Latent curing agent and curable polyurethane composition

Abstract

A compound of formula (I) having advantageous properties when used as a latent curing agent for compositions containing isocyanate groups, and to compositions containing the compound of formula (I). The compound of formula (I) is odourless, is liquid and has comparatively low viscosity at room temperature and is stable in storage together with isocyanates. It makes possible odourless single-component polyurethane compositions which have good stability in storage, do not produce bubbles when cured in the presence of moisture, and cause no problematic odour emissions, giving a cured elastic material having good mechanical properties, good heat stability, a surprisingly non-adhesive surface and little tendency towards plasticizer migration.

Claims

1. A composition comprising at least one compound of formula (I) and at least one polyisocyanate and/or at least one polyurethane polymer containing isocyanate groups; wherein the least one compound of the formula (I) is ##STR00028## where n is 1, 2 or 3, Z is an aryl radical substituted by an alkyl or alkoxy group and having a total of 12 to 26 carbon atoms, A is an n-valent organic radical having a molecular weight in the range from 15 to 10,000 g/mol, X is O or S or NR.sup.0 where R.sup.0 is a monovalent organic radical having 1 to 18 carbon atoms, and Y is a 1,2-ethylene or 1,3-propylene radical which is optionally substituted, where A and Y in the case that n =1 may also be bonded to a trivalent radical having 4 to 10 carbon atoms.

2. The composition as claimed in claim 1, wherein it is an adhesive or a sealant or a coating.

3. The composition as claimed in claim 1, wherein the composition is odorless.

4. The composition as claimed in claim 1, wherein the at least one compound of formula (I) is obtained from a reaction of at least one amine of the formula (III) with at least one aldehyde of the formula (IV) ##STR00029## in a condensation reaction with removal of water, where A, n, X, Y and Z have the same definitions as provided above.

5. The composition as claimed in claim 1, wherein Z is the aryl radical substituted by an alkyl group and having a total of 12 to 26 carbon atoms.

6. The composition as claimed in claim 1, wherein Z is a radical of the formula (II) ##STR00030## where R is a branched alkyl radical having 8 to 12 carbon atoms.

Description

EXAMPLES

(1) Working examples are adduced hereinafter, which are intended to further elucidate the invention described. Of course, the invention is not limited to these described working examples.

(2) Chemicals otherwise specified in the examples were purchased from Sigma-Aldrich or Merck (in purum or puriss. quality) and used as obtained. “Standard climatic conditions” (“SCC”) refer to a temperature of 23±1° C. and a relative air humidity of 50±5%.

(3) Aldehydes Used: Aldehyde-1: Fractionated aldehyde mixture obtained from formylation, catalyzed by means of HF—BF.sub.3, of C.sub.10-14-alkylbenzene, containing mainly branched 4-(C.sub.10-14-alkyl)benzaldehydes. (Average aldehyde equivalent weight 290 g/eq) Benzaldehyde (106.1 g/mol) Isobutyraldehyde (72.1 g/mol) 2,2-Dimethyl-3-lauroyloxypropanal (284.4 g/mol)

(4) Aldehyde-1 is a mixture of aldehydes of the formula (IV).

(5) Benzaldehyde and 2,2-dimethyl-3-lauroyloxypropanal do not conform to the formula (IV).

(6) Production of Latent Curing Agents:

(7) The amine value (including blocked amino groups) was determined by means of titration (with 0.1N HCIO.sub.4 in acetic acid versus crystal violet).

(8) Viscosity was measured with a thermostated Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 10 s.sup.−1 for viscosities <150 Pa.Math.s, shear rate 1 s.sup.−1 for viscosities >150 Pa.Math.s).

(9) 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).

(10) Oxazolidine A-1:

(11) To an initial charge of 63.09 g of diethanolamine in a round-bottom flask were added 178.09 g of aldehyde-1 and 0.50 g of salicylic acid, and the reaction mixture was stirred at 80° C. under reduced pressure until all the water had been removed. A yellowish liquid having an amine value of 141.6 mg KOH/g was obtained.

(12) FT-IR: 2954, 2923, 2871, 2857, 1704, 1607, 1509, 1465, 1425, 1378, 1343, 1298, 1213, 1174, 1045, 1018, 937, 884, 825, 722.

(13) The oxazolidine A-1 is a monooxazolidine and conforms to the formula (I a).

(14) Oxazolidine A-2:

(15) An initial charge of 37.80 g of oxazolidine A-1, prepared as described above, under a nitrogen atmosphere in a round-bottom flask was heated up. At 80° C., 8.33 g of hexamethylene 1,6-diisocyanate was added dropwise and then the mixture was stirred at 80° C. until no isocyanate groups were detectable any longer by means of IR spectroscopy. A highly viscous yellow oil that was liquid at room temperature and had a viscosity of 16.9 Pa.Math.s at 60° C. and an amine value of 116.4 mg KOH/g was obtained. After a storage time of 18 months in a closed container, consistency and viscosity were unchanged.

(16) FT-IR: 2955, 2923, 2853, 1704, 1634, 1532, 1463, 1376, 1352, 1242, 1213, 1178, 1105, 1057, 1019, 825, 772, 722.

(17) The oxazolidine A-2 is a bisoxazolidine and conforms to the formula (I d).

(18) Oxazolidine A-3:

(19) To an initial charge of 44.50 g of polyoxypropylene having a terminal 2-hydroxypropylamino group at each end and an average molecular weight of about 350 g/mol (Jeffamine® C-346 from Huntsman) in a round-bottom flask were added 80.00 g of aldehyde-1 and 0.50 g of salicylic acid, and the reaction mixture was stirred at 80° C. under reduced pressure until all the water had been removed. A yellowish liquid having a viscosity of 1.1 Pa.Math.s at 20° C. and an amine value of 111.8 mg KOH/g was obtained.

