Dioxomolybdenum (VI) complex compounds as catalysts for polyurethane compositions

Abstract

The invention relates to dioxomolybdenum (VI) complex compounds of the formula MoO.sub.2(L).sub.x(Y).sub.2-x, where the ligand L has the formula (I). Such complex compounds are suitable in particular as catalysts for one- and two-component 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 dioxomolybdenum (VI) complex compound as the catalyst. The invention further relates to one-component polyurethane compositions comprising at least one polyurethane prepolymer with isocyanate groups, which are made from at least one polyisocyanate with at least one polyol, and comprising such a dioxomolybdenum (VI) complex compound as the catalyst. The invention additionally relates to different uses of said polyurethane compositions. ##STR00001##

Claims

1. A curable composition comprising (1) at least one curable component selected from the group consisting of an epoxy resin, an acrylate and a silicone, and (2) at least one dioxomolybdenum(VI) complex compound of formula MoO.sub.2(L).sub.x(Y).sub.2-x, where x stands for 1 or 2, Y for a ligand with a single negative charge, and L for a ligand of formula (I), ##STR00005## where R.sup.1 and R.sup.2 independently of one another stand for a hydrogen residue, for a monovalent saturated or unsaturated hydrocarbon residue having 1 to 10 carbon atoms, or together stand for a bivalent alkylene residue having 3 to 6 carbon atoms, and R.sup.3 and R.sup.4 independently of one another stand for a hydrogen residue, a monovalent saturated hydrocarbon residue, which optionally contains heteroatoms, having 1 to 12 carbon atoms, or together stand for a bivalent alkylene residue, which optionally contains heteroatoms, having 3 to 6 carbon atoms, wherein said dioxomolybdenum(VI) complex compound is present in an amount sufficient to catalyze the curing of said curable component.

2. The curable composition according to claim 1, wherein the component comprises an epoxy resin.

3. The curable composition according to claim 1, wherein the component comprises an acrylate.

4. The curable composition according to claim 1, wherein the component comprises a silicone.

5. The curable composition according to claim 1, wherein x stands for 2.

6. The curable composition according to claim 1, wherein x stands for 1.

7. The curable composition according to claim 6, wherein Y is a carbonylate.

8. The curable composition according to claim 7, wherein the carbonylate is 1,3-dicarbonylate.

9. The curable composition according to claim 8, wherein the 1,3-dicarbonylate is acetylacetonate or 2,2,6,6,-tetramethylheptane-3-5,dionate.

Description

EXAMPLES

Description of the Measurement Methods

(1) The infrared spectra were measured with a Perkin-Elmer 1600 FT-IR apparatus (horizontal ATR measurement unit with ZnSe crystals; measurement window 4000-650 cm.sup.−1). Undiluted liquid samples were applied as films, and solid samples were dissolved in CH.sub.2Cl.sub.2. The absorption bands are indicated using wave numbers (cm.sup.−1).

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

(3) The viscosity was measured with a thermostated Physica MCR 300 cone-plate viscometer (cone diameter 20 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 0.1 to 100 s.sup.−1).

(4) The UV-vis spectra of samples (40 mg/L) dissolved in dichloromethane were measured in 1 cm quartz cuvettes with a Varian Cary 50 spectrometer in the wavelength range 800-200 nm. The extinction maxima δ.sub.max are indicated in nm, and the associated extinction coefficients ε are given in 1.Math.g.sup.−1.Math.cm.sup.−1 in parentheses.

(5) Preparation of the Dioxomolybdenum(VI) Complex Compounds

(6) General Preparation Procedure A

(7) In a round-bottom flask, dried dioxomolybdenum(VI) bis(acetylacetonate) and a 1,3-ketoamide were mixed, and the mixture was heated under stirring for 2 hours at 80° C. Subsequently, the volatile components were removed from the reaction mixture in a vacuum.

(8) General Preparation Procedure B

(9) In a round-bottom flask, sodium molybdate dihydrate (Na.sub.2MoO.sub.4.2H.sub.2O) was mixed in 15 mL hydrochloric acid solution (0.1 M). A 1,3-ketoamide was mixed into this solution, and the mixture was stirred for 18 hours at 23° C. Subsequently the reaction mixture was filtered and the resulting solid was dried in a vacuum.

(10) General Preparation Procedure C

(11) In a round-bottom flask, a mixture of dried dioxomolybdenum(VI) bis(acetylacetonate) and a 1,3-ketoamide in tetraethylene glycol dimethyl ether (TEGDME) was heated under stirring for 3 hours at 80° C. Subsequently, the reaction mixture was cooled to room temperature.

Example 1

Dioxomolybdenum(VI) Bis(N,N-Diethyl-3-Oxobutane Amidate)

(12) 3.26 g Dioxomolybdenum(VI) bis(acetylacetonate) and 3.33 g N,N-diethyl-3-oxobutane amide were reacted according to General Preparation Procedure A. The product consisted of 4.49 g of a yellow, microcrystalline solid.

