony, or bismuth, k stands for a whole number in a range of from 1 to 20, x stands for 1, 2, 3 or 4, z stands for 2, 3, or 4, n stands for 1, 2, or 3, Y stands for a single negatively charged ligand, L stands for a ligand of formula (I), and kz-nx may be 0, ##STR00012## where: each of R.sup.1 and R.sup.2 independently stands for a hydrogen residue, a monovalent saturated or unsaturated hydrocarbon residue with 1 to 10 carbon atoms, or together stand for a divalent alkylene residue with 3 to 6 carbon atoms, R.sup.3 stands for a hydrogen residue or a monovalent saturated hydrocarbon residue with 1 to 12 carbon atoms that optionally contains heteroatoms, and A stands for a polyoxyalkylene-containing residue with a mean molecular weight M.sub.n of 200 to 5000 g/mol, optionally with one or two terminal 1,3-ketoamide groups of formula ##STR00013##

13. A method comprising: mixing the metal complex compound according to claim 1 with a curable mass to catalyze curing of the curable mass.

14. A two-component polyurethane composition, comprising at least one polyol as a first component, at least one polyisocyanate as a second component, and at least one metal complex compound according to claim 1.

15. The two-component polyurethane composition according to claim 13, wherein the metal complex compound is contained in the first component.

16. A casting compound, sealant, adhesive, lining, coating, lacquer, primer, molded piece, or elastomer for construction and industrial applications comprising: the two-component polyurethane composition according to claim 13.

Description

EXAMPLES

(1) Description of the Measurement Methods

(2) Infrared spectra were measured on a FT-IR 1600 instrument from Perkin-Elmer (horizontal ATR measuring unit with ZnSe crystal; measurement window 4000-650 cm.sup.−1). Liquid samples were deposited undiluted as films, solid samples were dissolved in CH.sub.2Cl.sub.2. The absorption bands are indicated in wave numbers (cm.sup.−1).

(3) .sup.1H-NMR spectra were measured on a spectrometer of type Bruker DPX-300 at 300.13 MHz; the chemical shifts δ are indicated in ppm relative to tetramethylsilane (TMS). No distinction was made between true and pseudo coupling patterns.

(4) The viscosity was measured on a thermostatically controlled cone-plate viscosimeter Physica MCR 300 (cone diameter 20 mm, cone angle 1°, distance between cone tip and plate 0.05 mm, shear rate 0.1 to 100 s.sup.−1).

(5) Mass spectra (FIMS) were measured on a high-resolution mass spectrometer of type Thermo Scientific LTQ Orbitrap XL, by injecting 500 μl of the sample dissolved in methanol (100 μg/ml) at an injection rate of 10 μl/min and a flow rate of the carrier (1 mM ammonium formate in methanol) of 500 μl/min directly into the mass spectrometer; the detection was done by means of Electrospray Ionization (ESI.sup.+).

(6) Preparation of 1,3-ketoamides

(7) General Preparation Procedure A

(8) In a round-bottom flask, a mixture of a polyether amine and tert.-butyl-acetoacetate was heated under stirring at 300 mbar for around 4 hours to 110° C. After this, the reaction mixture was liberated of the volatile components in vacuum.

(9) General Preparation Procedure B

(10) In a round-bottom flask, tert.-butyl-acetoacetate was added slowly to a polyether amine heated to 130° C. and the reaction mixture was held for another 18 hours at 130° C. After this, it was cooled down to room temperature and liberated of the volatile components in vacuum. The obtained residue was dissolved in ethyl acetate, the solution washed with hydrochloric acid solution (0.1 M), dried with MgSO.sub.4 and concentrated down completely.

(11) 1,3-Ketoamide 1

(12) According to general preparation procedure A, 12.00 g of Jeffamine® ST-404 and 12.27 g of tert.-butyl-acetoacetate were combined. One obtained 17.39 g of a reddish oil.

(13) FT-IR: 2968, 2931, 2871, 1719, 1362, 1584, 1443, 1371, 1324, 1229, 1216, 1102, 929, 850, 775.

(14) 1,3-Ketoamide 2

(15) According to general preparation procedure A, 41.92 g of Jeffamine® SD-2001 and 7.80 g of tert.-butyl-acetoacetate were reacted. One obtained 45.37 g of a light yellow oil.