(20) FT-IR: 2957, 2923, 2870, 2853, 1726, 1704, 1645, 1606, 1575, 1456, 1375, 1304, 1212, 1194, 1168, 1094, 1062, 1017, 826, 722.

(21) The oxazolidine A-3 is a bisoxazolidine and conforms to the formula (I d).

(22) Oxazolidine A-4:

(23) To an initial charge of 29.79 g of N-(3-(2-methylphenyloxy)-2-hydroxy-1-propyl)propane-1,2-diamine, prepared as described hereinafter, in a round-bottom flask were added 80.00 g of aldehyde-1 and 0.50 g of salicylic acid, and the reaction mixture was stirred at 80° C. under reduced pressure until all the water had been removed. An orange liquid having a viscosity of 3.0 Pa.Math.s at 20° C. and an amine value of 116.5 mg KOH/g was obtained.

(24) FT-IR: 2955, 2923, 2870, 2853, 1704, 1645, 1605, 1495, 1461, 1378, 1304, 1245, 1213, 1168, 1122, 1051, 1018, 826, 748, 722.

(25) The oxazolidine A-4 is an iminooxazolidine and conforms to the formula (I c).

(26) N-(3-(2-methylphenyloxy)-2-hydroxy-1-propyl)propane-1,2-diamine was prepared by heating an initial charge of 4.74 kg of propane-1,2-diamine under a nitrogen atmosphere to 70° C. and then, with good stirring, gradually adding 2.93 kg of o-cresyl glycidyl ether (Araldite® DY-K, from Huntsman), in the course of which the temperature of the reaction mixture was 70 to 80° C. After 1 hour at 80° C., the reaction mixture was cooled down and propane-1,2-diamine and further volatile constituents were removed by distillation by means of a thin-film evaporator (0.5-1 mbar, jacket temperature 115° C.). What was obtained was a clear yellowish liquid having an amine value of 478.7 mg KOH/g and a viscosity of 3.3 Pa.Math.s at 20° C.

(27) Oxazolidine A-5:

(28) To an initial charge of 35.05 g of N-(3-(2-methylphenyloxy)-2-hydroxy-1-propyl)-2(4)-methylpentane-1,5-diamine, prepared as described hereinafter, in a round-bottom flask were added 80.00 g of aldehyde-1 and 0.50 g of salicylic acid, and the reaction mixture was stirred at 80° C. under reduced pressure on a rotary evaporator until all the water had been removed. An orange liquid having a viscosity of 3.1 Pa.Math.s at 20° C. and an amine value of 112.0 mg KOH/g was obtained.

(29) FT-IR: 2955, 2923, 2870, 2853, 1704, 1647, 1605, 1495, 1461, 1377, 1304, 1245, 1168, 1122, 1051, 1038, 1018, 827, 748, 712.

(30) The oxazolidine A-5 is an iminooxazolidine and conforms to the formula (I c).

(31) N-(3-(2-methylphenyloxy)-2-hydroxy-1-propyl)-2(4)-methylpentane-1,5-diamine was prepared by heating an initial charge of 4.65 kg of 1,5-diamino-2-methylpentane (Dytek® A, from Invista) under a nitrogen atmosphere to 70° C. and then, with good stirring, gradually adding 1.83 kg of o-cresyl glycidyl ether (Araldite® DY-K, from Huntsman), in the course of which the temperature of the reaction mixture was 70 to 80° C. After 1 hour at 80° C., the reaction mixture was cooled down and 1,5-diamino-2-methylpentane and further volatile constituents were removed by distillation by means of a thin-film evaporator (0.5-1 mbar, jacket temperature 160° C.). What was obtained was a clear yellowish liquid having an amine value of 367.1 mg KOH/g and a viscosity of 6.5 Pa.Math.s at 20° C.

(32) Oxazolidine A-6:

(33) An initial charge of 30.16 g of polyoxypropylenediamine having an average molecular weight of about 240 g/mol (Jeffamine® D-230 from Huntsman) in a round-bottom flask was heated up to 70° C. While stirring, 37.55 g of phenyl glycidyl ether was added gradually and then the mixture was stirred at 80° C. for 2 hours under a nitrogen atmosphere, forming a bis(α,β-hydroxylamine). To this reaction product were added 80.00 g of aldehyde-1 and 0.50 g of salicylic acid, and the reaction mixture was stirred at 80° C. under reduced pressure until all the water had been removed. A yellowish liquid having a viscosity of 3.5 Pa.Math.s at 20° C. and an amine value of 100.9 mg KOH/g was obtained.

(34) FT-IR: 2956, 2923, 2870, 2853, 1704, 1645, 1600, 1587, 1496, 1456, 1376, 1301, 1244, 1170, 1101, 1077, 1042, 1018, 827, 752, 690.

(35) The oxazolidine A-6 is a bisoxazolidine and conforms to the formula (I d).

(36) Oxazolidine A-7:

(37) The procedure was as described for oxazolidine A-6, except that 250.00 g of a polyoxypropylenediamine having an average molecular weight of about 2′000 g/mol (Jeffamine® D-2000 by Huntsman) was used rather than the polyoxypropylenediamine having an average molecular weight of about 240 g/mol. An orange liquid having a viscosity of 1.8 Pa.Math.s at 20° C. and an amine value of 31.3 mg KOH/g was obtained.

(38) FT-IR: 2968, 2926, 2897, 2858, 1704, 1601, 1497, 1456, 1372, 1343, 1245, 1098, 1015, 925, 828, 753, 691.

