Polymer containing silane groups

Abstract

The invention relates to polymers containing silane groups, to a method for their production and to their use as a component of curable compositions, in particular of moisture-curing sealants, adhesives or coatings that can be applied at ambient temperature, or of hot-melt adhesives containing silane groups. The polymers containing silane groups are obtained in particular by means of a special hydroxysilane which can be produced in particular from the reaction of lactides with aminosilanes.

Claims

1. A polymer having end groups of the formula (I) ##STR00006## where R.sup.1a is a methyl radical; R.sup.1b is a hydrogen atom; R.sup.2 is a hydrogen atom or a monovalent hydrocarbyl radical which has 1 to 12 carbon atoms and optionally contains ether groups, ester groups, nitrile groups, amino groups or silane groups; R.sup.3 is a linear or branched alkylene or cycloalkylene radical having 1 to 20 carbon atoms, optionally having aromatic moieties, and optionally having one or more heteroatoms; R.sup.4 is an alkyl radical having 1 to 8 carbon atoms; R.sup.5 is an alkyl radical which has 1 to 10 carbon atoms and optionally contains ether groups; and x is 0, 1 or 2.

2. The polymer as claimed in claim 1, wherein R.sup.2 is a hydrogen atom or an alkyl radical or a cycloalkyl radical or an alkoxysilyl-alkyl radical.

3. The polymer as claimed in claim 1, wherein R.sup.3 is selected from the group consisting of 1,3-propylene, 2-methyl-1,3-propylene, 1,4-butylene, 3-methyl-1,4-butylene and 3,3-dimethyl-1,4-butylene.

4. The polymer as claimed in claim 1, wherein R.sup.5 is a methyl radical or ethyl radical.

5. The polymer as claimed in claim 1, wherein x is 1 or 0.

6. The polymer as claimed in claim 1, which has a functionality, based on the end groups of the formula (I), in the range from 1 to 4.

7. The polymer as claimed in claim 1, which has an average molecular weight in the range from 1,000 to 30,000 g/mol.

8. The polymer as claimed in claim 1, which is liquid at room temperature and has a majority of polyoxyalkylene units.

9. The polymer as claimed in claim 1, which is solid at room temperature and has a majority of polyester units and/or polycarbonate units.

10. A process for preparing the polymer as claimed in claim 1, comprising reacting: at least one polyol, at least one diisocyanate, either at least one lactide of the formula (II) or at least one hydroxy ester of the formula (III), and at least one aminosilane of the formula (IV) with one another, ##STR00007## where m is an integer from 1 to 100; and R.sup.6 is a monovalent hydrocarbyl radical having 1 to 12 carbon atoms.

11. The process as claimed in claim 10, wherein a hydroxy-silane of the formula (V) is obtained as an intermediate ##STR00008##

12. The process as claimed in claim 11, wherein the hydroxysilane of the formula (V) is prepared using a lactide of the formula (II).

13. A curable composition comprising the polymer as claimed in claim 1 and at least one further constituent.

14. The curable composition as claimed in claim 13, wherein the curable composition is either a moisture-curing composition applicable at room temperature or a hotmelt adhesive containing silane groups.

15. A process for preparing a polymer having end groups of the formula (I) ##STR00009## where R.sup.1a and R.sup.1b are each independently a hydrogen atom or a monovalent hydrocarbyl radical having 1 to 12 carbon atoms, or together are an alkylene radical having 2 to 6 carbon atoms; R.sup.2 is a hydrogen atom or a monovalent hydrocarbyl radical which has 1 to 12 carbon atoms and optionally contains ether groups, ester groups, nitrile groups, amino groups or silane groups; R.sup.3 is a linear or branched alkylene or cycloalkylene radical having 1 to 20 carbon atoms, optionally having aromatic moieties, and optionally having one or more heteroatoms; R.sup.4 is an alkyl radical having 1 to 8 carbon atoms; R.sup.5 is an alkyl radical which has 1 to 10 carbon atoms and optionally contains ether groups; and x is 0, 1 or 2, the method comprising reacting: at least one polyol, at least one diisocyanate, either at least one lactide of the formula (II) or at least one hydroxy ester of the formula (III), and at least one aminosilane of the formula (IV) with one another, ##STR00010## where m is an integer from 1 to 100; and R.sup.6 is a monovalent hydrocarbyl radical having 1 to 12 carbon atoms.