(13) .sup.1H-NMR(CDCl.sub.3):δ1.5 and 1.9(2×t,12H,CH.sub.3CH.sub.2),2.0(s,6H,CH.sub.3CO),3.15,3.3 and 3.55(3×dq,8H,CH.sub.3CH.sub.2),5.2(s,2H,enol-CH).

(14) FT-IR:2974,2932,2872,1720,1594,1491,1437,1358,1308,1276,1197,1081,1015, 961,929,903,773,660.

(15) UV-vis: 309(0.11) and 275(0.23). (compare dioxomolybdenum(VI) bis(acetylacetonate):314(0.13) and 270(0.27).)

Example 2

Dioxomolybdenum(VI) Bis(n,n-Diethyl-3-Oxobutane Amidate) in TEGDME

(16) 6.54 g Dioxomolybdenum(VI) bis(acetylacetonate) and 7.21 g N,N-diethyl-3-oxobutane amide were reacted in 18.00 g TEGDME according to General Preparation Procedure C. The product consisted of 31.75 g of an orange-colored solution.

Example 3

Dioxomolybdenum(VI) Bis(N,N-Dibutyl-3-Oxobutane Amidate)

(17) 3.26 g Dioxomolybdenum(VI) bis(acetylacetonate) and 4.48 g N,N-dibutyl-3-oxobutane amide were reacted according to General Preparation Procedure A. The product consisted of 6.12 g of a yellow solid.

(18) .sup.1H-NMR(CDCl.sub.3):δ0.9(dt, 12H,Me),1.2-1.5(m,8H, CH.sub.2Me),1.5-1.6(m,8H, CH.sub.2CH.sub.2N),2.0(s,6H,MeCO),2.9-3.0(m,4H,NCH.sub.2),3.1-3.3(m,8H,NCH.sub.2),3.5-3.65(m, 4H,NCH.sub.2),5.15(s,2H,enol-CH).

(19) FT-IR:3500,2916,2854,1717,1582,1505,1445,1361,1255,1192,1112,987,958, 904,860,771,731,670.

Example 4

Dioxomolybdenum(VI) Bis(N,N-Bis(2-Methoxyethyl)-3-Oxobutane Amidate)

(20) 3.26 g Dioxomolybdenum(VI) bis(acetylacetonate) and 4.56 g N,N-bis(2-methoxyethyl)-3-oxobutane amide were reacted according to General Preparation Procedure A. The product consisted of 6.15 g of a brownish, highly viscous oil.

(21) .sup.1H-NMR(CDCl.sub.3):δ1.95,2.0,2.05,2.15(4×s,6H,MeCO),3.35 (s,12H,OMe),3.4-3.8(m,16H,NCH.sub.2and OCH.sub.2),5.3,5.4,5.5and 5.7(4×s,2H,enol-CH)

(22) FT-IR:2925,2889,1718,1636,1587,1501,1430,1355,1274,1191,1110,1007,960, 927, 898, 774, 662.

Example 5

Dioxomolybdenum(VI) Bis(N,N-Bis(2-Methoxyethyl)-3-Oxobutane Amidate) in TEGDME

(23) 3.26 g Dioxomolybdenum(VI) bis(acetylacetonate) and 4.79 g N,N-bis(2-methoxyethyl)-3-oxobutane amide were reacted in 9.16 g TEGDME according to General Preparation Procedure C. The product consisted of 17.21 g of an orange-colored solution.

Example 6

Dioxomolybdenum(VI) Bis(N-Cyclohexyl-N-Methyl-3-Oxobutane Amidate)

(24) 3.26 g Dioxomolybdenum(VI) bis(acetylacetonate) and 4.14 g N-cyclohexyl-N-methyl-3-oxobutane amide were reacted according to General Preparation Procedure A. The product consisted of 5.94 g of an orange-colored, highly viscous oil.

(25) .sup.1H-NMR(CDCl.sub.3):δ1.0-1.9(m, 20H,CH.sub.2),2.0-2.1 (m,6H,MeCO),2.3(s,3H,Me from the ligand),2.75-2.9(4×s,6H,NMe),4.2-4.5(m,2H, CHN),5.15-5.6(8×s,2H,enol-CH).

(26) FT-IR:2926,2854,1719,1601,1508,1449,1346,1316,1265,1199,1164,1010,956, 932,902,773,731,701.

Example 7

Dioxomolybdenum(VI) Bis(N-Cyclohexyl-N-Methyl-3-Oxobutane Amidate) in TEGDME

(27) 3.31 g Dioxomolybdenum(VI) bis(acetylacetonate) and 4.49 g N-cyclohexyl-N-methyl-3-oxobutane amide were reacted in 10.50 g TEGDME according to General Preparation Procedure C. The product consisted of 18.30 g of an orange-colored solution.

Example 8

Dioxomolybdenum(VI) Bis(1-Morpholinobutane-1,3-Dionate)

(28) 3.26 g Dioxomolybdenum(VI) bis(acetylacetonate) and 3.59 g 1-morpholinobutane-1,3-dione were reacted according to General Preparation Procedure A. The product consisted of 5.41 g of a yellow solid.

