Polyurethane composition having long processing time and high strength

Abstract

A composition including a first component containing at least one polyol and at least one compound having at least one reactive group of the formula (I), and a second component containing at least one aromatic polyisocyanate and/or at least one polymer containing aromatic isocyanate groups. The composition has a long open time and, even in the case of small amounts of compound having at least one reactive group of the formula (I), enables elastic coatings having improved mechanical properties without causing problems with odor emissions or migration effects. It is thus particularly suitable as a coating for floors or roof areas.

Claims

1. A composition comprising: a first component containing: at least one polyol, and at least one of the formula (II a) ##STR00016## where: R.sup.1 is an alkyl radical having 1 to 8 carbon atoms or a phenyl radical, s is 2 or 3, A.sup.1 is a di- or trivalent organic radical having 6 to 100 carbon atoms and at least 2 ether groups, X is: an alkyl or alkoxy radical having 1 to 8 carbon atoms, or a radical of the formula NR.sup.2R.sup.3 where R.sup.2 and R.sup.3 are each independently H or an alkyl, cycloalkyl, aralkyl or aryl radical optionally having ether oxygen and having 1 to 12 carbon atoms, or together are an alkylene radical optionally having ether oxygen and having 3 to 6 carbon atoms, and the compound has an average molecular weight M.sub.n of not more than 2,500 g/mol, and a second component containing at least one aromatic polyisocyanate and/or at least one polymer containing aromatic isocyanate groups.

2. The composition as claimed in claim 1, wherein: s is 2 and A.sup.1 is ?,?-polyoxypropylene having an average molecular weight M.sub.n in the range from 170 to 500 g/mol, or s is 3 and A.sup.1 is a trivalent polyoxypropylene radical started from trimethylolpropane or glycerol and having an average molecular weight M.sub.n in the range from 300 to 500 g/mol.

3. The composition as claimed in claim 1, wherein the polyol has an average molecular weight M.sub.n in the range from 500 to 10,000 g/mol and an average OH functionality in the range from 1.8 to 3.

4. The composition as claimed in claim 1, wherein the polyol comprises at least one fatty acid-based polyol having an average molecular weight M.sub.n in the range from 500 to 2,000 g/mol.

5. The composition as claimed in claim 1, wherein the polyol comprises at least one polyether triol having an average molecular weight M.sub.n in the range from 3,000 to 6,000 g/mol.

6. The composition as claimed in claim 1, wherein the second component comprises diphenylmethane 4,4-diisocyanate.

7. The composition as claimed in claim 1, further comprising at least one further constituent selected from fillers, adhesion promoters, desiccants, catalysts and stabilizers.

8. The composition as claimed in claim 1, containing 1% to 50% by weight of compounds of the formula (II a), based on the sum total of the constituents reactive with isocyanate groups in the first component.

9. A cured composition obtained from the composition as claimed in claim 1 after the two components have been mixed and cured.

10. A coating comprising the cured composition as claimed in claim 9 coated on a floor or roof area.

11. The composition as claimed in claim 6, wherein the second component further comprises fractions of diphenylmethane 2,4- or 2,2-diisocyanate or derivatives of diphenylmethane 4,4-diisocyanate or homologs of diphenylmethane 4,4-diisocyanate.

Description

EXAMPLES

(1) Working examples are presented hereinbelow, which are intended to further elucidate the invention described. The invention is of course not limited to these described working examples.

(2) Standard climatic conditions refer to a temperature of 23?1? C. and a relative air humidity of 50?5%.

(3) The chemicals used, unless stated otherwise, were from Sigma-Aldrich and were used without further pretreatment.

(4) Preparation of Compounds Having Reactive Groups of the Formula (I):

(5) Amine value was determined by titration (with 0.1N HClO.sub.4 in acetic acid versus crystal violet).

(6) Viscosity was measured with a thermostated Rheotec RC30 cone-plate viscometer (Brookfield, cone diameter 50 mm, cone angle 1?, cone tip-plate distance 0.05 mm, shear rate 10 s.sup.?1).

(7) Infrared spectra (FT-IR) were measured as undiluted films on a Nicolet iS5 FT-IR instrument from Thermo Scientific equipped with a horizontal ATR measurement unit with a diamond crystal. The absorption bands are reported in wavenumbers (cm.sup.?1).