16. The process as claimed in claim 15, wherein a hydroxy-silane of the formula (V) is obtained as an intermediate ##STR00011##

Description

EXAMPLES

(1) Detailed hereinafter are working examples which are intended to illustrate the invention described in detail. It will be appreciated that the invention is not restricted to these described working examples.

(2) “Standard climatic conditions” are understood to mean a temperature of 23±1° C. and a relative air humidity of 50±5%. “SCC” stands for standard climatic conditions.

(3) .sup.1H NMR spectra were measured in CDCl.sub.3 on a Bruker Ascend 400 spectrometer at 400.14 MHz; the chemical shifts δ are reported in ppm relative to tetramethylsilane (TMS); the coupling constants J are reported in Hz.

(4) Infrared spectra (FT-IR) were measured as undiluted films on a Nicolet iS5 FT-IR system, equipped with a horizontal ATR measurement unit with a diamond crystal, from Thermo Scientific; the absorption bands are reported in wavenumbers (cm.sup.−1) (measurement window: 4000-650 cm.sup.−1). The addition “sh” indicates a band that appears as a shoulder.

(5) Gas chromatograms (GC) were measured in the temperature range from 60 to 320° C. with a heating rate of 30° C./min and a dwell time of 15 min at 320° C. The injector temperature was 200° C. Detection was effected by means of flame ionization (FID), with evaluation of the signals via the area percent method.

(6) Viscosities at 20° C. were measured on a thermostatted 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).

(7) Viscosities at 160° C. were measured on a thermostatted Rheotec RC30 plate-plate viscometer (plate diameter 25 mm, distance 1 mm, shear rate 10 s.sup.−1).

(8) 1. Preparation of Hydroxysilanes

Hydroxysilane HS-1a: N-(3-triethoxysilylpropyl)-2-hydroxypropanamide

(9) In a round-bottom flask, 36.00 g (162.6 mmol) of 3-aminopropyltriethoxysilane, 12.07 g (83.7 mmol) of L-lactide and 0.15 g of vinyltriethoxysilane were stirred under a nitrogen atmosphere at 80° C. for 3 h, until the reaction was found to have progressed no further by means of IR spectroscopy. The crude product was aftertreated at 60° C. and about 10 mbar for 15 minutes. A liquid product having a theoretical OH equivalent weight of 293.4 g/eq was obtained.

(10) FT-IR: 3406 sh (O—H), 3322 (N—H amide), 2974, 2928, 2885, 2736, 1741 (C═O ester), 1651 (C═O amide), 1535 (C═O amide), 1482, 1444, 1411, 1390, 1365, 1279, 1192, 1165, 1100, 1073, 996, 954, 886, 863, 775, 678.

(11) .sup.1H NMR: δ 6.69 (s, 1 H, O═C—NH), 4.21 (q, 1 H, (R).sub.3CH, J=6.8), 3.82 (q, 6 H, Si—O—CH.sub.2—CH.sub.3, J=7.0), 3.28 (m, 2 H, NH—CH.sub.2—CH.sub.2—CH.sub.2—Si), 1.65 (m, 2 H, NH—CH.sub.2—CH.sub.2—CH.sub.2—Si), 1.42 (d, 3 H, CH.sub.3—CH(R).sub.2, J=6.8), 1.23 (t, 9 H, Si—O—CH.sub.2—CH.sub.3, J=7.0), 0.65 (t, 2 H, NH—CH.sub.2—CH.sub.2—CH.sub.2—Si, J=8.1).

(12) GC (3 days after preparation): 96.2% N-(3-triethoxysilylpropyl)-2-hydroxypropanamide, 1.7% 3-aminopropyltriethoxysilane and 2.1% ethyl lactate.

(13) GC (6 weeks after preparation): 95.8% N-(3-triethoxysilylpropyl)-2-hydroxypropanamide, 1.3% 3-aminopropyltriethoxysilane and 2.9% ethyl lactate.