(29) .sup.1H-NMR(CDCl.sub.3):δ2.05(s,3H,MeCO),3.4-3.8(m,16H, NCH.sub.2and OCH.sub.2),5.25(s,2H, enol-CH).

(30) FT-IR:2955,2870,1734,1606,1505,1464,1433,1366,1293,1228,1193,955,931, 901,772,734,697.

Example 9

Dioxomolybdenum(VI) Bis(1-(4-Methylpiperazin-1-Yl)Butane-1,3-Dionate)

(31) 3.26 g Dioxomolybdenum(VI) bis(acetylacetonate) and 3.87 g 1-(4-methylpiperazin-1-yl)butane-1,3-dione were reacted according to General Preparation Procedure A. The product consisted of 6.02 g of an orange-colored, highly viscous oil. .sup.1H-NMR(CDCl.sub.3):δ2.05(s,6H,MeCO),2.3(d, 6H,NMe),2.4(dd,8H,NCH.sub.2),3.45 (dd,4H,CH.sub.2N),3.65(dd,2H,CH.sub.2N),5.15,5.25,5.5(3×s, 2H,enol-CH).

(32) FT-IR:3411,2938,2791,1719,1606,1499,1446,1360,1291,1260,1142,991,959, 930,903,772,669.

Example 10

Dioxomolybdenum(VI) Bis(N,N-Dibutyl-3-Oxoheptane Amidate)

(33) 3.19 g Dioxomolybdenum(VI) bis(acetylacetonate) and 5.26 g N,N-dibutyl-3-oxoheptane amide were reacted according to General Preparation Procedure A. The product consisted of 6.52 g of an orange-yellow, highly viscous oil.

(34) .sup.1H-NMR (CDCl.sub.3):δ0.85-1.0(m, 18H,Me),1.3-1.45(m, 12H,CH.sub.2Me),1.5-1.65(m, 12H,CH.sub.2CH.sub.2Me),2.05-2.3(m, 4H,CH.sub.2CO),2.9-3.0 (m,2H,CH.sub.2N),3.15-3.45(m,6H, CH.sub.2N),3.5-3.65(br s,2H, remaining CH.sub.2),5.15,5.25and 5.7 (3×s,2H,enol-CH).

(35) FT-IR:2954,2870,1737,1604,1584,1501,1463,1369,1292,1226,1185,930,902, 774,733.

Example 11

Dioxomolybdenum(VI) Bis(N,N-Dibutyl-3-Oxoheptane Amidate) in TEGDME

(36) 3.24 g Dioxomolybdenum(VI) bis(acetylacetonate) and 5.58 g N,N-dibutyl-3-oxoheptane amide were reacted in 6.70 g TEGDME according to General Preparation Procedure C. The product consisted of 15.52 g of an orange-colored solution.

Example 12

Dioxomolybdenum(VI) Bis(N,N-Bis(2-Methoxyethyl)-3-Oxoheptane Amidate)

(37) 3.72 g Dioxomolybdenum(VI) bis(acetylacetonate) and 6.21 g N,N-bis(2-methoxyethyl)-3-oxoheptane amide were reacted according to General Preparation Procedure A. The product consisted of 7.66 g of an orange-yellow solid.

(38) .sup.1H-NMR(CDCl.sub.3):δ0.9(t, 6H,Me),1.35(dq,4H,CH.sub.2Me),1.5-1.7 (m,4H, CH.sub.2CH.sub.2Me),2.25(t,4H,CH.sub.2CO),3.35(s,12H,OMe),3.3-3.8(m,20H,CH.sub.2O,CH.sub.2N and CH.sub.2),5.3(s,2H,enol-CH).

(39) FT-IR:2927,2871,1746,1716,1602,1502,1372,1274,1185,1115,1012,957,927, 904,775.

Example 13

Dioxomolybdenum(VI) Bis(N-Cyclohexyl-N-Methyl-3-Oxoheptane Amidate)

(40) 3.66 g Dioxomolybdenum(VI) bis(acetylacetonate) and 5.03 g N-cyclohexyl-N-methyl-3-oxoheptane amide were reacted according to General Preparation Procedure A. The product consisted of 6.86 g of a brownish, highly viscous oil.

(41) .sup.1H-NMR(DMSO-d.sub.6):δ0.7-0.9(m,6H,Me),1.0-1.9(m,28H,CH.sub.2Me,CH.sub.2CH.sub.2Me, CH.sub.2),2.2-2.3(m,4H,CH.sub.2CO),2.7-2.9(m,6H,NMe),4.2-4.3(m,2H,CHN),5.4,5.5,5.7, 5.9(4×s,2H,enol-CH).

(42) FT-IR:2926,2855,1739,1717,1601,1498,1449,1350,1318,1254,1189,1164,1025, 970,930,900,774,729,667.

Example 14

Dioxomolybdenum(VI) Bis(1-Morpholinoheptane-1,3-Dionate)

(43) 3.66 g Dioxomolybdenum(VI) bis(acetylacetonate) and 5.03 g 1-morpholinoheptane-1,3-dione were reacted according to General Preparation Procedure A. The product consisted of 6.58 g of a brownish, highly viscous oil.