(8) .sup.1H- and .sup.13C NMR spectra were measured at room temperature on a spectrometer of the Bruker Ascend type at 400.14 MHz (.sup.1H) or 100.63 MHz (.sup.13C); the chemical shifts ? are reported in ppm relative to tetramethylsilane (TMS). Coupling constants J are reported in Hz. No distinction was made between true coupling and pseudo-coupling patterns.

Compound H-1: N,N-Bis(ethylcrotonat-3-yl)-?,?-polyoxypropylenediamine

(9) 136.5 g (1.05 mol) of ethyl acetoacetate was initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 153.0 g (0.50 mol) of ?,?-polyoxypropylenediamine having average molecular weight M.sub.n of 306 g/mol (mixture of 84.1 g of Jeffamine? D-230 and 68.9 g of Jeffamine? D-400, both from Huntsman) was added, in the course of which the temperature of the reaction mixture was kept between 15 and 25? C. by means of cooling. Subsequently, the reaction mixture was stirred at room temperature for 20 min and then the volatile constituents were removed at 80? C. and a reduced pressure of 10 mbar. A clear, pale yellow, slightly odorous liquid having a viscosity at 20? C. of 460 mPa.Math.s and an amine value of 211 mg KOH/g was obtained. On the basis of the data from

(10) .sup.1H NMR and .sup.13C NMR, compound H-1 is mainly in the form of the enamino ester.

(11) .sup.1H NMR (CDCl.sub.3): 8.54 (s, 2H, NH), 4.40 (s, 2H, C?CHC(O)O), 4.07 (q, 4H, OCH.sub.2CH.sub.3), 3.81-3.14 (m, 15H, CH.sub.2O and CHO of polyether), 1.95 (s, 6H, NC(CH.sub.3)?CH), 1.24 (t, 6H, CH.sub.3CH.sub.2O), 1.24-1.22 (m, 6H, CH.sub.3CHN), 1.17-1.06 (m, 9H, CH.sub.3CHO of polyether).

(12) .sup.13C NMR (CDCl.sub.3) (evaluated only in the range of 80 to 180 ppm): 170.5 (OC(O) ester), 161.3 (CH?CNH), 82.3 (CH?CNH).

(13) FT-IR: 2973, 2931, 2871, 1651, 1600, 1498, 1444, 1375, 1362, 1300, 1263, 1133, 1094, 1056, 1026, 976, 963, 783, 697.

Compound H-2: N,N-Bis(diethylcrotonamid-3-yl)-?,?-polyoxypropylenediamine

(14) Prepared as described for compound H-1, except using 165.1 g (1.05 mol) of N,N-diethylacetoacetamide in place of ethyl acetoacetate. A clear, yellow-orange, slightly odorous liquid having a viscosity at 20? C. of 2500 mPa.Math.s and an amine value of 198 mg KOH/g was obtained.

(15) FT-IR: 2969, 2929, 2870, 1601, 1578, 1506, 1477, 1443, 1405, 1373, 1358, 1312, 1276, 1253, 1139, 1095, 1081, 1019, 959, 927, 827, 769, 693.

Compound H-3: N,N-Bis(pent-3-en-2-on-4-yl)-?,?-polyoxypropylenediamine

(16) Prepared as described for compound H-1, except using 105.1 g (1.05 mol) of acetylacetone in place of ethyl acetoacetate. A clear, yellowish, slightly odorous liquid having a viscosity at 20? C. of 435 mPa.Math.s and an amine value of 249 mg KOH/g was obtained.

(17) FT-IR: 2970, 2870, 1607, 1570, 1512, 1441, 1353, 1296, 1101, 1009, 960, 930, 795, 735.

Compound H-4: N,N-Bis(ethylcrotonat-3-yl)-1,3-bis(aminomethyl)benzene

(18) 136.5 g (1.05 mol) of ethyl acetoacetate and 68.1 g (0.5 mol) of 1,3-bis(aminomethyl)benzene (from Mitsubishi Gas Chem.) were converted as described for compound H-1. A clear, yellow, slightly odorous liquid having a viscosity at 20? C. of 4800 mPa.Math.s and an amine value of 306 mg KOH/g was obtained, which crystallized to give a solid after a storage time of several months at room temperature.