Hydroxysilane HS-1b: N-(3-triethoxysilylpropyl)-2-hydroxypropanamide

(14) In a round-bottom flask, 14.01 g (118.6 mmol) of ethyl-lactate, 10.00 g of ethanol and 0.15 g of vinyltriethoxysilane were stirred under a nitrogen atmosphere at 60° C. for 10 minutes. Then 25.00 g (112.9 mmol) of 3-amino-propyltriethoxysilane and 0.20 g of Tytan® TAA (titanium acetylacetonate; from Borica Company Ltd) were added and the mixture was stirred at reflux at 100° C. for 5 h, until the reaction was found to have progressed no further by means of IR spectroscopy. The crude product was aftertreated at 80° C. and about 10 mbar for 30 minutes. A liquid product having a theoretical OH equivalent weight of 293.4 g/eq was obtained.

(15) GC (3 days after preparation): 80.4% N-(3-triethoxysilylpropyl)-2-hydroxypropanamide, 19.6% 3-aminopropyltriethoxysilane and <0.1% ethyl lactate.

Hydroxysilane HS-2a: N-(3-trimethoxysilylpropyl)-2-hydroxypropanamide

(16) In a round-bottom flask, 16.21 g (90.4 mmol) of 3-aminopropyltrimethoxysilane, 6.20 g (43.05 mmol) of L-lactide and 0.10 g of vinyltrimethoxysilane were stirred under a nitrogen atmosphere at 60° C. for a few minutes, until all the solids were in solution. The mixture was then left to stand under nitrogen at 23° C. for 48 h. According to IR spectroscopy, the reaction was complete. A liquid product having a theoretical OH equivalent weight of 251.4 g/eq was obtained.

(17) FT-IR: 3410 sh (O—H), 3349 (N—H amide), 2969, 2940, 2841, 1746 (C═O ester), 1651 (C═O amide), 1532 (C═O amide), 1446, 1412, 1367, 1347, 1311, 1279, 1191, 1080, 1038, 963, 884, 864, 808, 776 sh, 677.

Hydroxysilane HS-2b: N-(3-trimethoxysilylpropyl)-2-hydroxypropanamide

(18) In a round-bottom flask, 12.34 g (118.6 mmol) of methyl L-lactate, 10.00 g of methanol and 0.15 g of vinyltrimethoxysilane were stirred under a nitrogen atmosphere at 60° C. for 10 minutes. Then 20.25 g (112.9 mmol) of 3-aminopropyltrimethoxysilane and 0.20 g of Tytan® TAA were added and the mixture was stirred at reflux at 90° C. for 6 h, until the reaction was found to have progressed no further by means of IR spectroscopy. The crude product was aftertreated at 60° C. and about 30 mbar for 30 minutes. A liquid product having a theoretical OH equivalent weight of 251.4 g/eq was obtained.

Hydroxysilane HS-3: N-(3-triethoxysilylpropyl)-2-hydroxyacetamide

(19) In a round-bottom flask, 21.29 g (96.2 mmol) of 3-aminopropyltriethoxysilane, 5.47 g (47.1 mmol) of 1,4-dioxane-2,5-dione and 0.10 g of vinyltriethoxysilane were stirred under a nitrogen atmosphere at 100° C. for 2 h, until the reaction was found to have progressed no further by means of IR spectroscopy. The crude product was aftertreated at 40° C. and about 30 mbar for 10 minutes. A liquid product having a theoretical OH equivalent weight of 279.4 g/eq was obtained.

(20) FT-IR: 3418 sh (O—H), 3326 (N—H amide), 2973, 2927, 2885, 2735, 1756 (C═O ester), 1655 (C═O amide), 1536 (C═O amide), 1482, 1443, 1411, 1390, 1366, 1350, 1293, 1192, 1165, 1100, 1072, 953, 880, 849, 772, 680.

Hydroxysilane HS-4: N-(3-trimethoxysilylpropyl)-2-hydroxyacetamide

(21) In a round-bottom flask, 16.21 g (90.4 mmol) of 3-aminopropyltrimethoxysilane, 5.14 g (44.3 mmol) of 1,4-dioxane-2,5-dione and 0.10 g of vinyltrimethoxy-silane were stirred at 100° C. under a nitrogen atmosphere for 2 h, until the reaction was found to have progressed no further by means of IR spectroscopy. The crude product was aftertreated at 40° C. and about 50 mbar for 10 minutes. A liquid product having a theoretical OH equivalent weight of 237.3 g/eq was obtained.