(16) FT-IR: 2939, 2868, 1737, 1589, 1202, 1449, 1371, 1269, 1217, 1092, 934, 906, 868, 800, 772.

(17) FIMS: m/2149.52 (15), 2148.51733 (10, [MNa.sup.+] for the oligomer with x=31), 2144.56 (100), 2143.56.055 (80, [MH.sup.+] for the oligomer with x=31).

(18) 1,3-Ketoamide 3

(19) According to general preparation procedure A, 103.10 g of Jeffamine® SD-401 and 65.13 g of tert.-butyl-acetoacetate were reacted. One obtained 133.90 g of a light yellow oil.

(20) FT-IR: 2969, 2929, 2870, 1718, 1633, 1584, 1444, 1372, 1341, 1208, 1099, 1018, 928, 862, 773.

(21) 1,3-Ketoamide 4

(22) According to general preparation procedure B, 76.50 g of Jeffamine® D-230 and 130.02 g of tert.-butyl-acetoacetate were reacted. One obtained 51.93 g of a light yellow oil.

(23) FT-IR: 3305, 2973, 2875, 1714, 1645, 1542, 1452, 1410, 1358, 1323, 1254, 1147, 1103, 1024, 922, 847, 668.

(24) FIMS: m/z 497.28 (90), 475.30 (54), 439.24 (43), 417.26047 (100, [MH.sup.+] for the oligomer with x=3), 359.22 (41).

(25) 1,3-Ketoamide 5

(26) According to general preparation procedure B, 15.76 g of Jeffamine® D-400 and 14.99 g of tert.-butyl-acetoacetate were reacted. One obtained 13.21 g of a light yellow oil.

(27) FT-IR: 3306, 2971, 2929, 2869, 1715, 1646, 1540, 1453, 1409, 1369, 1252, 1143, 1098, 1015, 924, 848, 775, 750.

(28) FIMS: m/z 649.42 (30), 623.45 (63), 607.41339 (100, [MNH.sub.4.sup.+] for the oligomer with x=6), 591.38 (36).

(29) 1,3-Ketoamide 6

(30) According to general preparation procedure B, 82.10 g of Jeffamine® D-2000 and 17.14 g of tert.-butyl-acetoacetate were reacted. One obtained 87.77 g of a light yellow oil.

(31) FT-IR: 3322, 2969, 2867, 1715, 1649, 1535, 1451, 1371, 1343, 1296, 1253, 1095, 1013, 921, 866.

(32) 1,3-Ketoamide 7

(33) According to general preparation procedure B, 62.33 g of Jeffamine® M-600 and 22.39 g of tert.-butyl-acetoacetate were reacted. One obtained 58.14 g of a light yellow oil.

(34) FT-IR: 3323, 2969, 2867, 1720, 1649, 1547, 1452, 1371, 1342, 1297, 1095, 1013, 924, 817.

(35) FIMS: m/z 655.47 (95), 641.46 (65), 597.43359 (100, [MNH.sub.4.sup.+] for the oligomer with x=8), 583.42 (54), 539.39 (100).

(36) 1,3-Ketoamide 8

(37) According to general preparation procedure B, 56.15 g of Jeffamine® XTJ-581 and 15.82 g of tert.-butyl-acetoacetate were reacted. One obtained 32.14 g of a brownish oil.

(38) FT-IR: 3324, 2978, 2864, 1715, 1668, 1540, 1456, 1348, 1275, 1256, 1094, 946, 849, 760.

(39) 1,3-Ketoamide 9

(40) According to general preparation procedure A, 12.72 g of Jeffamine® SD-231 and 17.94 g of tert.-butyl-acetoacetate were reacted. One obtained 20.62 g of a reddish-orange oil.

(41) FT-IR: 2974, 2931, 2872, 1715, 1633, 1444, 2362, 1106, 1025, 934, 848, 774.

(42) Preparation of Polyurethane Catalysts

(43) General Preparation Procedure C

(44) In a round-bottom flask, dioxomolybdenum (VI) bis(acetylacetonate) and a 1,3-ketoamide prepared as described were mixed and the mixture was heated under stirring for 2 hours to 80° C. After this, the reaction mixture was liberated of volatile components in vacuum.