(44) .sup.1H-NMR(DMSO-d.sub.6):δ0.8-0,9(m,6H,Me),1.2-1.35(m, 4H,CH.sub.2Me),1.4-1.5(m,4H,CH.sub.2CH.sub.2Me),3.3-3.7 (m, 16H,CH.sub.2O,CH.sub.2N and CH.sub.2),5.55,5.65,5.95(3×s,2H,enol-CH).

(45) FT-IR:2956,2857,1717,1600,1500,1441,1370,1251,1185,1113,929,900,861,772, 667.

Example 15

Dioxomolybdenum(VI) Bis(N,N-Diethyl-3-Phenyl-3-Oxopropane Amidate)

(46) 2.05 g sodium molybdate dihydrate and 4.33 g N,N-diethyl-3-phenyl-3-oxopropanamide were reacted according to General Preparation Procedure B. The product consisted of 5.18 g of a yellow, microcrystalline solid.

(47) .sup.1H-NMR(DMSO-d.sub.6):δ0.9and 1.15(2×t,12H,Me),3.1-3.6(m, 8H,CH.sub.2Me),6.1(s,2H,enol-CH),7.45-7.5(m,6H,arom-H),7.8-7.85(m, 4H,arom-H).

(48) FT-IR:2975,1605,1573,488,1439,1357,1282,1238,1101,929,899,765,694,673.

Example 16

Dioxomolybdenum(VI) Bis(N,N-Dibutyl-3-Oxo-3-Phenyl Propane Amidate)

(49) 3.26 g Dioxomolybdenum(VI) bis(acetylacetonate) and 5.78 g N,N-dibutyl-3-oxo-3-phenyl propanamide were reacted according to General Preparation Procedure A. The product consisted of 7.35 g of a yellow solid.

(50) .sup.1H-NMR(CDCl.sub.3):δ0.7(t,12H,Me),0.9-1.0(m,12H, Me),1.3-1.45(m,8H, CH.sub.2Me),1.5-1.7(m,8H,CH.sub.2CH2Me),2.9-3.05(m,2H,CH.sub.2N),3.2-3.4(m,2H,CH.sub.2N), 3.45-3.6(m,2H,CH.sub.2N),5.7,5.9,5.95(4×s,2H,enol-CH), 7.35-7.45(m, 6H,arom-H),7.75-7.8 (m, 4H, arom-H).

(51) FT-IR: 2955,2869,1740,1684,1604,1572,1488,1358,1294,1215,1104,1022,932, 901,765,734,692.

Example 17

Dioxomolybdenum(VI) Bis(N,N-Dibutyl-3-Oxo-3-Phenyl Propanamidate) in TEGDME

(52) 3.37 g Dioxomolybdenum(VI) bis(acetylacetonate) and 6.25 g N,N-dibutyl-3-oxo-3-phenyl propanamide were reacted in 6.76 g TEGDME according to General Preparation Procedure C. The product consisted of 16.38 g of a yellow orange solution.

Example 18

Dioxomolybdenum(VI) Bis(1-Morpholino-3-Phenylpropane-1,3-Dionate)

(53) 3.26 g Dioxomolybdenum(VI) bis(acetylacetonate) and 4.90 g 1-morpholino-3-phenylpropane-1,3-dione were reacted according to General Preparation Procedure A. The product consisted of 7.09 g of an orange-yellow solid.

(54) .sup.1H-NMR(CDCl.sub.3):δ3.4-3.85(m, 16H,CH.sub.2N and CH.sub.2O),5.5,5.75,5.8,5.9and 5.05(5×s,2H,enol-CH),7.35-7.5(m,6H,arom-H),7.75-7.85(m, 2H,arom-H),8.0-8.1(m,2H, arom-H).

(55) FT-IR:3056,2967,2918,2856,2359,1684,1571,1496,1358,1263,1234,1114,1051, 1026,933,901,763,731,689.

Example 19

Dioxomolybdenum(VI) Bis(N,N-Dibutyl-2-Oxocyclopentane Carboxamidate)

(56) 3.26 g Dioxomolybdenum(VI) bis(acetylacetonate) and 5.02 g N,N-dibutyl-2-oxocyclopentane carboxamide were reacted according to General Preparation Procedure A. The product consisted of 7.90 g of a yellow solid.

(57) .sup.1H-NMR(CDCl.sub.3):δ0.9-1.0(2×t,6H,CH.sub.2CH.sub.3),1.25-1.4(m,8H,CH.sub.2CH.sub.3),1.4-1.6(m,8H,CH.sub.2CH.sub.2CH.sub.3),1.8-1.95(m,2H,CH.sub.2.sup.cy),2.15-2.55(m,10H,CH.sub.2.sup.cy),3.1-3.2(m,4H, NCH.sub.2),3.35(t,1H,CHCO),3.45-3.6(m,4H,NCH.sub.2),5.5,5.7 and 5.8(3×s,2H,enol-CH).

(58) FT-IR:2955,2871,1739,1632,1587,1562,1516,1456,1371,1265,1230,1104,1026, 932,903,796,734,699,668.