(19) FT-IR: 3290, 2977, 2931, 2900, 2869, 1646, 1600, 1499, 1438, 1385, 1362, 1289, 1265, 1230, 1169, 1147, 1110, 1057, 1022, 830, 782, 694.

Compound H-5: N-(Ethylcrotonat-3-yl)-2-(2-aminoethoxy)ethan-1-ol

(20) 136.5 g (1.05 mol) of ethyl acetoacetate and 105.0 g (1.0 mol) of 2-(2-aminoethoxy)ethan-1-ol were converted as described for compound H-1. A clear, pale yellow, slightly odorous liquid having a viscosity at 20? C. of 118 mPa.Math.s and an amine value of 253 mg KOH/g was obtained.

(21) FT-IR: 3426 (br), 3296, 2976, 2929, 2869, 1646, 1596, 1503, 1443, 1385, 1363, 1257, 1233, 1171, 1123, 1095, 1054, 1019, 979, 922, 887, 783, 699.

Compound H-6: N-(Ethylcrotonat-3-yl)-2-aminoethanol

(22) 136.5 g (1.05 mol) of ethyl acetoacetate and 62.1 g (1.0 mol) of 2-aminoethanol were converted as described for compound H-1. A clear, pale yellow, slightly odorous liquid having a viscosity at 20? C. of 127 mPa.Math.s and an amine value of 325 mg KOH/g was obtained.

(23) FT-IR: 3398 (br), 3303, 2978, 2933, 2875, 1646, 1634, 1593, 1503, 1441, 1385, 1364, 1269, 1253, 1218, 1169, 1125, 1095, 1051, 1017, 979, 964, 881, 782, 696.

Compound H-7: ?,?-Polyoxypropylenebis(3-(N-cyclohexylamino) but-2-enoate)

(24) A round-bottom flask was initially charged with 316.1 g (0.79 mol) of polyoxypropylenediol having average molecular weight M.sub.n of about 400 g/mol (Voranol? P 400, from Dow). 249.8 g (1.58 mol) of tert-butyl acetoacetate and 0.5 g of methanesulfonic acid were added while stirring. Subsequently, the volatile constituents (tert-butanol) were removed at 80 to 120? C. and a reduced pressure of 5 mbar. The ?,?-polyoxypropylenebis(acetoacetate) intermediate was obtained in the form of a clear, pale yellow liquid having a viscosity at 20? C. of 126 mPa.Math.s. To an initial charge of 85.2 g (0.15 mol) of the intermediate thus prepared in a round-bottom flask was added 29.8 g (0.30 mol) of cyclohexylamine while stirring. Subsequently, the reaction mixture was stirred at room temperature for 20 min and then the volatile constituents were removed at 80? C. and a reduced pressure of 10 mbar. A clear, orange-yellow, slightly odorous liquid having a viscosity at 20? C. of 8400 mPa.Math.s and an amine value of 140 mg KOH/g was obtained. FT-1R: 2971, 2929, 2855, 1647, 1604, 1496, 1448, 1374, 1346, 1305, 1271, 1237, 1171, 1149, 1103, 1017, 997, 983, 927, 782, 695.

Compound H-8: N,N-Bis(ethylcrotonat-3-yl)-2,2(4),4-trimethylhexane-1,6-diamine

(25) 136.5 g (1.05 mol) of ethyl acetoacetate and 79.2 g (0.5 mol) of 2,2(4),4-trimethylhexane-1,6-diamine (Vestamin? TMD, from Evonik) were converted as described for compound H-1. A clear, yellow-orange, slightly odorous liquid having a viscosity at 20? C. of 874 mPa.Math.s and an amine value of 290 mg KOH/g was obtained.

Compound H-9

(26) 136.5 g (1.05 mol) of ethyl acetoacetate and 162.0 g (1.0 mol of amino groups) of polyoxypropylenetriamine having an average molecular weight M.sub.n of about 440 g/mol (Jeffamine? T-403, from Huntsman) were converted as described for compound H-1. A clear, yellow, slightly odorous liquid having a viscosity at 20? C. of 4870 mPa.Math.s and an amine value of 199 mg KOH/g was obtained.