Example 1

Catalyst Mo1

(45) According to general preparation procedure C, 3.24 g of dioxomolybdenum (VI) bis(acetylacetonate) and 5.67 g of 1,3-ketoamide 1 were reacted. One obtained 7.86 g of a reddish, glasslike solid.

(46) FT-IR: 2969, 2930, 2873, 1717, 1588, 1496, 1371, 1333, 1266, 1195, 1104, 1028, 991, 931, 903, 776, 734.

Example 2

Catalyst Mo2

(47) According to general preparation procedure C, 3.70 g of dioxomolybdenum (VI) bis(acetylacetonate) and 5.60 g of 1,3-ketoamide 4 were reacted. One obtained 7.42 g of a brownish, glasslike solid.

(48) FT-IR: 3305, 2972, 2930, 2873, 1715, 1588, 1514, 1446, 1401, 1361, 1267, 1182, 1104, 1028, 969, 932, 898, 795, 733, 701, 668.

Example 3

Catalyst Mo3

(49) According to general preparation procedure C, 1.80 g of dioxomolybdenum (VI) bis(acetylacetonate) and 3.66 g of 1,3-ketoamide 5 were reacted. One obtained 4.46 g of a brownish oil.

(50) FT-IR: 2968, 2869, 1720, 1626, 1564, 1517, 1446, 1401, 1369, 1266, 1182, 1092, 1007, 968, 931, 896, 794, 668.

Example 4

Catalyst Mo4

(51) According to general preparation procedure C, 1.52 g of dioxomolybdenum (VI) bis(acetylacetonate) and 11.00 g of 1,3-ketoamide 6 were reacted. One obtained 11.35 g of a greenish, glasslike solid.

(52) FT-IR: 3307, 2969, 2868, 1737, 1629, 1566, 1522, 1451, 1371, 1091, 1011, 934, 906.

Example 5

Catalyst Mo5

(53) According to general preparation procedure C, 2.83 g of dioxomolybdenum (VI) bis(acetylacetonate) and 13.32 g of 1,3-ketoamide 7 were reacted. One obtained 14.42 g of a brownish oil.

(54) FT-IR: 3296, 2969, 2870, 1630, 1566, 1521, 1450, 1403, 1372, 1342, 1268, 1093, 1009, 967, 933, 904, 796.

(55) General Preparation Procedure D

(56) In a round-bottom flask, dried iron (III) tris(acetylacetonate) and a 1,3-ketoamide prepared as described were mixed and the mixture was heated under stirring for 3 hours to 90° C. After this, the reaction mixture was liberated of volatile components in vacuum.

Example 6

Catalyst Fe1

(57) According to general preparation procedure D, 2.65 g of iron (III) tris(acetylacetonate) and 16.54 g of 1,3-ketoamide 7 were reacted. One obtained 17.40 g of a reddish-brown oil.

(58) FT-IR: 3324, 2970, 2868, 1651, 1577, 1523, 1450, 1372, 1342, 1272, 2097, 1016, 968, 926, 864, 775, 667.

Example 7

Catalyst Fe2

(59) According to general preparation procedure D, 1.41 g of iron (III) tris(acetylacetonate) and 15.70 g of 1,3-ketoamide 2 were reacted. One obtained 16.17 g of a brownish-red oil.

(60) FT-IR: 2967, 2865, 1638, 1558, 1512, 1456, 1372, 1335, 1296, 1095, 1013, 926, 865, 763, 657.

Example 8

Catalyst Fe3

(61) According to general preparation procedure D, 0.71 g of iron (III) tris(acetylacetonate) and 7.26 g of 1,3-ketoamide 6 were reacted. One obtained 7.69 g of a brownish red oil.

(62) FT-IR: 2967, 2865, 1638, 1558, 1512, 1456, 1372, 1335, 1296, 1095, 1013, 926, 865, 763, 657.

Example 9

Catalyst Fe4

(63) According to general preparation procedure D, 3.54 g of iron (III) tris(acetylacetonate), 3.99 g of N,N-dibutyl-3-oxoheptane amide and 5.32 g of 1,3-Ketoamid 3 were reacted. One obtained 10.32 g of a dark red oil.