(39) The oxazolidine A-7 is a bisoxazolidine and conforms to the formula (I d).

(40) Oxazolidine A-8:

(41) To an initial charge of 16.97 g of methylpentanediol diacrylate (SR341, from Sartomer) in a round-bottom flask was added 9.16 g of ethanolamine, and the reaction mixture was heated up to 50° C. and stirred for 2 hours, forming a bis(α,β-hydroxylamine). To this reaction product were added 45.83 g of aldehyde-1 and 0.50 g of salicylic acid, and the reaction mixture was stirred at 80° C. under reduced pressure until all the water had been removed. A yellowish liquid having a viscosity of 1.6 Pa.Math.s at 20° C. and an amine value of 121.0 mg KOH/g was obtained.

(42) FT-IR: 2955, 2923, 2871, 2853, 1734, 1704, 1647, 1607, 1458, 1378, 1301, 1212, 1179, 1109, 1054, 1018, 826, 722.

(43) The oxazolidine A-8 is a bisoxazolidine and conforms to the formula (I d).

(44) Oxazinane A-9:

(45) The procedure was as described for oxazolidine A-8, except that 11.27 g of 3-amino-1-propanol was used rather than ethanolamine. A yellowish liquid having a viscosity of 2.9 Pa.Math.s at 20° C. and an amine value of 118.6 mg KOH/g was obtained.

(46) FT-IR: 2954, 2923, 2853, 1734, 1705, 1461, 1378, 1305, 1177, 1157, 1117, 1079, 1051, 977, 924, 826, 781, 722.

(47) The oxazinane A-9 is a bisoxazinane and conforms to the formula (I d).

(48) Oxazolidine A-10:

(49) To an initial charge of 5.21 g of N-(2-aminoethyl)ethanolamine in a round-bottom flask with a water separator (Dean-Stark apparatus) were added 30.56 g of aldehyde-1, 50 ml of cyclohexane and 0.10 g of salicylic acid, and the reaction mixture was boiled under reflux at 120° C. until all the water had separated out. Subsequently, the reaction mixture was cooled and filtered, and the volatile constituents were removed under reduced pressure on a rotary evaporator at 80° C. An orange liquid having a viscosity of 1.1 Pa.Math.s at 20° C. and an amine value of 160.2 mg KOH/g was obtained.

(50) FT-IR: 2955, 2920, 2852, 1705, 1647, 1608, 1572, 1457, 1377, 1343, 1301, 1220, 1174, 1138, 1060, 1018, 986, 962, 826, 722.

(51) The oxazolidine A-10 is an iminooxazolidine and conforms to the formula (I c).

(52) Aminal A-11:

(53) To an initial charge of 11.62 g of N,N′-diethylethylenediamine in a round-bottom flask was added 32.01 g of aldehyde-1 while stirring. Thereafter, the reaction mixture was freed of the water of reaction at 80° C. under reduced pressure on a rotary evaporator. An orange liquid having a viscosity of 0.09 Pa.Math.s at 20° C. and an amine value of 265.7 mg KOH/g was obtained.

(54) FT-IR: 2957, 2924, 2871, 2853, 2792, 2525, 1706, 1607, 1508, 1465, 1423, 1377, 1340, 1280, 1226, 1164, 1055, 1019, 995, 958, 861, 824, 805, 722. The aminal A-11 conforms to the formula (I) where n is 1, X is NR.sup.0, R.sup.0 and A are each ethyl and Y is ethylene.

(55) Aminal A-12:

(56) To an initial charge of 24.04 g of N,N′-dibenzylethylenediamine in a round-bottom flask was added 32.01 g of aldehyde-1 while stirring. Thereafter, the reaction mixture was freed of the water of reaction at 80° C. under reduced pressure on a rotary evaporator. An orange liquid having a viscosity of 1.41 Pa.Math.s at 20° C. and an amine value of 210.4 mg KOH/g was obtained.

(57) FT-IR: 3085, 3062, 2954, 2923, 2870, 2852, 2792, 2722, 2520, 1804, 1705, 1605, 1507, 1453, 1423, 1377, 1338, 1295, 1248, 1212, 1153, 1120, 1072, 1028, 975, 911, 861, 827, 735, 690, 667.

(58) The aminal A-12 conforms to the formula (I) where n is 1, X is NR.sup.0, R.sup.0 and A are each benzyl and Y is ethylene.

(59) Oxazolidine A-13:

(60) To an initial charge of 11.72 g of N-butylethanolamine in a round-bottom flask with a water separator (Dean-Stark apparatus) were added 29.68 g of aldehyde-1, 75 ml of cyclohexane and 0.10 g of salicylic acid, and the reaction mixture was boiled under reflux at 120° C. until all the water had separated out. Subsequently, the reaction mixture was cooled and filtered, and the volatile constituents were removed under reduced pressure on a rotary evaporator at 80° C. A yellowish liquid having a viscosity of 0.07 Pa.Math.s at 20° C. and an amine value of 142.1 mg KOH/g was obtained.

(61) FT-IR: 2955, 2921, 2854, 2800, 1706, 1614, 1576, 1464, 1426, 1377, 1341, 1296, 1217, 1178, 1152, 1067, 1019, 957, 925, 826, 741, 722.

(62) The oxazolidine A-13 conforms to the formula (I a) where A.sup.1 is n-butyl. It is especially suitable as a desiccant.