Compound H-10: ?,?-Polyoxypropylenebis(3-(N-2-hydroxyethylamino) but-2-enoate)

(27) 85.2 g (0.15 mol) of the (?,?-polyoxypropylenebis(acetoacetate)) intermediate prepared for compound H-7 was reacted with 18.3 g (0.30 mol) of 2-aminoethanol as described for compound H-7. A clear, orange, slightly odorous liquid having a viscosity at 20? C. of 6710 mPa.Math.s and an amine value of 177 mg KOH/g was obtained.

Compound H-11: ?,?-Polyoxypropylenebis(3-aminobut-2-enoate)

(28) To an initial charge of 184.20 g (0.32 mol) of the (?,?-polyoxypropylenebis(acetoacetate)) intermediate prepared for compound H-7 in a round-bottom flask equipped with reflux condenser and water separator were added 54.72 g (0.90 mol) of 28% aqueous ammonia solution, 200 ml of toluene and 1 ml of formic acid, and the mixture was boiled at reflux for 3 hours while separating water out. A total of 39 ml of water was collected. Subsequently, the volatile constituents were removed at 140? C. and standard pressure, followed by 2 hours on a rotary evaporator (bath temperature 120? C., reduced pressure of 8 mbar). 176.95 g of a clear, orange, slightly odorous liquid having a viscosity at 20? C. of 175 mPa.Math.s was obtained.

(29) Compounds H-1 to H-6, H-8 and H-9 are compounds of the formula (II), with compounds H-1, H-2, H-3 and H-9 conforming to the formula (II a) and compounds H-5 and H-6 to the formula (II b). Compounds H-7 and H-10 are compounds of the formula (III), with compound H-10 conforming to the formula (III a).

(30) Compound H-11 does not conform to the formula (III) and serves as comparison for compounds of the formula (III).

(31) Preparation of Compounds as Comparison:

Compound R-1 (Dialdimine)

(32) 298.7 g (1.05 mol) of 2,2-dimethyl-3-lauroyloxypropanal was initially charged in a round-bottom flask under a nitrogen atmosphere. Then 153.0 g (0.50 mol) of polyoxypropylenediamine having average molecular weight M.sub.n of 306 g/mol (mixture of 84.1 g of Jeffamine? D-230 and 68.9 g of Jeffamine? D-400, both from Huntsman) was added with good stirring, and then the volatile constituents were removed at 80? C. and a reduced pressure of 10 mbar. A clear, pale yellow, odorless liquid having a viscosity at 20? C. of 122 mPa.Math.s and an amine value of 129 mg KOH/g was obtained.

Compound R-2 (Dialdimine)

(33) 193.5 g (1.05 mol) of dodecanal (lauraldehyde) was converted as described for compound R-1.

(34) Prepared as described for compound R-1, except using 193.5 g (1.05 mol) of lauraldehyde rather than 2,2-dimethyl-3-lauroyloxypropanal. A clear, pale yellow, slightly odorous liquid having a viscosity at 20? C. of 147 mPa.Math.s and an amine value of 171 mg KOH/g was obtained.

Compound R-3 (Diketimine)

(35) Prepared as described for compound H-1, except using 103.1 g (1.05 mol) of cyclohexanone in place of ethyl acetoacetate. A clear, yellow, intensely odorous liquid having a viscosity at 20? C. of 99 mPa.Math.s and an amine value of 253 mg KOH/g was obtained.

(36) Production of Two-Component Compositions:

(37) Substances Used:

(38) Setathane? D 1150: branched polyol, reaction product of castor oil with ketone resin, OH equivalent weight 360 g/eq (from Allnex) Desmophen? 4011 T: polyether triol having OH equivalent weight 102 g/eq (from Covestro) Voranol? CP 4755 EO-endcapped polyoxypropylenetriol, OH number 35 mg KOH/g (from Dow) Lupranol? 4003/1 EO-endcapped polyoxypropylenetriol with 45% by weight of grafted SAN polymer, OH number 20.0 mg KOH/g (from BASF) Desmodur? VL polyisocyanate based on MDI, NCO equivalent weight 133 g/eq (from Covestro) Desmodur? CD-L modified polyisocyanate based on MDI, NCO equivalent weight 142 g/eq (from Covestro) Zeolite paste 3 ? molecular sieve powder in castor oil, 1:1 by weight BYK-E 410 rheology additive (from Altana)