(64) FT-IR: 2957, 2930, 2871, 1636, 1556, 1511, 1461, 1370, 1331, 1271, 1226, 1200, 1102, 1019, 986, 956, 763, 661.

(65) General Preparation Procedure E

(66) In a round-bottom flask, zinc (II) bis(acetylacetonate) hydrate (contains around 2 equivalents of water) and a 1,3-ketoamide prepared as described were mixed and the mixture heated under stirring for 3 hours to 90° C. After this, the reaction mixture was liberated of volatile components in vacuum.

Example 10

Catalyst Zn1

(67) According to general preparation procedure E, 2.53 g of zinc (II) bis(acetylacetonate) hydrate and 17.99 g of 1,3-ketoamide 7 were reacted. One obtained 18.24 g of a light yellow oil. FT-IR: 3325, 2968, 2867, 1652, 1547, 1450, 1372, 1341, 1298, 1263, 1096, 1015, 964, 925, 866, 782.

Example 11

Catalyst Zn2

(68) According to general preparation procedure E, 1.33 g of zinc (II) bis(acetylacetonate) hydrate and 15.57 g of 1,3-ketoamide 2 were reacted. One obtained 16.15 g of a light yellow oil.

(69) FT-IR: 2969, 2930, 2866, 1718, 1637, 1587, 1517, 1450, 1372, 1341, 1296, 1259, 1094, 1014, 925, 866, 768.

Example 12

Catalyst Zn3

(70) According to general preparation procedure E, 1.31 g of zinc (II) bis(acetylacetonate) hydrate and 9.04 g of 1,3-ketoamide 3 were reacted. One obtained 9.49 g of a light yellow oil.

(71) FT-IR: 2968, 2927, 2874, 1717, 1634, 1579, 1513, 1444, 1372, 1333, 1258, 1199, 1100, 1017, 927, 859, 769.

Example 13

Catalyst Zn4

(72) According to general preparation procedure E, 0.86 g of zinc (II) bis(acetylacetonate) hydrate and 9.77 g of 1,3-ketoamide 8 were reacted. One obtained 9.88 g of a light brown oil.

(73) FT-IR: 3325, 2865, 1712, 1666, 1585, 1546, 1451, 1348, 1251, 1095, 995, 947, 849, 780.

(74) General Preparation Procedure F

(75) In a round-bottom flask, Coscat® 83 (bismuth (III) tris(neodecanoate) in neodecanoic acid; 16% Bi; from Erbslöh) and a 1,3-ketoamide prepared as described were mixed and the mixture was heated under stirring for 2 hours to 80° C. After this, the reaction mixture was cooled to room temperature.

Example 14

Catalyst Bi1

(76) According to general preparation procedure F, 1.51 g of Coscat® 83 and 3.98 g of 1,3-ketoamide 2 were reacted. One obtained 5.48 g of a light yellow oil.

(77) FT-IR: 2967, 2929, 2867, 1721, 1636, 1609, 1539, 1458, 1372, 1342, 1296, 1253, 1097, 1013, 926, 867.

Example 15

Catalyst Bi2

(78) According to general preparation procedure F, 2.76 g of Coscat® 83 and 1.40 g of 1,3-ketoamide 4 were reacted. One obtained 4.16 g of a light yellow oil.

(79) FT-IR: 3330, 2959, 2931, 2874, 1698, 1636, 1544, 1460, 1360, 1254, 1156, 1108, 1015, 908, 817, 741.

Example 16

Catalyst Bi3

(80) According to general preparation procedure F, 1.38 g of Coscat® 83 and 2.18 g of 1,3-ketoamide 3 were reacted. One obtained 3.56 g of a light yellow oil.

(81) FT-IR: 2964, 2932, 2873, 1717, 1635, 1602, 1459, 1372, 1341, 1102, 1021, 928, 817, 772.

Example 17

Catalyst Bi4

(82) According to general preparation procedure F, 1.45 g of Coscat® 83 and 1.39 g of 1,3-ketoamide 4 were reacted. One obtained 2.84 g of a light yellow oil.

(83) FT-IR: 3304, 2962, 2932, 2872, 1714, 1644, 1545, 1458, 1359, 1253, 1153, 1106, 1022, 923, 817, 741.