(63) Oxazolidine A-14:

(64) To an initial charge of 13.92 g (50 mmol) of 3-glycidoxypropyltriethoxysilane (Dynasylan® GLYEO, from Evonik) in a round-bottom flask was added 22.14 g (100 mmol) of 3-aminopropyltriethoxysilane (Dynasylan® AMEO, from Evonik), and the mixture was stirred at 70° C. until the epoxy groups had been converted. Subsequently, 30.56 g of aldehyde-1 was added and the reaction mixture was freed of the water of reaction at 80° C. under reduced pressure on a rotary evaporator. A pale orange liquid having a viscosity of 0.35 Pa.Math.s at 20° C. and an amine value of 87.6 mg KOH/g was obtained.

(65) FT-IR: 2957, 2924, 2854, 1705, 1647, 1607, 1573, 1508, 1456, 1389, 1343, 1297, 1166, 1102, 1076, 1017, 954, 827, 774.

(66) The oxazolidine A-14 contains a mixture of oxazolidinosilane and aldiminosilane. The oxazolidinosilane conforms to the formula (I b) where A.sup.2 is 3-triethoxysilylpropyl and Y is an ethylene radical 5-triethoxysilyl-2-oxapentyl-substituted in the alpha position to the oxazolidine oxygen. It is especially suitable as an adhesion promoter.

(67) Oxazolidine B-1:

(68) The procedure was as described for oxazolidine A-1, except that 64.95 g of benzaldehyde was used rather than aldehyde-1. A pale brown liquid having an amine value of 288.2 mg KOH/g was obtained.

(69) Oxazolidine B-2:

(70) An initial charge of 37.80 g of oxazolidine B-1, prepared as described above, under a nitrogen atmosphere in a round-bottom flask was heated up. At 80° C., 8.33 g of hexamethylene 1,6-diisocyanate was added dropwise and then the mixture was stirred at 80° C. until no isocyanate groups were detectable any longer by means of IR spectroscopy. What was obtained was a yellow material that was solid at room temperature and had an amine value of 181.4 mg KOH/g, which has a viscosity at 60° C. of 583.5 Pa.Math.s.

(71) Oxazolidine B-3:

(72) The procedure was as described for oxazolidine A-3, except that 29.18 g of benzaldehyde was used rather than aldehyde-1. A pale brown liquid having a viscosity of 1.9 Pa.Math.s at 20° C. and an amine value of 219.4 mg KOH/g was obtained.

(73) Oxazolidine B-4:

(74) The procedure was as described for oxazolidine A-4, except that 29.18 g of benzaldehyde was used rather than aldehyde-1. What was obtained was a viscous dark orange oil having a viscosity of 1′945 Pa.Math.s at 20° C. and an amine value of 249.0 mg KOH/g, which gradually solidified over a few weeks when left to stand at room temperature.

(75) Oxazolidine B-5:

(76) The procedure was as described for oxazolidine A-5, except that 29.18 g of benzaldehyde was used rather than aldehyde-1. An orange oil having a viscosity of 93.5 Pa.Math.s at 20° C. and an amine value of 226.0 mg KOH/g was obtained.

(77) Oxazolidine B-6:

(78) The procedure was as described for oxazolidine A-6, except that 29.18 g of benzaldehyde was used rather than aldehyde-1. An orange oil having a viscosity of 84.5 Pa.Math.s at 20° C. and an amine value of 161.0 mg KOH/g was obtained.

(79) Oxazolidine B-7:

(80) The procedure was as described for oxazolidine A-7, except that 29.18 g of benzaldehyde was used rather than aldehyde-1. An orange liquid having a viscosity of 2.0 Pa.Math.s at 20° C. and an amine value of 40.9 mg KOH/g was obtained.

(81) Oxazolidine B-8:

(82) The procedure was as described for oxazolidine A-8, except that 16.72 g of benzaldehyde was used rather than aldehyde-1. A yellowish liquid having a viscosity of 2.0 Pa.Math.s at 20° C. and an amine value of 216.6 mg KOH/g was obtained.

(83) Oxazinane B-9:

(84) The procedure was as described for oxazolidine A-9, except that 16.72 g of benzaldehyde was used rather than aldehyde-1. A yellowish liquid having a viscosity of 10.5 Pa.Math.s at 20° C. and an amine value of 205.1 mg KOH/g was obtained.

(85) Oxazolidine B-10:

(86) To an initial charge of 15.00 g of N-(2-aminoethyl)ethanolamine in a round-bottom flask with a water separator (Dean-Stark apparatus) were added 32.10 g of benzaldehyde, 50 ml of cyclohexane and 0.10 g of salicylic acid, and the reaction mixture was boiled under reflux at 120° C. until all the water had separated out. Subsequently, the reaction mixture was cooled and filtered, and the volatile constituents were removed under reduced pressure on a rotary evaporator at 80° C. An orange liquid having a viscosity of 0.83 Pa.Math.s at 20° C. and an amine value of 385.1 mg KOH/g was obtained.

(87) Oxazolidine L-1:

(88) The procedure was as described for oxazolidine A-1, except that 174.65 g of 2,2-dimethyl-3-lauroyloxypropanal was used rather than aldehyde-1. A yellowish liquid having an amine value of 141.2 mg KOH/g was obtained.

(89) Oxazolidine L-2:

(90) An initial charge of 39.73 g of oxazolidine L-1, prepared as described above, under a nitrogen atmosphere in a round-bottom flask was heated up. At 80° C., 8.33 g of hexamethylene 1,6-diisocyanate was added dropwise and then the mixture was stirred at 80° C. until no isocyanate groups were detectable any longer by means of IR spectroscopy. A yellowish liquid having a viscosity of 6 Pa.Math.s at 20° C. and an amine value of 115.2 mg KOH/g was obtained.