(22) FT-IR: 3414 sh (O—H), 3308 (N—H amide), 2941, 2841, 1757 (C═O ester), 1652 (C═O amide), 1533 (C═O amide), 1444, 1412, 1350, 1281, 1191, 1076, 892, 808, 771, 679.

Hydroxysilane HS-5: N-(3-triethoxysilylpropyl)-2-hydroxy-2-methylpropanamide

(23) In a round-bottom flask, 15.67 g (118.6 mmol) of ethyl 2-hydroxyisobutyrate and 0.15 g of vinyltriethoxysilane were stirred under a nitrogen atmosphere at and 60° C. for 10 minutes. Then 25.00 g (112.9 mmol) of 3-aminopropyltriethoxysilane and 0.20 g of Tytan® TAA were added and the mixture was stirred at 130° C. for 6 h, until the reaction was found to have progressed no further by means of IR spectroscopy. The crude product was aftertreated at 80° C. and about 10 mbar for 30 minutes. A liquid product having a theoretical OH equivalent weight of 307.5 g/eq was obtained.

(24) FT-IR: 3414 sh (O—H), 3349 (N—H amide), 2973, 2926, 2881, 2735 sh, 1727 (C═O ester), 1649 (C═O amide), 1605 sh, 1533 (C═O amide), 1465, 1446, 1390, 1359, 1344, 1280, 1240, 1163, 1101, 1077, 993, 953, 842, 777, 679.

Hydroxysilane HS-6: N-(3-trimethoxysilylpropyl)-2-hydroxy-2-methylpropanamide

(25) In a round-bottom flask, 14.00 g (118.6 mmol) of methyl 2-hydroxyisobutyrate and 0.15 g of vinyltrimethoxysilane were stirred under a nitrogen atmosphere at 60° C. for 10 minutes. Then 20.25 g (112.9 mmol) of 3-aminopropyltrimethoxysilane and 0.20 g of Tytan® TAA were added and the mixture was stirred at 110° C. for 5 h, until the reaction was found to have progressed no further by means of IR spectroscopy. The crude product was aftertreated at 60° C. and about 30 mbar for 30 minutes. A liquid product having a theoretical OH equivalent weight of 265.4 g/eq was obtained.

(26) FT-IR: 3410 sh (O—H), 3353 (N—H amide), 2969, 2940, 2840, 1746 (C═O ester), 1650 (C═O amide), 1609 sh, 1531 (C═O amide), 1464, 1411, 1368, 1280, 1188, 1078, 1019, 969, 936, 909, 854, 804, 678.

(27) 2. Preparation of Polyurethane Polymers Having Isocyanate Groups

(28) Polymer NCO-1:

(29) With exclusion of moisture, 1000 g of Acclaim® 12200 polyol (polyoxypropylenediol having a low unsaturation level, from Bayer; OH number 11.0 mg KOH/g), 43.6 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik), 126.4 g of diisodecyl phthalate (DIDP) and 0.1 g of bismuth tris(neodecanoate) (10% by weight in DIDP) were heated at 90° C. while stirring constantly and left at this temperature until the content of free isocyanate groups, determined by titrimetry, had reached a stable value of 0.63% by weight. The product was cooled to room temperature and stored with exclusion of moisture. The day after the preparation, it had a viscosity at 20° C. of 31 Pa.Math.s.

(30) Polymer NCO-2:

(31) With exclusion of moisture, 1000 g of Acclaim® 12200 polyol (polyoxypropylenediol having a low unsaturation level, from Bayer; OH number 11.0 mg KOH/g), 34.2 g of tolylene 2,4-diisocyanate (Desmodur® T-100, from Bayer), 126.4 g of diisodecyl phthalate (DIDP) and 0.1 g of bismuth tris(neodecanoate) (10% by weight in DIDP) were heated at 90° C. while stirring constantly and left at this temperature until the content of free isocyanate groups, determined by titrimetry, had reached a stable value of 0.65% by weight. The product was cooled to room temperature and stored with exclusion of moisture. The day after the preparation, it had a viscosity at 20° C. of 35 Pa.Math.s.