(39) Compositions Z-1 to Z-31 and Ref-1 to Ref-14: (Compositions for high mechanical stress, suitable as floor coating)

(40) For each composition, the ingredients specified in table 1 or 2 were processed in the specified amounts (in parts by weight) of the first component (component-1) by means of a centrifugal mixer (SpeedMixer? DAC 150, FlackTek Inc.) at 1600 rpm for 3 min with exclusion of moisture to give a homogeneous liquid and stored for at least 2 h. Subsequently, the amount of the second component specified in table 1 was added to the first component and the two components were processed by means of the centrifugal mixer with exclusion of moisture at 1600 rpm for 3 minutes to give a homogeneous liquid, which was immediately tested as follows:

(41) Open time was determined by using a spatula to agitate 20 grams of the mixed composition at regular intervals. When the composition felt for the first time as if it had thickened too much for feasible processing, the open time from the start of the mixing process was read off.

(42) To determine the mechanical properties, the composition was poured onto a PTFE-coated film to give a film of thickness 2 mm, which was cured by storage under standard climatic conditions for 14 days, and a few dumbbells having a length of 75 mm with a bar length of 30 mm and a bar width of 4 mm were punched out of the film and these were tested in accordance with DIN EN 53504 at a strain rate of 200 mm/min for maximum tensile strength, elongation at break, and modulus of elasticity (between 0.5-5% elongation). Furthermore, a number of test specimens were punched out for determination of tear propagation resistance and were tested in accordance with DIN ISO 34-1, Method B (angular test specimens) at a strain rate of 500 mm/min.

(43) For determination of Shore hardness to DIN 53505, cylindrical test specimens (diameter 20 mm, thickness 5 mm) were produced from the still-liquid reaction mixture, and were stored before the measurement under standard climatic conditions for 14 d. Each of the results is specified as being a Shore A or Shore D value.

(44) Appearance was assessed visually on the films which had been produced under standard climatic conditions for the determination of the mechanical properties.

(45) Nice describes a blister-free film having a homogeneous, non-sticky surface. Uneven describes a film which has not leveled out owing to the short open time. Odor was assessed by smelling by nose at a distance of 2 cm from the freshly produced films. No means that no odor was perceptible. Yes means that an odor was clearly perceptible. Strong means that an intense, solvent-like odor was perceptible.

(46) The results are reported in table 1 or 2.

(47) The compositions labeled Ref are comparative examples.