(84) General Preparation Procedure G

(85) In a round-bottom flask, zirconium (IV) propoxide solution (70% in propanol; 19.5% Zr) and a 1,3-ketoamide prepared as described were mixed and stirred for 3 hours at room temperature. After this, the reaction mixture was heated to 60° C. and partly liberated of volatile components in vacuum.

Example 36

Catalyst Zr1

(86) According to general preparation procedure G, 1.28 g of zirconium (IV) propoxide solution and 13.54 g of 1,3-ketoamide 3 were reacted. One obtained 14.70 g of a viscous, light yellow oil. FT-IR: 2970, 2931, 2871, 1717, 1635, 1568, 1516, 1445, 1372, 1333, 1257, 1202, 1100, 1018, 989, 963, 928, 861, 764, 740, 721, 668.

Example 37

Catalyst Zr2

(87) According to general preparation procedure G, 2.05 g of zirconium (IV) propoxide solution and 30.66 g of 1,3-ketoamide 2 were reacted. One obtained 31.27 g of a viscous, orange-colored oil. FT-IR: 2970, 2930, 2867, 1718, 1640, 1568, 1517, 1455, 1372, 1339, 1297, 1267, 1100, 1013, 990, 864, 925, 866, 834, 764, 668.

Example 38

Catalyst Zr3

(88) According to general preparation procedure G, 1.42 g of zirconium (IV) propoxide solution and 9.86 g of 1,3-ketoamide 9 were reacted. One obtained 10.04 of a viscous, light yellow oil.

(89) Two-Component Polyurethane Compositions

Examples 18 to 21 and 39 and Comparison Examples V1 to V5

(90) For the preparation of the first component, for each example a polyether triol (Voranol® CP 4755, from Dow) and a catalyst according to Table 1 were intimately mixed in a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) for 30 seconds at 3000 rpm. A portion of the freshly prepared first component was then placed in an interior-lacquered aluminum tube, this was closed air-tight and kept for 7 days in a circulating air oven at 60° C.

(91) The remaining potion of the freshly prepared first component was mixed in the manner described for each example with a modified diphenylmethane diisocyanate (Desmodur® CD-L, from Bayer), liquid at room temperature, as the second component according to Table 1 to form a polyurethane composition.

(92) Likewise, for each example, the first component that was kept for 7 days at 60° C. was mixed with the second component according to Table 1 in the same manner to form a polyurethane composition.

(93) The polyurethane compositions were tested for appearance, time until tack-free, bubble formation, Shore A hardness, and this both for the composition with the freshly prepared first component and for the composition with the first component kept for 7 days at 60° C. Furthermore, only for the composition with the freshly prepared first component the mechanical properties were measured in the tensile strength test, and this before and after various storage times for accelerated aging of the samples.

(94) The appearance of the composition was judged purely visually and given a grade of “clear”, “cloudy” or inhomogeneous (“inh.”).

(95) To determine the time until tack-free (skin formation time), the compositions at room temperature were applied in a layer thickness of around 3 mm to cardboard and the time was determined in normal climate (“NK”; 23±1° C., 50±5% relative humidity) until when the surface of a composition was touched lightly by means of a pipette of LDPE there was no longer any residue on the pipette for the first time.

(96) The bubble formation was judged visually by means of the quantity (“many”, “some”, “none”) of gas bubbles occurring during the hardening for the composition used to determine the skin formation time.

(97) The Shore A hardness was determined by DIN 53505 on test bodies cured for 7 days in normal climate.

(98) To determine the mechanical properties in the tensile strength test, films of around 3 mm thickness were prepared from the compositions, by pouring out the composition into a flat PTFE mold and curing for 7 days in the normal climate. Tack-free and elastic films were obtained. From the films, dumbbells were punched out with a length of 75 mm, web length of 30 mm and web width of 4 mm and one part of these was tested according to DIN EN 53504 at a pulling rate of 200 mm/min for tensile strength, elongation at break, and E modulus (at 0.5 to 5.0% elongation). The remaining part of the dumbbells was kept for 1 day at 100° C. in the circulating air oven and for 10 days under “Kataplasma” (40° C. and 100% relative humidity), or for 10 days under “Kataplasma” and 1 day at 100° C., then each was kept for one day in the normal climate and tested as described according to DIN EN 53504.