Example 20

Dioxomolybdenum(VI) Bis(N,N-Bis-Dibutyl-2-Oxocyclopentane Carboxamidate) in TEGDME

(59) 3.29 Dioxomolybdenum(VI) bis(acetylacetonate) and 5.10 g N,N-dibutyl-2-oxocyclopentane carboxamide were reacted in 8.78 g TEGDME according to General Preparation Procedure C. The product consisted of 17.17 g of an orange brown solution in which crystals formed as the solution was left to stand.

Example 21

Dioxomolybdenum(VI) Acetylacetonate (N,N-Diethyl-3-Oxobutanamidate)

(60) 4.24 g Dioxomolybdenum(VI) bis(acetylacetonate) and 2.12 g N,N-diethyl-3-oxobutane amide were reacted according to General Preparation Procedure A. The product consisted of 4.95 g of a yellow, microcrystalline solid. .sup.1H-NMR(DMSO-d.sub.6):δ0.9and 1.1(2×t,12H,Me),1.9,2.0and 2.15(3×s,9H,MeCO), 3.1-3.4(m,4H,CH.sub.2N),5.45-6.0(6×s,2H,enol-CH).

(61) FT-IR:2976,2934,1715,1588,1504,1437,1357,1308,1265,1197,1080,1017,963, 931,904,783,666.

Example 22

Dioxomolybdenum(VI) (N,N-Diethyl-3-Oxobutanamidate) (N,N-Bis(2-Methoxyethyl)-3-Oxobutanamidate))

(62) 3.35 g Dioxomolybdenum(VI) bis(acetylacetonate) and a combination of 1.71 g N,N-diethyl-3-oxobutane amide and 2.35 g N,N-bis(2-methoxyethyl)-3-oxobutane amide were reacted according to General Preparation Procedure A. The product consisted of 5.42 g of a reddish, highly viscous oil.

(63) .sup.1H-NMR(DMSO-d.sub.6):δ0.95-1.0(dt,6H,Me),1.05-1.15(m,6H,Me),1.9-2.5(3×s,6H,MeCO),3.2-3.6(m,12H,CH.sub.2N and CH.sub.2O),5.5(dd,2H,enol-CH),5.9(d,1H,enol-CH).

(64) FT-IR:2980,2889,1718,1587,1499,1453,1436,1355,1305,1275,1195,1112,1013, 960,925,897,773,658.

(65) Single-component polyurethane compositions

Examples 23 to 26 and Comparative Examples V1 to V2

(66) For each example, the polyurethane polymer P1, whose preparation is described below, was mixed in a polypropylene beaker with screw cap by means of a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.; 1 min at 2500 rpm) with a catalyst to form a homogeneous composition, and the composition so obtained was filled into an internally painted aluminum tube and this tube was closed in an airtight manner.

(67) The polyurethane polymer P1 was prepared as follows:

(68) 1300 g Polyoxypropylenediol (Acclaim® 4200 N, from Bayer; OH number 28.5 mg KOH/g), 2600 g polyoxypropylene polyoxyethylenetriol (Caradol® MD34-02, from Shell; OH number 35.0 mg KOH/g), 600 g 4,4′-methylene diphenyl diisocyanate (4,4′-MDI; Desmodure® 44 MC L, from Bayer) and 500 g diisodecyl phthalate (DIDP; Palatinol® Z, from BASF) were reacted according to known methods at 80° C. to form an NCO-terminated polyurethane polymer with a content of free isocyanate groups of 2.05 wt %.

(69) The resulting compositions were tested to determine their storage stability as well as their curing rate.

(70) As a measurement of the storage stability, the change in the viscosity during storage with exposure to heat was determined. For this purpose, the compositions were stored in the closed tube in the oven at 60° C. and the viscosity at 20° C. was measured the first time after 4 hours (=“viscosity fresh”) and a second time after 7 days (=“viscosity stored”) storage duration. The storage stability is determined as the percent increase of the second viscosity value compared to the first one. For this purpose, the viscosity increase in % was calculated according to the following formula:
[(Viscosity after 7 d/viscosity after 4 h)−1]×100%.

(71) As a measurement for the curing rate, the tack-free time (skin formation time [HBZ]) was determined, in particular for the compositions which had been stored for 4 hours at 60° C. (=“HBZ fresh”) and for the compositions which had been stored for 7 days at 60° C. (=“HBZ stored”). For this purpose, the room-temperature compositions were applied in a layer thickness of approximately 3 mm to cardboard, and, under standard atmospheric conditions (“NK;” 23±1° C., 50±5% relative humidity), the time was determined in each case until the first time that no residues remained on the pipette after slightly tapping the surface of composition with a pipette made of LDPE.

(72) The results of these tests are listed in Table 1.