(48) TABLE-US-00001 TABLE 1 Composition (in parts by weight) and properties of Z-1 t- Z-26 Ref-1 to Ref-12 Composition Ref-1 Z-1 Z-2 Z-3 Z-4 Z-5 Z-6 Ref-2 Component-1: Setathane? D 90.8 89.8 88.5 86.2 81.7 68.1 45.4 1150 Desmophen? 4.0 4.0 3.9 3.8 3.6 3.0 2.0 4011 T Compound H-1 H-1 H-1 H-1 H-1 H-1 H-1 1.0 2.5 5.0 10.0 25.0 50.0 100.00 Zeolite paste 5.0 5.0 4.9 4.8 4.5 3.8 2.5 BYK-E 410 0.2 0.2 0.2 0.2 0.2 0.2 0.1 Component-2: Desmodur? VL 41.0 41.0 41.0 42.0 43.0 44.0 47.0 52.0 Open time [min] 40 32 29 26 24 20 10 5 Tensile strength 20.3 19.2 19.2 19.6 21.4 25.5 32.1 n.d. [MPa] Elongation at 92 101 101 93 97 62 43 n.d. break [%] Modulus of 226 233 227 300 372 499 657 n.d. elasticity [MPa] Tear propagation 65.0 64.2 65.8 72.2 79.7 95.0 105.6 n.d. resistance [N/mm] Shore D 59 66 65 69 71 69 73 71 Appearance nice nice nice nice nice nice nice uneven Odor no no no no no no no no Composition Z-7 Z-8 Z-9 Z-10 Z-11 Z-12 Component-1: Setathane? D 1150 88.5 86.2 81.7 88.5 86.2 81.7 Desmophen? 4011 T 3.9 3.8 3.6 3.9 3.8 3.6 Compound H-2 H-2 H-2 H-3 H-3 H-3 2.5 5.0 10.0 2.5 5.0 10.0 Zeolite paste 4.9 4.8 4.5 4.9 4.8 4.5 BYK 410 0.2 0.2 0.2 0.2 0.2 0.2 Component-2: Desmodur?VL 41.0 41.0 42.0 41.0 42.0 43.0 Open time [min] 40 30 20 35 25 20 Tensile strength [MPa] 15.6 18.9 18.8 19.4 15.2 23.5 Elongation at break [%] 79 97 77 89 57 49 Modulus of elasticity 193 233 346 228 264 451 [MPa] Tear propagation 67 69 81 69 73 92 resistance [N/mm] Shore D 65 65 70 64 69 70 Appearance nice nice nice nice nice nice Odor no no no no no no Composition Z-13 Z-14 Z-15 Z-16 Z-17 Z-18 Z-19 Z-20 Component-1: Setathane? D 88.5 86.2 81.7 88.5 86.2 81.7 88.5 86.2 1150 Desmophen 3.9 3.8 3.6 3.9 3.8 3.6 3.9 3.8 4011 T Compound H-4 H-4 H-4 H-5 H-5 H-5 H-6 H-6 2.5 5.0 10.0 2.5 5.0 10.0 2.5 5.0 Zeolite paste 4.9 4.8 4.5 4.9 4.8 4.5 4.9 4.8 BYK 410 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Component-2: Desmodur? VL 42.0 43.0 45.0 43.0 45.0 49.0 44.0 47.0 Open time [min] 35 30 25 40 35 30 40 35 Tensile strength 17.7 19.4 29.8 21.5 24.4 33.4 21.6 29.0 [MPa] Elongation at break 75 66 38 95 85 72 89 72 [%] Modulus of elasticity 257 357 601 367 486 674 420 538 [MPa] Tear propagation 72 74 89 76 83 n.d. 80 88 resistance [N/mm] Shore D 65 70 73 61 68 72 68 73 Appearance nice nice nice nice nice nice nice nice Odor no no no no no no no no Composition Z-21 Z-22 Z-23 Z-24 Z-25 Z-26 Component-1: Setathane? D 1150 89.8 88.5 86.2 81.6 86.2 81.7 Desmophen? 4011 T 4.0 3.9 3.8 3.6 3.8 3.6 Compound H-7 H-7 H-7 H-7 H-10 H-10 1.0 2.5 5.0 10.0 5.0 10.0 Zeolite paste 4.9 4.8 4.7 4.5 4.8 4.5 BYK 410 0.2 0.2 0.2 0.2 0.2 0.2 Component-2: Desmodur? VL 41.0 41.0 41.0 41.0 43.0 45.0 Open time [min] 40 35 28 24 28 23 Tensile strength [MPa] 20.8 20.4 20.6 21.0 22.9 21.1 Elongation at break 93 92 94 92 101 74 [%] Modulus of elasticity 319 307 322 385 282 348 [MPa] Tear propagation 73 69 73 75 71 75 resistance [N/mm] Shore D 67 66 70 69 70 72 Appearance nice nice nice nice nice nice Odor no no no no no no Composition Ref-3 Ref-4 Ref-5 Ref-6 Ref-7 Component-1: Setathane? D 1150 88.4 86.2 88.5 86.2 81.7 Desmophen? 4011 T 3.9 3.8 3.9 3.8 3.6 Compound Et 300.sup.1 Et 300.sup.1 R-1 R-1 R-1 2.5 5.0 2.5 5.0 10.0 Zeolite paste 4.9 4.8 4.9 4.8 4.5 BYK 410 0.2 0.2 0.2 0.2 0.2 Component-2: Desmodur? VL 43.0 45.0 41.0 41.0 40.0 Open time [min] 10 <4 40 45 50 Tensile strength [MPa] n.d. n.d. 21.3 17.5 13.2 Elongation at break n.d. n.d. 101 88 91 [%] Modulus of elasticity n.d. n.d. 190 135 55 [MPa] Tear propagation n.d. n.d. 60 50 31 resistance [N/mm] Shore D 58 50 57 54 43 Appearance uneven uneven nice nice nice Odor yes yes no no no Composition Ref-8 Ref-9 Ref-10 Ref-11 Ref-12 Component-1: Setathane? D 1150 88.5 86.2 81.7 88.5 86.2 Desmophen? 4011 T 3.9 3.8 3.6 3.9 3.8 Compound R-2 R-2 R-2 R-3 R-3 2.5 5.0 10.0 2.5 5.0 Zeolite paste 4.9 4.8 4.5 4.9 4.8 BYK 410 0.2 0.2 0.2 0.2 0.2 Component-2: 42.0 Desmodur? VL 41.0 41.0 41.0 41.0 Open time [min] 20 20 15 15 10 Tensile strength [MPa] 18.5 17.6 14.8 15.3 14.5 Elongation at break 85 85 85 70 59 [%] Modulus of elasticity 176 136 87 172 222 [MPa] Tear propagation 57 51 41 59 72 resistance [N/mm] Shore D 60 59 57 60 67 Appearance nice nice nice nice nice Odor no no no strong strong n.d. stands for not determined (reaction too fast) .sup.1Ethacure? 300 (3,5-dimethylthio-2,4(6)-tolylenediamine, from Albemarle)