(99) The results of these tests are given in Table 2.

(100) It is evident from Table 2 that the two-component polyurethane compositions with the catalysts according to the invention constitute clear, homogeneous mixtures, which have relatively short skin formation times both before and after storage and harden bubble-free into a material with relatively high strength and good toughness.

(101) TABLE-US-00001 TABLE 1 Two-component polyurethane compositions (quantities in parts by weight). Example 18 V1 19 V2 20 V3 21 V4 39 V5 First component: Voranol ® CP 4755 50 50 50 50 50 50 50 50 50 50 Catalyst Mo5 0.34 — — — — — — — — — MoO.sub.2(acac).sub.2.sup.a — 0.30 — — — — — — — — Catalyst Fe1 — — 0.58 — — — — — — — Fe(acac).sub.3.sup.b — — — 0.43 — — — — — — Catalyst Zn3 — — — — 0.27 — — — — — Zn(acac).sub.2.sup.c — — — — — 0.20 — — — — Catalyst Bi4 — — — — — — 0.026 — — — Coscat ® 83.sup.d — — — — — — — 0.013 — — Catalyst Zr1 — — — — — — — — 1.08 — Bicat ® 4130.sup.f — — — — — — — — — 0.15 mmoi-equiv./100 g.sup.e 0.37 0.41 0.45 0.45 0.23 0.23 0.018 0.018 0.36 0.36 Second component: Desmodur ® CD-L 5.10 5.10 5.10 5.10 5.10 5.10 5.10 5.10 5.10 5.10 .sup.a25% suspension of dioxomolybdän (VI) bis(acetylacetonate) in N-ethyl-2-pyrrolidone. .sup.b20.6% suspension of iron (III) tris(acetylacetonate) in N-ethyl-2-pyrrolidone. .sup.c19.3% suspension of zinc (II) bis(acetylacetonate) hydrate in methylethylketone. .sup.dBismuth tris(neodecanoate) in neodecanoic acid (16% Bi, from Erbslöh). .sup.fZirconium tetrakis(neodecanoate) (12.1% Zr, from Shepherd). .sup.emmol-equivalents of metal atoms of the catalyst per 100 g of composition.

(102) TABLE-US-00002 TABLE 2 Properties of the two-component polyurethane compositions Example 18 V1 19 V2 20 V3 21 V4 39 V5 Composition with freshly prepared first component: Appearance clear inh. clear inh. clear inh. clear clear clear clear Skin forming time (min.) 20 18 35 120 83 85 25 160 35 300 Shore A hardness 43 42 44 32 40 45 47 44 46 <20 Bubble formation none none none some none none none none none some Tensile strength (MPa): 7d/NK 0.90 0.84 0.90 0.78 0.82 1.00 0.90 1.08 0.85 0.34 + 10d/Kataplasma 0.97 0.90 0.96 0.75 0.77 0.74 0.77 0.76 0.94 0.34 + 1d/100° C. 0.91 0.89 0.82 0.93 0.86 0.90 0.84 0.94 0.82 0.38 + 10d/Kataplasma + 1d/100° C. 1.00 0.85 0.97 0.73 0.97 0.98 0.89 0.85 0.82 0.35 Elongation at break (%): 7d/N 70 62 63 86 119 94 87 129 81 54 + 10d/Kataplasma 82 72 70 89 107 62 74 74 100 61 + 1d/100° C. 85 71 181 97 85 64 96 99 113 104 + 10d/Kataplasma + 1d/100° C. 95 62 81 83 114 74 97 87 92 86 E modulus (MPa): 7d/NK 1.99 1.91 1.92 1.46 1.00 1.75 1.60 1.39 1.46 0.81 + 10d/Kataplasma 1.75 2.16 1.96 1.30 1.25 1.63 1.62 1.48 1.54 0.62 + 1d/100° C. 1.68 1.95 0.65 1.28 1.58 1.96 1.42 1.55 1.26 0.54 + 10d/Kataplasma + 1d/100° C. 1.70 1.94 1.65 1.34 1.42 1.89 1.52 1.47 1.39 0.59 Composition with first component from storage: Appearance clear clear clear inh. clear clear clear clear clear clear Skin forming time (min.) 15 7 34 73 80 70 50 >300 24 >300 Shore A hardness 48 41 46 37 45 45 48 45 46 <20 Bubble formation none none none none none some none some none some

Examples 22 to 41

(103) As described for Example 18, each time for the preparation of the first component a polyether triol (Voranol® CP 4755, from Dow) and a catalyst according to Table 3 were mixed. A portion of the freshly prepared first component was then placed in an interior-lacquered aluminum tube, this was closed air-tight and kept for 7 days in a circulating air oven at 60° C.