(91) Oxazolidine IB-2: (Corresponding to Incozol 4, from Incorez)

(92) An initial charge of 15.92 g of N-(2-hydroxyethyl)-2-isopropyloxazolidine (Incozol 3, from Incorez) under a nitrogen atmosphere in a round-bottom flask was heated up. At 80° C., 8.33 g of hexamethylene 1,6-diisocyanate was added dropwise and then the mixture was stirred at 80° C. until no isocyanate groups were detectable any longer by means of IR spectroscopy. What was obtained was a yellowish liquid having a viscosity of 36 Pa.Math.s at 20° C. and an amine value of 220.0 mg KOH/g, which crystallized within a few weeks and had to be melted for further use.

(93) Oxazolidine IB-10:

(94) To an initial charge of 15.00 g of N-(2-aminoethyl)ethanolamine in a round-bottom flask with a water separator (Dean-Stark trap) were added 21.81 g of isobutyraldehyde, 50 ml of cyclohexane and 0.10 g of salicylic acid, and the reaction mixture was boiled under reflux at 120° C. until all the water had separated out. Subsequently, the reaction mixture was cooled and filtered, and the volatile constituents were removed under reduced pressure on a rotary evaporator at 80° C. A yellowish liquid having a viscosity of 0.01 Pa.Math.s at 20° C. and an amine value of 521.7 mg KOH/g was obtained.

(95) Incozol 2:

(96) Monooxazolidine based on N-butylethanolamine and 2-ethylhexanal, from Incorez.

(97) The oxazolidines A-1 to A-8, A-10, A-13 and A-14, the oxazinane A-9 and the aminals A-11 and A-12 are compounds of the formula (I).

(98) The oxazolidines B-1 to B-8 and B-10, the oxazinane B-9 and the oxazolidines L-1, L-2, IB-2, IB-10 and Incozol 2 do not conform to the formula (I) and serve as comparison.

(99) Aldimine C-1:

(100) 50.00 g of 2,2-dimethyl-3-lauroyloxypropanal were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 13.93 g of 3-aminomethyl-3,5,5-trimethylcyclohexylamine was added and then the volatile constituents were removed at 80° C. and a reduced pressure of 10 mbar. A pale-yellow odorless liquid having a viscosity of 0.2 Pa.Math.s at 20° C. and an amine value of 153.0 mg KOH/g was obtained.

(101) The aldimine A-1 is a dialdimine and conforms to the formula (VI).

(102) Preparation of Polymers Containing Isocyanate Groups

(103) Polymer P1:

(104) 400 g of polyoxypropylenediol (Acclaim® 4200, from Covestro; OH number 28.5 mg KOH/g) and 52 g of diphenylmethane 4,4′-diisocyanate (Desmodur® 44 MC L, from Covestro) were reacted by a known method at 80° C. to give an NCO-terminated polyurethane polymer which was liquid at room temperature and had a content of free isocyanate groups of 1.85% by weight.

(105) Polymer P2:

(106) 590 g of polyoxypropylenediol (Acclaim® 4200, from Covestro; OH number 28.5 mg KOH/g), 1180 g of polyoxypropylene/polyoxyethylenetriol (Caradol® MD34-02, from Shell; OH number 35.0 mg KOH/g) and 230 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) were reacted by a known method at 80° C. to give an NCO-terminated polyurethane polymer which was liquid at room temperature and had a content of free isocyanate groups of 2.10% by weight.

(107) Polymer P3:

(108) 356 g of polyoxypropylenediol (Acclaim® 4200, from Covestro; OH number 28.5 mg KOH/g), 100 g of polyoxypropylenetriol (Acclaim® 6300, from Covestro; OH number 28.0 mg KOH/g) and 40 g of a mixture of tolylene 2,4- and 2,6-diisocyanate in an 80/20 ratio (Desmodur® T 80, from Covestro) were reacted by a known method at 80° C. to give an NCO-terminated polyurethane polymer which was liquid at room temperature and had a content of free isocyanate groups of 1.80% by weight.

(109) Polymer P4:

(110) 300.0 g of polyoxypropylene/polyoxyethylenediol (Desmophen® L300, from Covestro; OH number 190.0 mg KOH/g) and 228.8 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) were reacted by a known method at 60° C. to give an NCO-terminated polyurethane polymer which was liquid at room temperature and had a content of free isocyanate groups of 7.91% by weight.

(111) Polymer P5:

(112) 1300 g of polyoxypropylenediol (Acclaim® 4200 N, from Covestro; OH number 28.5 mg KOH/g), 2600 g of polyoxypropylenetriol (Caradol® MD34-02, from Shell; OH number 35.0 mg KOH/g), 600 g of diphenylmethane 4,4′-diisocyanate (Desmodur® 44 MC L, from Covestro) and 500 g of diisodecyl phthalate (Palatinol® Z, BASF) were reacted at 80° C. to give an NCO-terminated polyurethane polymer having a content of free isocyanate groups of 2.05% by weight.

(113) Polyurethane Compositions (One-Component)

(114) Compositions Z1 to Z27:

(115) For each composition, the ingredients specified in tables 1 to 2 were mixed in the amounts specified (in parts by weight) by means of a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) with exclusion of moisture at 3000 rpm for one minute and stored with exclusion of moisture. Each composition was tested as follows:

(116) As a measure of storage stability, Viscosity (1d RT) was determined the day after production and Viscosity (7d 60° C.) after storage for 7 days in a closed container in a circulation oven at 60° C., as described above.

(117) As a measure of the open time, Tack-free time was determined. For this purpose, a few grams of the composition were applied to cardboard in a layer thickness of about 2 mm and, under standard climatic conditions, the time until, when the surface of the composition was gently tapped by means of an LDPE pipette, there were for the first time no residues remaining any longer on the pipette was determined.