(73) TABLE-US-00002 TABLE 1 Single-component polyurethane compositions (Quantities in parts by weight). Example 23 24 25 26 V1 V2 Polyurethane polymer P1 50 50 50 50 50 50 Catalyst Example 2 0.72 — — — — — Catalyst Example 5 — 0.78 — — — — Catalyst Example 10 — — 0.30 — — — Catalyst Example 20 — — — 0.77 — — MoO.sub.2(acac).sub.2.sup.a — — — — 0.73 — Molybdenum carboxylate.sup.b — — — — — 0.29 mmol-equiv./100 g.sup.c 0.9 0.9 0.9 0.9 0.9 0.9 Viscosity fresh (Pa .Math. s) 57.7 57.3 81.6 59.7 122 64.7 Viscosity stored (Pa .Math. s) 98.0 87.1 111 104 gelled 84.6 Viscosity increase (%) 70 52 36 74 >300 31 HBZ fresh (min) 86 94 145 95 83 >360 HBZ stored (min) 150 154 170 110 — >360 .sup.a20% solution in methyl ethyl ketone. .sup.bMolybdenum-2-ethyl hexanoate (15% Mo, from Shepherd). .sup.cmmol-equivalents of molybdenum atoms of the catalyst per 100 g of the composition.

(74) It is evident from Table 1 that the single-component polyurethane compositions with the catalysts according to the invention have comparatively satisfactory storage stabilities and skin formation times.

(75) Two-component polyurethane compositions

Examples 27 to 28 and Comparative Examples V3 to V7

(76) For the preparation of the first component, for each example, a polyethertriol (Voranol® CP 4755, from Dow) and a catalyst according to Table 2 were intimately mixed in a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) for 30 s at 3000 rpm. A portion of the freshly prepared first component was subsequently filled into an internally painted aluminum tube; this tube was closed in an airtight manner and stored for 7 days in a convection oven at 60° C.

(77) For each example, the rest of the freshly prepared first component was mixed in the described manner with a modified diphenylmethane diisocyanate (Desmodur® CD-L, produced by Bayer), which is liquid at room temperature, as second component according to Table 2 to form a polyurethane composition.

(78) Likewise, for each example, the first component which had been stored for 7 days at 60° C. was mixed with the second component according to Table 2 in the same manner to form a polyurethane composition.

(79) TABLE-US-00003 TABLE 2 Two-component polyurethane compositions (Quantities in parts by weight). Example 27 28 V3 V4 V5 V6 V7 First component: Voranol ® CP 4755 50 50 50 50 50 50 50 Catalyst Example 2 0.71 — — — — — — Catalyst Example 11 — 0.75 — — — — — MoO.sub.2(acac).sub.2.sup.a — — 1.74 — — — — Molybdenum carboxylate.sup.b — — — 0.81 — — — DBTDL.sup.c — — — — 0.46 — — Coscat ® 83.sup.d — — — — — 0.02 — DABCO 33-LV ® .sup.e — — — — — — 0.10 mmol-equiv./100 g.sup.f 0.80 0.86 2.68 2.27 0.13 0.03 1.07 Second component: Desmodur  ® CD-L 5.10 5.10 5.10 5.10 5.10 5.10 5.10 .sup.a28.6% suspension in methyl ethyl ketone. .sup.bMolybdenum-2-ethylhexanoate (15% Mo, from Shepherd). .sup.c10% solution of dibutyltin dilaurate in diisodecyl phthalate. .sup.dBismuth tris(neodecanoate) in neodecanoic acid (16% Bi, from Erbslöh). .sup.e33% solution of 1,4-diazabicyclo[2.2.2]octane in dipropylene glycol (from Air Products). .sup.fmmol equivalents of metal atoms or amino groups of the catalyst per 100 g of the composition.

(80) The polyurethane compositions were checked to determine the appearance, tack-free time, bubble formation and Shore A hardness, in particular in each case both for the composition with the freshly prepared first component and also for the composition with the first component which had been stored for 7 days at 60° C. Moreover, exclusively for the composition with the freshly prepared first component, the mechanical properties were also measured in the tensile test, in particular before and after various storage procedures for accelerated aging of the samples.

(81) The appearance of the composition was evaluated purely visually and ranked as “clear,” “turbid” or “inhomogeneous” (“inh.”).

(82) The tack-free time (skin formation time) was measured as described in Example 23.

(83) The bubble formation was evaluated visually using the number (“many,” “some,” “none”) of gas bubbles which occurred in the composition prepared for the determination of the skin formation time during its curing.

(84) The Shore A hardness was determined according to DIN 53505 on test specimens that had been cured for 7 days under standard atmospheric conditions.

(85) For the determination of the mechanical properties in the tensile test, films having a thickness of approximately 3 mm were prepared from the compositions, by pouring the composition into a flat PTFE mold and curing it for 7 days under standard atmospheric conditions. Tack-free, elastic films were obtained. From the films, dumbbell shaped samples were punched, having a length of 75 mm, with a bar length of 30 mm, and a bar width of 4 mm, and some of them were tested according to DIN EN 53504 at a traction rate of 200 mm/min to determine the tensile strength, the elongation at rupture, and the E modulus (at an elongation of 0.5 to 5.0%). The rest of the dumbbells were stored for 1 day at 100° C. in the convection oven, for example, for 10 days under “cataplasm” (40° C. and 100% relative humidity) or for 10 days under “cataplasm” as well as for 1 day at 100° C., whereafter, in each case, they were kept for one day under standard atmospheric conditions and tested as described according to DIN EN 53504.