(49) It is apparent from table 1 that the inventive compounds H-1 to H-7, by comparison with reference composition Ref-1, even in the case of a small use amount, brought about a distinct increase in modulus of elasticity and in tear propagation resistance, coupled with similar or higher tensile strength.

(50) Particularly good properties were achieved with the preferred compounds H-1, H-5 and H-6, which conform to the formulae (II a) and (II b). Compositions Z-3 and Z-4 comprising compound H-1 (formula II a), with unchanged high tensile strength and elongation at break, enabled a distinct increase in modulus of elasticity and tear propagation resistance, as did compositions Z-16, Z-17 and Z-19 comprising compound H-5 or H-6 (formula II b), and these additionally had a similarly long open time to reference composition Ref-1.

(51) Compound H-4, which does not conform to the preferred formulae (II a) or (II b), resulted in a reduction in elongation at break (Z-13 to Z-15).

(52) TABLE-US-00002 TABLE 2 Composition (in parts by weight) and properties of Z-27 to Z-31 and Ref-13 to Ref-14 Composition Ref-13 Z-27 Z-28 Z-29 Z-30 Ref-14 Z-31 Component-1: Setathane? D 1150 91.0 82.4 87.5 86.2 81.5 Desmophen? 4.0 2.6 2.5 3.8 3.5 4.0 4.0 4011 T Voranol? CP 4755 82.0 73.4 Butane-1,4-diol 9.0 7.6 Compound H-1 H-8 H-11 H-11 H-1 10.0 5.0 5.0 10.0 10.0 Zeolite paste 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Component-2: Desmodur? VL 41.0 41.0 41.0 41.0 41.0 41.0 41.0 Open time [min] 53 37 22 28 51 93 48 Tensile strength 21.3 22.8 19.0 19.3 18.4 3.2 4.6 [MPa] Elongation at break 118 113 105 115 119 92 129 [%] Modulus of 182 276 162 119 85 3.6 5.4 elasticity [MPa] Tear propagation 62.6 83.2 53.7 42.8 39.8 5.1 7.5 resistance [N/mm] Shore 98A 99A 68D 60D 61D 54A 63A Appearance nice nice nice nice nice nice nice Odor no no no no no no no

(53) It is apparent from table 2 that particularly high strengths coupled with high elongation at break are achieved with the castor oil-based polyol Setathane? D 1150 (Ref-13 and Z-27 to Z-30), whereas a system comprising a combination of polyether triol and butanediol, with similar extensibility, showed significantly lower strength (Ref-14 and Z-31). For each of the systems, the compound H-1 achieves a distinct increase in modulus of elasticity and in tear propagation resistance (Z-27 compared to Ref-13 and Z-31 compared to Ref-14).

(54) Composition Z-28 comprising compound H-8, which does not conform to the preferred formulae (II a) or (II b), showed a short open time and no increase in modulus of elasticity or tear propagation resistance.