(118) To determine the mechanical properties, each composition was poured onto a PTFE-coated film to give a film of thickness 2 mm and stored under standard climatic conditions for 7 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 pull rate of 200 mm/minute for Tensile strength (breaking force), Elongation at break, Modulus of elasticity 5% (at 0.5%-5% elongation) and Modulus of elasticity 50% (at 0.5%-50% elongation).

(119) Appearance was assessed visually on the films produced. “Nice” was used to describe a clear film with a nontacky surface without blisters.

(120) Odor was assessed by smelling by nose at a distance of 2 cm from the freshly produced films. “Yes” means that an odor was clearly perceptible. “No” means that no odor was perceptible.

(121) The results are reported in tables 1 to 2.

(122) The compositions labeled with (Ref) are comparative examples.

(123) TABLE-US-00001 TABLE 1 Composition (in parts by weight) and properties of Z1 to Z13. Composition Z1 Z2 (Ref) Z3 (Ref) Z4 (Ref) Z5 Z6 (Ref) Polymer P1 50.00 50.00 50.00 50.00 50.00 50.00 Oxazolidine A-2 B-2 L-2 IB-2 A-3 B-3 8.48 5.44 8.57 4.49 5.80 2.95 Salicylic acid solution.sup.1 1.00 1.00 1.00 1.00 1.00 1.00 DBTDL solution.sup.2 0.10 0.10 0.10 0.10 0.10 0.10 Viscosity [Pa .Math. s] 20° C. (1 d RT) 53 62 41 51 95 113 (7 d 60° C.) 96 125 45 gelated 134 178 Tack-free time 50′ 70′ 10 h 15′ 40′ 50′ Tensile strength [MPa] 1.02 0.99 0.63 1.56 0.67 0.78 Elongation at break [%] 131 125 95 182 71 82 Modulus of elasticity 1.55 1.61 1.10 2.12 1.37 1.50 5% [MPa] Modulus of elasticity 0.96 1.01 0.65 1.29 0.92 1.00 50% Appearance nice nice tacky, fine nice nice nice blisters Odor no yes no yes no yes Composition Z7 Z8 (Ref) Z9 Z10 (Ref) Z11 Z12 Z13 Polymer P1 50.00 50.00 50.00 50.00 50.00 50.00 50.00 Oxazolidine A-4 B-4 A-5 B-5 A-6 A-8 Oxazinane A-9 8.48 3.97 8.82 4.37 6.42 5.35 5.46 Salicylic acid solution.sup.l 1.00 1.00 1.00 1.00 1.00 1.00 1.00 DBTDL solution.sup.2 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Viscosity [Pa .Math. s] 20° C. (1 d RT) 47 61 44 61 75 43 45 (7 d 60° C.) 80 90 72 77 116 133 108 Tack-free time 165′ 120′ 95′ 55′ 55′ 85′ 180′ Tensile strength [MPa] 0.47 0.88 0.58 0.80 0.63 0.66 0.62 Elongation at break [%] 283 334 214 303 99 83 85 Modulus of elasticity 0.41 0.45 0.76 0.91 1.05 1.21 1.05 5% [MPa] Modulus of elasticity 0.20 0.25 0.43 0.51 0.69 0.80 0.72 50% Appearance nice nice nice nice nice nice nice Odor no yes no yes no no no .sup.15% in dioctyl adipate .sup.25% dibutyltin dilaurate in diisodecyl phthalate

(124) TABLE-US-00002 TABLE 2 Composition (in parts by weight) and properties of Z14 to Z27. Z15 Z16 Z18 Composition Z14 (Ref) (Ref) Z17 (Ref) Polymer P2 50.00 50.00 50.00 50.00 50.00 Oxazolidine A-2 B-2 IB-2 A-4 B-4  9.64  6.19  5.10  9.64  4.51 Salicylic acid solution.sup.1  1.00  1.00  1.00  1.00  1.00 DBTDL solution.sup.2  0.50  0.50  0.50  0.50  0.50 Viscosity [Pa .Math. s] 20° C. (1 d RT) 30   38   23   14   32   (7 d 60° C.) 83   133    89   26   45   Tack-free time 20′   30′   15′   240′     170′    Tensile strength [MPa]  0.85  1.09  1.11  0.54  0.82 Elongation at break [%] 136    136    110    131    177    Modulus of elasticity  1.04  1.63  1.80  0.63  0.87 5% [MPa] Modulus of elasticity  0.72  1.04  1.20  0.45  0.60 50% Appearance nice nice nice nice nice Odor no yes yes no yes Composition Z19 Z20 (Ref) Z21 Z22 Polymer P2 50.00 50.00 50.00 50.00 Oxazinane A-5 B-5 A-8 Oxazolidine 10.02  4.96  6.09 A-9  6.21 Salicylic acid solution.sup.1  1.00  1.00  1.00  1.00 DBTDL solution.sup.2  0.50  0.50  0.50  0.50 Viscosity [Pa .Math. s] 20° C. (1 d RT) 18   27   18   18   (7 d 60° C.) 26   37   85   33   Tack-free time 100′    75′   70′   165′    Tensile strength [MPa]  0.63  0.80  0.68  0.44 Elongation at break [%] 145    137    77   107    Modulus of elasticity  0.72  1.04  1.19  0.72 5% [MPa] Modulus of elasticity  0.49  0.72  0.87  0.44 50% Appearance nice nice nice nice Odor no yes no no Z24 Z25 Composition Z23 (Ref) (Ref) Z26 Z27 Polymer P2 .sub.IS-21 50.00 50.00 50.00 50.00 50.00 Oxazolidine A-10 B-10 IB-10 Aminal Aminal A-11 A-12  7.01  2.91  2.15  3.71  4.70 Salicylic acid solution.sup.1  1.00  1.00  1.00  1.00  1.00 DBTDL solution.sup.2  0.50  0.50  0.50  0.50  0.50 Viscosity [Pa .Math. s] 20° C. (1 d RT) 18   24   23   23   17   (7 d 60° C.) 53   70   309    37   40   Tack-free time 50′   35′   15′   275′    about 15 h Tensile strength [MPa]  0.69  0.90  1.03  0.92  0.82 Elongation at break 77   79   97   202    201    [%] Modulus of elasticity  1.27  1.72  1.77  0.91  0.79 5% [MPa] Modulus of elasticity  0.87  1.16  1.18  0.63  0.56 50% Appearance nice nice nice nice nice Odor no yes yes no no .sup.15% in dioctyl adipate .sup.25% dibutyltin dilaurate in diisodecyl phthalate