(32) Polymer NCO-3:

(33) A mixture of 1,200.0 g of room temperature solid, amorphous polyesterdiol (Dynacoll® 7150, from Evonik; OH number 43 mg KOH/g) and 1,200.0 g of polyesterdiol (Dynacoll® 7250, from Evonik; OH number 22 mg KOH/g) was dried at 120° C. under reduced pressure for 2 h and degassed, then 348.4 g of diphenylmethane 4,4′-diisocyanate (Desmodur® 44 MC L, from Bayer) were added, and the mixture was stirred at 130° C. under reduced pressure for 2 h and then cooled and stored with exclusion of moisture. The polyurethane polymer obtained was solid at room temperature and had a content of free isocyanate groups, determined by titrimetry, of 2.15% by weight.

(34) 3. Preparation of Isocyanatosilanes

(35) Isocyanatosilane IS-1:

(36) In a round-bottom flask, 8.00 g (27.3 mmol) of hydroxysilane HS-1a, 6.06 g (27.3 mmol) of isophorone diisocyanate (Vestanat® IPDI, from Evonik) and 0.03 g of bismuth tris(neodecanoate) (10% by weight in DIDP) were stirred under a nitrogen atmosphere at 80° C. for 4 h and then stored with exclusion of moisture at room temperature for 4 days. A highly viscous product having a content of free isocyanate groups, determined by titrimetry, of 8.2% by weight was obtained.

(37) FT-IR: 3436 sh, 3312 (N—H amide), 3090, 2973, 2927, 2894, 2254 (N═C═O), 1704 (C═O urethane), 1661 (C═O amide), 1532 (C═O amide), 1462, 1445, 1411, 1388, 1365, 1303, 1237, 1194, 1164, 1102, 1075, 955, 904, 857, 773.

(38) Isocyanatosilane IS-2:

(39) In a round-bottom flask, 8.00 g (27.3 mmol) of hydroxysilane HS-1a, 4.74 g (27.3 mmol) of tolylene 2,4-diisocyanate (Desmodur® T-100, from Bayer) were stirred under a nitrogen atmosphere at 80° C. for 4 h and then stored with exclusion of moisture at room temperature for 4 days. A very highly viscous product having a content of free isocyanate groups, determined by titrimetry, of 6.5% by weight was obtained.

(40) FT-IR: 3427 sh, 3295 (N—H amide), 3099, 2974, 2927, 2885, 2267 (N═C═O), 1732 (C═O urethane), 1658 (C═O amide), 1617, 1596, 1537 (C═O amide), 1445, 1413, 1387, 1367, 1306, 1276, 1221, 1165, 1099, 1074, 995, 953, 874, 767, 703, 677.

(41) 4. Preparation of Polymers Having End Groups of the Formula (I)

(42) Polymers SP-1 to SP-8 (Liquid at Room Temperature)

(43) For each polymer, 100 parts by weight of polymer NCO-1 were mixed with the hydroxysilane specified in table 1 in the amount specified (OH/NCO=1.10). The mixture was stirred under a nitrogen atmosphere at 70° C. until no isocyanate groups were detectable any longer by means of IR spectroscopy (about 2 hours). Subsequently, the reaction mixture was cooled and stored with exclusion of moisture. The viscosity in each case was measured the day after the preparation at a temperature of 20° C. The properties of the polymers obtained are reported in table 1.

(44) TABLE-US-00001 TABLE 1 Composition and properties of the polymers containing silane groups SP-1 to SP-8. Polymer SP-1 SP-2 SP-3 SP-4 SP-5 SP-6 SP-7 SP-8 Polymer NCO-1 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Hydroxysilane HS-1a, HS-1b, HS-3, HS-5, HS-2a, HS-2b, HS-4, HS-6, 4.84 4.84 4.61 5.07 4.15 4.15 3.92 4.38 Viscosity [Pa .Math. s] 63 125 120 85 128 179 114 295

(45) Polymer SP-9: (Liquid at Room Temperature)

(46) 100.00 g of polymer NCO-2 were mixed with 4.99 g of hydroxysilane HS-1a. This mixture was stirred under a nitrogen atmosphere at 60° C. until no isocyanate groups were detectable any longer by means of IR spectroscopy (about 2 hours). Subsequently, the reaction mixture was cooled and stored with exclusion of moisture.