(86) The results of these tests are listed in Table 3.

(87) TABLE-US-00004 TABLE 3 Properties of the two-component polyurethane compositions Example 27 28 V3 V4 V5 V6 V7 Composition with freshly prepared first component: Appearance clear clear inh. clear clear clear clear Skin formation time 9 15 35 110 10 3 15 (min) Shore A hardness 42 42 16 25 48 44 33 Bubble formation none none none some some none some Tensile strength 0.86 0.76 0.54 0.66 0.76 0.54 0.90 (MPa): 7 d/NK +10 d/cataplasm 0.75 0.80 0.62 0.71 0.71 0.79 0.82 +1 d/100° C. 0.92 0.82 0.66 0.68 0.60 0.73 0.86 +10 d/cataplasm + 0.85 0.86 0.61 0.77 0.65 0.73 0.89 1 d/100° C. Elongation at rupture 78 67 81 83 65 42 100 (%): 7 d/NK +10 d/cataplasm 63 72 105 85 56 73 85 +1 d/100° C. 90 91 123 108 168 72 105 +10 d/cataplasm + 83 97 110 124 170 74 108 1 d/100° C. E modulus (MPa): 1.66 1.58 0.85 1.21 1.68 1.46 1.44 7 d/NK +10 d/cataplasm 1.66 1.57 0.85 1.21 1.68 1.56 1.47 +1 d/100° C. 1.57 1.36 0.92 1.00 0.60 1.49 1.23 +10 d/cataplasm + 1.50 1.36 0.80 1.06 0.71 1.41 1.23 1 d/100° C. Composition with stored Appearance clear clear inh. clear clear clear clear Skin formation time 9 15 30 120 10 45 15 (min) Shore A hardness 44 46 32 34 48 45 32 Bubble formation none none none some some some some

(88) From Table 3 it is evident that the two-component polyurethane compositions with the catalysts according to the invention represent clear, homogeneous mixtures which have both before and also after storage comparatively short skin formation times and which cure without bubbles to form a material with comparatively high strength and satisfactory resistance.

Examples 29 to 30 and Comparative Examples V8 to V12

(89) For the preparation of the first component, for each example, a polyether triol (Voranol®CP 4755, from Dow), a polyether diol (Acclaim® 4200, from Bayer), and a catalyst according to Table 4 were intimately mixed in a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) for 30 s at 3000 rpm. A portion of the freshly prepared first component was then filled into an internally painted aluminum tube; this tube was closed in an airtight manner, and stored for 7 days in a convection oven at 60° C.

(90) For each example, the rest of the freshly prepared first component was mixed in the described manner with a modified diphenylmethane diisocyanate (Desmodur® CD-L, from Bayer), which is liquid at room temperature, as second component according to Table 4 to form a polyurethane composition.

(91) Likewise, for each example, the first component which had been stored for 7 days at 60° C. was mixed with the second component according to Table 4 in the same manner to form a polyurethane composition.

(92) TABLE-US-00005 TABLE 4 Two-component polyurethrane compositions (Quantities in parts by weight). Example 29 30 V8 V9 V10 V11 V12 First component: Voranol ® CP 4755 33.3 33.3 33.3 33.3 33.3 33.3 33.3 Acclaim ® 4200 16.7 16.7 16.7 16.7 16.7 16.7 16.7 Catalyst Example 2 0.71 — — — — — — Catalyst Example 11 — 0.48 — — — — — MoO.sub.2(acac).sub.2.sup.a — — 1.64 — — — — Molybdenum carboxylate.sup.b — — — 0.70 — — — DBTDL.sup.c — — — — 0.49 — — Coscat ® 83.sup.d — — — — — 0.02 — DABCO 33-LV ® .sup.e — — — — — — 0.14 mmol-equiv./100 g.sup.f 0.81 0.55 2.54 1.96 0.14 0.03 1.50 Second component: Desmodur ® CD-L 5.00 5.00 5.00 5.00 5.00 5.00 5.00 .sup.a28.6% suspension in methyl ethyl ketone. .sup.bMolybdenum-2-ethylhexanoate (15.5% Mo, from Shepherd). .sup.c10% solution of dibutyltin dilaurate in diisodecyl phthalate. .sup.dBismuth tris(neodecanoate) in neodecanoic acid (16% Bi, from Erbslöh). .sup.e33% solution of 1,4-diazabicyclo[2.2.2]octane in dipropylene glycol (from Air Products). .sup.fmmol equivalents of metal atoms or amino groups of the catalyst per 100 g of the composition.

(93) The polyurethane compositions were checked as for Example 27 to determine the appearance, tack-free time, bubble formation and Shore A hardness, in particular in each case both for the composition with the freshly prepared first component and also for the composition with the first component which had been stored for 7 days at 60° C. Moreover, as described in Example 27, exclusively for the composition with the freshly prepared first component, the mechanical properties were also measured in the tensile test, in particular before and after various storage procedures for accelerated aging of the samples.