(125) Compositions Z28 to Z32:

(126) For each composition, the ingredients specified in table 3 were mixed in the amounts specified (in parts by weight) by means of a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) with exclusion of moisture at 3000 rpm for one minute and stored with exclusion of moisture.

(127) The Premixture-1 used was produced by mixing 24.0 parts by weight of Polymer P3, 2.5 parts by weight of diisodecyl phthalate, 40.8 parts by weight of chalk, 28 parts by weight of thickener, 4.5 parts by weight of titanium dioxide and 0.2 part by weight of p-tosyl isocyanate with exclusion of moisture by means of the centrifugal mixer and stored with exclusion of moisture.

(128) The thickener was produced beforehand by gently heating an initial charge of 300 g of diisodecyl phthalate and 48 g of diphenylmethane 4,4′-diisocyanate (Desmodur® 44 MC L, from Covestro) in a vacuum mixer and then slowly adding 27 g of monobutylamine dropwise while stirring vigorously. The resultant paste was stirred for a further hour under reduced pressure while cooling.

(129) Each composition was tested as described for composition Z1.

(130) The results are reported in table 3.

(131) The compositions labeled with (Ref) are comparative examples.

(132) TABLE-US-00003 TABLE 3 Composition (in parts by weight) and properties of Z28 to Z32. Z32 Composition Z28 Z29 Z30 Z31 (Ref) Premixture-1 80.00 80.00 80.00 80.00 80.00 Oxazolidine A-4 A-5 A-6 A-7 —  2.69  2.81  1.34  4.30 Aldimine C-1 — —  1.47  1.47  2.05 Salicylic acid solution.sup.1  0.40  0.40  0.40  0.40  0.40 DBTDL solution.sup.2  0.10  0.10  0.10  0.10  0.10 Viscosity [Pa .Math. s] 118    110    160    101    168    20° C. (1 d RT) Tack-free time 100′    75′   35′   40′   25′   Tensile strength [MPa]  1.43  1.51  1.40  1.04  1.70 Elongation at break 797    845    858    938    823    [%] Modulus of elasticity  1.13  1.13  1.02  0.75  1.43 5% [MPa] Modulus of elasticity  0.60  0.65  0.54  0.41  0.67 50% Appearance nice nice nice nice nice Odor no no no no no .sup.15% in dioctyl adipate .sup.25% dibutyltin dilaurate in diisodecyl phthalate

(133) Compositions Z33 to Z36:

(134) For each composition, the ingredients specified in table 4 were mixed in the amounts specified (in parts by weight) by means of a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) with exclusion of moisture at 3000 rpm for one minute and stored with exclusion of moisture.

(135) Each composition was tested as follows:

(136) As a measure of plasticizer migration, speck formation on cardboard was determined. For this purpose, each composition was applied to a piece of cardboard such that it had a round base area of diameter 15 mm and a height of 4 mm, and was stored under standard climatic conditions for 7 days. Around each composition, thereafter, a dark oval speck had formed on the cardboard. The dimensions thereof (height and width) were measured and reported in table 4 as Migration.

(137) The compositions labeled with (Ref) are comparative examples.

(138) TABLE-US-00004 TABLE 4 Composition (in parts by weight) and properties of Z33 to Z36. . Z34 Z35 Z36 Composition Z33 (Ref) (Ref) (Ref) Polymer P4 15.00 15.00 15.00 15.00 Chalk 15.00 15.00 15.00 15.00 Silica 1.13 1.13 1.13 1.13 Oxazolidine Oxazolidine Aldimine — Curing agent A-2 B-2 C-1 7.65 4.61 5.46 Salicylic acid 3.00 3.00 3.00 3.00 solution.sup.1 DBTDL solution.sup.2 1.50 1.50 1.50 1.50 Migration Height 20 19 33 19 (7 d) [mm] Width 21 19 28 19 Odor no yes no no .sup.15% in dioctyl adipate .sup.25% dibutyltin dilaurate in diisodecyl phthalate

(139) Use of Oxazolidine A-13 as Desiccant and/or Curing Agent:

(140) Compositions Z37 to Z40:

(141) For each composition, 105.0 parts by weight of Polymer P5, 60.0 parts by weight of the thickener described for composition Z28, 30.0 parts by weight of diisodecyl phthalate, 100.0 parts by weight of chalk, 7.0 parts by weight of silica (Aerosil® R972, from Evonik), the parts by weight of oxazolidine A-13 or Incozol 2 (from Incorez) specified in table 5, and 2.0 parts by weight of salicylic acid solution (5% by weight in dioctyl adipate) and 1.0 part by weight of DBTDL solution (5% by weight of dibutyltin dilaurate in diisodecyl phthalate) were mixed with exclusion of moisture by means of the centrifugal mixer and stored with exclusion of moisture.