(47) The day after the preparation, the viscosity was 106 Pa.Math.s at 20° C.

(48) Polymer SP-10: (Liquid at Room Temperature)

(49) To a predried mixture of 100.0 g (20 mmol OH) Acclaim® 12200 polyol (polyoxypropylenediol having a low unsaturation level, from Bayer; OH number 11.0 mg KOH/g) and 12.25 g of diisodecyl phthalate were added 10.83 g of isocyanatosilane IS-1 and 0.15 g of bismuth tris(neodecanoate) (10% by weight in DIDP). This mixture was stirred under a nitrogen atmosphere at 80° C. until no further change in the isocyanate band was detectable by means of IR spectroscopy (about 2 hours). Then 0.30 g of anhydrous ethanol was added, and the mixture was stirred at 70° C. for 5 minutes and degassed at 80° C. under reduced pressure for 15 minutes. Thereafter, no isocyanate groups were detectable any longer by means of IR spectroscopy.

(50) The day after the preparation, the viscosity was 128 Pa.Math.s at 20° C.

(51) Polymer SP-11: (Liquid at Room Temperature)

(52) Polymer SP-11 was prepared like polymer SP-10, except that, rather than the isocyanatosilane IS-1, 9.82 g of isocyanatosilane IS-2 were used.

(53) The day after the preparation, the viscosity was 46 Pa.Math.s at 20° C.

(54) Polymer SP-12 (Solid at Room Temperature)

(55) To 100.0 g of the molten polymer NCO-3 were added 17.28 g of hydroxysilane HS-1a. This mixture was stirred under a nitrogen atmosphere at 120° C. until no isocyanate groups were detectable any longer by means of IR spectroscopy (about 2 hours). Subsequently, the reaction mixture was cooled and stored with exclusion of moisture.

(56) The day after the preparation, the viscosity was 35 Pa.Math.s at 160° C.

(57) 5. Production of Room Temperature Applicable Moisture-Curing Compositions

(58) Compositions Z-1 to Z-12

(59) For each composition, the ingredients specified in table 2 or 3 in the amounts specified (in parts by weight) were processed in a vacuum mixer at 50° C. with exclusion of moisture for 30 minutes to give a homogeneous paste and stored. Each composition was tested as follows:

(60) To determine the skinning time, 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 tapped gently by means of an LDPE pipette, there were for the first time no remaining residues on the pipette was determined.

(61) To determine the mechanical properties, the composition was cast on a PTFE-coated film to give a film of thickness 2 mm, which was stored under standard climatic conditions for 2 weeks, some 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 pulling speed of 200 mm/min for tensile strength (breaking force), elongation at break and modulus of elasticity (modulus of elasticity at 0.5%-50% elongation).

(62) Shore A hardness was determined in accordance with DIN 53505 on test specimens which had been cured under standard climatic conditions for 14 days.

(63) These results are appended with “SCC:”.

(64) As a measure of thermal stability, some dumbbells and the Shore A test specimen after the 2 weeks under standard climatic conditions were additionally stored in an air circulation oven at 100° C. for four weeks and then tested in the same way for tensile strength, elongation at break and modulus of elasticity, or for Shore A hardness. These results are appended with “100° C.:”. The results are reported in tables 2 and 3.

(65) The thixotropic paste was produced by initially charging a vacuum mixer with 300 g of diisodecyl phthalate and 48 g of diphenylmethane 4,4′-diisocyanate (Desmodur® 44 MC L; from Bayer), gently heating and then slowly adding dropwise 27 g of monobutylamine while stirring vigorously. Stirring of the resultant paste continued under reduced pressure and with cooling for one hour.