(104) The remaining potion of the freshly prepared first component was mixed in the manner described for example 18 with a modified diphenylmethane diisocyanate (Desmodur® CD-L, from Bayer), liquid at room temperature, as the second component according to Table 3 to form a polyurethane composition.

(105) Likewise, for each example, the first component that was kept for 7 days at 60° C. was mixed with the second component according to Table 3 in the same manner to form a polyurethane composition.

(106) The polyurethane compositions were tested as in Example 18 for appearance, time until tack-free, bubble formation, Shore A hardness, as well as mechanical properties in the tensile strength test.

(107) The results of these tests are given in Table 4.

(108) It is evident from Table 4 that the two-component polyurethane compositions with the catalysts according to the invention constitute clear, homogeneous mixtures, which have relatively short skin formation times both before and after storage and harden largely bubble-free into a material with good Shore A hardness.

(109) TABLE-US-00003 TABLE 3 Two-component polyurethane compositions. Example 22 23 24 25 26 27 28 29 30 31 32 33 34 35 40 41 First component: Voranol ® CP 4755 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 Catalyst Mo1 0.31 — — — — — — — — — — — — — — — Catalyst Mo2 — 0.26 — — — — — — — — — — — — — — Catalyst Mo3 — — 0.31 — — — — — — — — — — — — — Catalyst Mo4 — — — 0.97 — — — — — — — — — — — — Catalyst Mo5 — — — — 0.67 — — — — — — — — — — — Catalyst Fe2 — — — — — 1.43 — — — — — — — — — — Catalyst Fe3 — — — — — — 1.16 — — — — — — — — — Catalyst Fe4 — — — — — — — 0.36 — — — — — — — — Catalyst Zn1 — — — — — — — — 0.43 — — — — — — — Catalyst Zn2 — — — — — — — — — 0.73 — — — — — — Catalyst Zn4 — — — — — — — — — — 0.66 — — — — — Catalyst Bi1 — — — — — — — — — — — 0.038 — — — — Catalyst Bi2 — — — — — — — — — — — — 0.016 — — — Catalyst Bi3 — — — — — — — — — — — — — 0.049 — — Catalyst Zr2 — — — — — — — — — — — — — — 1.25 — Catalyst Zr3 — — — — — — — — — — — — — — — 0.60 mmoi-equiv./100 g.sup.a 1.17 1.19 1.15 1.17 1.19 1.02 0.89 1.04 0.59 0.59 0.57 0.024 0.025 0.044 0.32 0.33 Second component: Desmodur ® CD-L 3.10 3.10 3.10 3.10 3.10 3.10 3.10 3.10 3.10 3.10 3.10 3.10 3.10 3.10 3.10 3.10 .sup.ammol-equivalents of metal atoms of catalyst per 100 g of composition.

(110) TABLE-US-00004 TABLE 4 Properties of the two-component polyurethane compositions. Example 22 23 24 25 26 27 28 29 30 31 32 33 34 35 40 41 Composition with freshly prepared first component: Appearance clear clear clear clear clear clear clear clear clear clear clear clear clear clear clear clear Skin forming time 50 15 20  8  9 60 44 32  7 10  7  2  1  4 10 20 (min.) Shore A hardness 44 46 45 39 43 41 45 46 41 43 49 47 49 50 47 48 Bubble formation none none none none none none none none none none none none none none none none Composition with first component from storage: Appearance clear clear clear clear clear clear clear clear clear clear clear clear clear clear clear clear Skin forming time 40 14  9 15  4 55 40 37  9  9  5  5  4  9 18 30 (min.) Shore A hardness 45 45 47 47 47 47 46 48 48 46 45 48 47 48 47 48 Bubble formation none none none none none none none none none none none none none none none none