(55) Compound H-11, the preparation of which is particularly complex and which does not conform to the preferred formula (III), likewise did not increase either the modulus of elasticity or the tear propagation resistance (Z-29 and Z-30 compared to Ref-13).

(56) Compositions Z-32 to Z-41 and Ref-15 to Ref-16: (Coatings with High Crack Bridging, Suitable as Roof Seal)

(57) For each composition, the ingredients of the first component specified in table 3 were produced and mixed with the amount of the second component specified in table 3, as described for composition Z-1.

(58) The mixed composition was tested in each case as described for composition Z-1.

(59) The results are reported in table 3.

(60) The compositions labeled Ref are comparative examples.

(61) TABLE-US-00003 TABLE 3 Composition (in parts by weight) and properties of Z-32 to Z-41 and Ref-15 to Ref-16 Composition Ref-15 Z-32 Z-33 Ref-16 Z-34 Z-35 Comp .-1: Voranol? CP 4755 74.5 66.0 65.3 58.0 53.8 49.5 Lupranol? 4003/1 30.0 30.0 30.0 Chalk 13.5 13.5 13.5 Butane-1,4-diol 7.0 5.5 6.2 7.0 6.2 5.5 Compound H-1 H-7 H-1 H- 10.0 10.0 5.0 10.0 Zeolite paste 5.0 5.0 5.0 5.0 5.0 5.0 Comp .-2: Desmodur? CD-L 30.0 30.0 30.0 30.0 30.0 30.0 Open time [min] 79 60 43 54 48 44 Tensile strength 1.4 8.5 1.8 2.1 4.5 13.6 [MPa] Elongation at break 40 207 152 55 222 257 [%] Modulus of 9.2 15.3 5.0 12.5 7.3 13.6 elasticity [MPa] Tear propagation 4.9 14.8 8.1 8.2 10.2 14.3 resistance [N/mm] Shore A 59 81 58 76 70 77 Appearance nice nice nice nice nice nice Odor no no no no no no Composition Z-36 Z-37 Z-38 Z-39 Z-40 Z-41 Comp .-1: Voranol? CP 4755 55.9 49.6 56.2 54.3 53.6 49.2 Lupranol? 4003/1 30.0 30.0 30.0 30.0 30.0 30.0 Chalk Butane-1,4-diol 6.6 5.4 6.3 5.7 6.4 5.8 Compound H-9 H-9 H-10 H-10 H-11 H-11 2.5 10.0 2.5 5.0 5.0 10.0 Zeolite paste 5.0 5.0 5.0 5.0 5.0 5.0 Comp.-2: Desmodur? CD-L 30.0 30.0 30.0 30.0 30.0 30.0 Open time [min] 48 35 45 36 93 90 Tensile strength 4.0 11.0 6.6 8.4 4.8 7.4 [MPa] Elongation at break 148 209 187 174 196 273 [%] Modulus of 9.8 11.1 9.1 10.1 10.7 11.0 elasticity [MPa] Tear propagation 9.7 12.4 9.8 10.6 11.4 12.9 resistance [N/mm] Shore A 73 78 76 78 74 74 Appearance nice nice nice nice nice nice Odor no no no no no no

(62) It is apparent from table 3 that the system comprising the SAN polymer-containing polyol Lupranol? 4003/1 enables higher tensile strengths coupled with high tear propagation resistance compared to a system comprising a conventional polyol and the corresponding amount of chalk in place of the SAN polymer, with a distinct improvement in mechanical properties in both systems by means of compound H-1, especially in relation to elongation, tensile strength and tear propagation resistance (Z-34 and Z-35 compared to Ref-16 and Z-32 compared to Ref-15). The further inventive compounds H-7, H-9, H-10 and H-11 also show a positive effect on mechanical properties, while compound H-11, the preparation of which is particularly complex and which does not conform to the preferred formula (III), results in an undesirably long open time (Z-40 and Z-41 compared to Ref-16). For good processibility, an open time in the range from about 30 to 60 minutes is particularly advantageous.

(63) Compound H-10, which conforms to the particularly preferred formula (III a), shows particularly high strength even in the case of a very small use amount (Z-38).