(142) The compositions were tested as follows:

(143) As a measure of storage stability, Viscosity (1d RT) was determined the day after production, Viscosity (7d RT) after storage for 7 days in a closed container at room temperature, and Viscosity (7d 60° C.) after storage for 7 days in a closed container in a circulation oven at 60° C., as described above. As a measure of the open time, Tack-free time was determined as described above.

(144) The mechanical properties of Tensile strength (breaking strength), Elongation at break, and Modulus of elasticity 5% (at 0.5-5% elongation) and Modulus of elasticity 25% (at 0.5-25% elongation) were determined as described above.

(145) Shore A hardness was determined according to DIN 53505 on test specimens cured under standard conditions for 7 days.

(146) The results are reported in table 5.

(147) The compositions labeled with (Ref) are comparative examples.

(148) TABLE-US-00005 TABLE 5 Composition (in parts by we ght) and properties of Z37 to Z40. “pbw” stands for parts by weight Z38 Z40 Z37 (Ref) Z39 (Ref) with with 1.6 with with 4.4 2.7 pbw of pbw of 7.5 pbw of pbw of oxazolidine Incozol oxazolidine Incozol Composition A13 2 A13 2 Viscosity [Pa .Math. s] 20° C. (1 d RT) 152    168    141    159    (7 d RT) 161    171    144    218    (7 d 60° C.) 188    264    189    516    Tack-free time 120′   75′   150′   80′   Tensile strength 1.75 1.84 1.79 1.95 [MPa] Elongation at break 420    400    940    875    [%] Modulus of elasticity 3.66 3.65 1.44 1.63 5% [MPa] Modulus of elasticity 2.58 2.61 1.19 1.39 25% Shore A 53    56    31    35   

(149) Use of oxazolidine A-14 as adhesion promoter:

(150) Activator-1:

(151) 2.5 g of oxazolidine A-14 were dissolved in 250 g of dry ethyl acetate and stored with exclusion of moisture.

(152) Composition Z-41:

(153) 1.5 g of oxazolidine A-14 were mixed under a nitrogen atmosphere with 150 g of polymer P1 and stored with exclusion of moisture.

(154) As a measure of action as adhesion promoter, spacer tape was applied longitudinally to a glass plate (float glass; from Rocholl, Schönbrunn, Germany) having dimensions of 10×15 cm on the air side so as to give three glass strips each of 2×8 cm. The first and second strips were each wiped once with an ethyl acetate-soaked hygiene wipe. The third strip was wiped once with a hygiene wipe wetted with activator-1. Subsequently, the glass plate treated in this way was stored under standard climatic conditions for flashoff for 2 h. Then 6 g of polymer P1 was applied in a layer thickness of about 3 mm to each of the first and third strips. 6 g of composition Z-41 was applied to the second strip in a layer thickness of about 3 mm.

(155) The glass plate thus coated was stored under standard climatic conditions for 7 days and then attempts were made to detach the cured polymer films from the glass plate. The bonding was described as “very good” when the cured polymer could not be removed from the glass substrate. (Even after several cuts transverse to the strip direction down to the glass substrate, by which the polymer was cut away from the glass, and pulling the polymer strip away vertically, it was not possible to detach the polymer from the glass substrate.) The bonding was described as “none” when the cured polymer could be fully detached from the glass substrate.

(156) The results are shown in table 6.

(157) TABLE-US-00006 TABLE 6 Pretreatment Polymer strip Bonding Ethyl acetate Polymer P1 none Ethyl acetate Composition Z-41 very good Activator-1 Polymer P1 very good

(158) Primer Compositions Z-42:

(159) 125.0 g of Sika® Primer-209 N (pigmented primer containing isocyanate groups, from Sika Schweiz AG) was mixed with 21.2 g of oxazolidine A-14 and stored with exclusion of moisture.

(160) Primer composition Z 42 was used as adhesion promoter on glass: a long flashoff time of 24 hours or 7 days was followed by application of Sikaflex®-250 DM-5 (one-component moisture-curing polyurethane adhesive, from Sika Switzerland AG) and curing thereof, and then the bonding thereof was tested. The reference used was Sika® Primer-209 N.

(161) For each test, a glass plate was cleaned with isopropanol, wiped with a hygiene wipe soaked with Sika® Aktivator-100 (adhesion-promoting cleaner, from Sika Schweiz AG) and, after a flashoff time of 10 min, the primer composition was applied in a thin layer with a sponge. After a flashoff time of 24 hours or 7 days under standard climatic conditions, Sikaflex®-250 DM-5 that had been preheated to 60° C. was applied in the form of a triangular bead of width 10 mm and length 100 mm to the primer layer and the glass plate was stored under standard climatic conditions for 7 days, in the course of which the adhesive applied cured. Subsequently, the bonding of the adhesive bead on the glass plate was tested by making an incision into the bead at the end just above the bonding surface, holding the cut end of the bead with rounded tweezers and trying to pull the bead away from the substrate. Then the bead was incised again down to the substrate, the part of the bead that had been cut away was rolled up with the rounded tweezers and an attempt was again made to pull the bead away from the substrate. In this way, the bead was cut away from the substrate by pulling over a length of 80 mm. Subsequently, bonding was assessed with reference to the failure profile using the following scale:

(162) 1 (=very good) represents more than 95% cohesive failure

(163) 2 (=good) represents 75% to 95% cohesive failure

(164) The results are reported in table 7.

(165) TABLE-US-00007 TABLE 7 Primer Sika ® composition: Z-42 Primer-209 N Bonding of Flashoff Sikaflex ® 250 DM-5 time: 24 h 1 2 7 d 1 1