(94) The results of these tests are listed in Table 5.

(95) TABLE-US-00006 TABLE 5 Properties of the two-component polyurethane compositions Example 29 30 V8 V9 V10 V11 V12 Composition with freshly prepared first component: Appearance clear clear inh. clear clear clear clear Skin formation time 15 35 17 105 27 90 35 (min) Shore A hardness 44 41 42 32 48 42 33 Bubble formation none none none some many none many Tensile strength 0.75 0.72 0.77 0.63 0.77 0.71 0.65 (MPa): 7 d/NK +10 d/cataplasm 0.73 0.71 0.77 0.59 0.77 0.73 0.66 +1 d/100° C. 0.77 0.75 0.76 0.62 0.48 0.70 0.72 +10 d/cataplasm + 0.75 0.72 0.87 0.66 0.52 0.74 0.69 1 d/100° C. Elongation at rupture 97 117 115 109 105 124 135 (%): 7 d/NK +10 d/cataplasm 95 125 116 112 105 119 148 +1 d/100° C. 136 188 148 181 341 137 193 +10 d/cataplasm + 122 139 171 156 303 178 181 1 d/100° C. E modulus (MPa): 1.42 0.99 1.12 0.89 1.20 0.82 0.88 7 d/NK +10 d/cataplasm 1.18 0.94 1.06 0.84 1.30 0.98 0.81 +1 d/100° C. 1.01 0.76 0.98 0.61 0.20 0.91 0.69 +10 d/cataplasm + 1.08 0.96 1.04 0.82 0.28 0.80 0.65 1 d/100° C. Composition with stored first component: Appearance clear clear inh. clear clear clear clear Skin formation time 8 30 14 100 27 300 35 (min.) Shore A hardness 45 44 45 40 45 41 40 Bubble formation none none none some some some some

(96) From Table 5 it is evident that the two-component polyurethane compositions with the catalysts according to the invention represent clear, homogeneous mixtures which have both before and also after storage comparatively short skin formation times and which cure without bubbles to form a material with comparatively high strength and satisfactory resistance.

Examples 31 to 39

(97) As described for Example 27, for the preparation of the first component, in each case, a polyether triol (Voranol® CP 4755, from Dow) and a catalyst according to Table 6 were mixed. A portion of the freshly prepared first component was then filled into an internally painted aluminum tube; this tube was closed in an airtight manner and stored for 7 days in a convection oven at 60° C.

(98) The rest of the freshly prepared first component was mixed for each example in the manner described for Example 27 with a modified diphenylmethane diisocyanate (Desmodur CD-L, from Bayer), which is liquid at room temperature, as second component according to Table 6 to form a polyurethane mixture.

(99) Likewise, for each example, the first component which had been stored for 7 days at 60° C. was mixed with the second component according to Table 6 in the same manner to form a polyurethane composition.

(100) The polyurethane compositions were checked as for Example 27 to determine the appearance, tack-free time, bubble formation and Shore A hardness as well as the mechanical properties in the tensile test.

(101) The results of these tests are listed in Table 7.

(102) TABLE-US-00007 TABLE 6 Two-component polyurethane compositions Example 31 32 33 34 35 36 37 38 39 First component: Voranol ® CP 4755 30 30 30 30 30 30 30 30 30 Catalyst Example 2 1.13 0.16 — — — — — — — Catalyst Example 5 — — 1.22 — — — — — — Catalyst Example 7 — — — 1.28 — — — — — Catalyst Example 10 — — — — 0.46 — — — — Catalyst Example 11 — — — — — 1.10 — — — Catalyst Example 14 — — — — — — 0.39 — — Catalyst Example 17 — — — — — — — 1.12 — Catalyst Example 22 — — — — — — — — 0.35 mmol-equiv./100 g.sup.a 2.09 0.30 2.06 2.06 2.06 2.06 1.99 2.06 1.98 Second component: Desmodur ® CD-L 3.10 3.10 3.10 3.10 3.10 3.10 3.10 3.10 3.10 .sup.ammol-equivalents of molybdenum atoms of the catalysts per 100 g of the composition.

(103) TABLE-US-00008 TABLE 7 Properties of the two-component polyurethane compositions. Example 31 32 33 34 35 36 37 38 39 Composition with fresh prepared first component: Appearance clear clear clear clear clear clear clear clear clear Skin formation time (min) 11 40 4 10 8 9 7 12 11 Shore A hardness 32 39 44 44 45 42 48 46 45 Bubble formation none none none none none none none none none Composition with stored first component: Appearance clear clear clear clear clear clear clear clear clear Skin formation time (min) 7 31 5 5 3 8 6 6 2 Shore A hardness 39 40 46 44 48 47 46 46 44 Bubble formation none none none none none some none none none

(104) As can be seen in Table 7, the two-component polyurethane compositions with the catalysts according to the invention represent clear, homogeneous mixtures which have relatively short skin formation times both before and after storage and which cure largely without bubbles to form a material with a satisfactory Shore A hardness.