(66) TABLE-US-00002 TABLE 2 Composition and properties of compositions Z-1 to Z-5. Composition Z-1 Z-2 Z-3 Z-4 Z-5 Polymer SP-1, SP-2, SP-3, SP-4, SP-5, 15.00 15.00 15.00 15.00 15.00 Diisodecyl phthalate 20.00 20.00 20.00 20.00 20.00 Thixotropic paste 2.00 2.00 2.00 2.00 2.00 Vinyltriethoxysilane 1.00 1.00 1.00 1.00 — Vinyltrimethoxysilane — — — — 1.00 Socal ® U1 S2 .sup.1 10.00 10.00 10.00 10.00 10.00 Omyacarb ® 5 GU .sup.2 50.00 50.00 50.00 50.00 50.00 Tyzor ® IBAY .sup.3 1.25 1.25 1.25 1.25 1.25 Skinning time [min] 55 35 30 60 15 SCC: Shore A 38 32 29 27 32 Tensile strength [MPa] 1.50 1.02 0.96 0.90 1.03 Elongation at break [%] 150 135 110 125 125 Modulus of elasticity 1.19 0.81 0.83 0.74 0.83 [MPa] 100° C.: Shore A 28 17 14 17 18 Tensile strength [MPa] 0.94 0.63 0.51 0.54 0.61 Elongation at break [%] 125 105 100 135 110 Modulus of elasticity 0.77 0.59 0.50 0.45 0.55 [MPa] .sup.1 precipitated calcium carbonate (from Solvay) .sup.2 ground calcium carbonate (from Omya) .sup.3 bis(ethylacetoacetato)diisobutoxytitanium(IV) (from Dorf Ketal)

(67) TABLE-US-00003 TABLE 3 Composition and properties of compositions Z-6 to Z-11. Composition Z-6 Z-7 Z-8 Z-9 Z-10 Z-11 Polymer SP-6 SP-7 SP-8, SP-9, SP-10, SP-11, 15.00 15.00 15.00 15.00 15.00 15.00 Diisodecyl phthalate 20.00 20.00 20.00 20.00 20.00 20.00 Thixotropic paste 2.00 2.00 2.00 2.00 2.00 2.00 Vinyltriethoxysilane — — — 1.00 1.00 1.00 Vinyltrimethoxysilane 1.00 1.00 1.00 — — — Socal ® U1 S2 .sup.1 10.00 10.00 10.00 10.00 10.00 10.00 Omyacarb ® 5 GU .sup.2 50.00 50.00 50.00 50.00 50.00 50.00 Tyzor ® IBAY .sup.3 1.25 1.25 1.25 1.25 1.25 1.25 Skinning time [min] 30 20 5 40 85 85 SCC: Shore A 15 16 19 39 25 21 Tensile strength [MPa] 0.45 0.42 0.55 1.37 0.85 0.62 Elongation at break 85 65 95 145 120 83 [%] Modulus of elasticity 0.48 0.53 0.57 1.12 0.66 0.64 [MPa] .sup.1 precipitated calcium carbonate (from Solvay) .sup.2 ground calcium carbonate (from Omya) .sup.3 bis(ethylacetoacetato)diisobutoxytitanium(IV) (from Dorf Ketal)
6. Production of Hotmelt Adhesives

(68) Hotmelt Adhesive K-1:

(69) To 100.00 g of polymer SP-12 melted at 140° C. was added 0.02 g of dibutyltin dilaurate. The resultant hotmelt adhesive was stored with exclusion of moisture.

(70) To determine the mechanical properties, the hotmelt adhesive was pressed in a heatable press between two PTFE-coated films to give a film of thickness 1 mm and cooled down, the PTFE-coated films were removed and the film was stored under SCC for 10 days. Thereafter, dumbbell-shaped test specimens 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 used to determine the tensile strength (breaking force), elongation at break and modulus of elasticity (within the extension range specified) in accordance with DIN EN 53504 at a pulling speed of 200 mm/min. The results are reported in table 4.

(71) TABLE-US-00004 TABLE 4 Mechanical properties of hotmelt adhesive K-1. Hotmelt adhesive K-1 Tensile strength [MPa] 0.20 Elongation at break [%] 500 Modulus of elasticity (0.5-5%) [MPa] 1.22 Modulus of elasticity (0.5-25%) [MPa] 0.39 Modulus of elasticity (0.5-50%) [MPa] 0.16 Appearance clear, bubble-free