FAST-CURING COMPOSITION CONTAINING SILANE GROUPS

Abstract

A polymer preparation consisting of silane-functional polymers, including at least one polymer having at least one terminal group of formula (I) and at least one further silane terminal group, a method for producing the polymer preparation and a composition containing it. The polymer preparation has a surprisingly low viscosity, cross-links surprisingly quickly even without the use of EHS-critical catalysts such as organotin compounds or DBU, and hardens into a non-sticky material with good strength and elasticity. It is especially well suited as an elastic adhesive or sealant or as an elastic coating. The invention further relates to a method for lowering the viscosity of a polymer having at least one terminal group of formula (I) by introducing at least one further silane terminal group.

Claims

1. A polymer formulation consisting of silane-functional polymers comprising at least one polymer having at least one end group of the formula (I) ##STR00010## where R.sup.1a, R.sup.1b, R.sup.1c and R.sup.1d are each independently a hydrogen atom or a monovalent hydrocarbyl radical having 1 to 12 carbon atoms, or in pairs are each 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 components, and optionally having one or more heteroatoms, especially nitrogen atoms, 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, x is 0 or 1 or 2, m is 0 or 1, and n is 0 or 1 or 2 or 3 or 4 or 5, where n, if m is 1, is 1 or 2 or 3 or 4; and at least one further silane end group that does not correspond to the formula (I).

2. The polymer formulation as claimed in claim 1, wherein the silane-functional polymers are polyethers and/or polyesters and/or polycarbonates containing silane groups.

3. The polymer formulation as claimed in claim 1, wherein the silane-functional polymers overall have an average molecular weight in the range from 1,000 to 30,000 g/mol.

4. The polymer formulation as claimed in claim 1, wherein m is 0, n is 0, R.sup.1a is a methyl radical and R.sup.1b is a hydrogen atom.

5. The polymer formulation as claimed in claim 1, wherein m is 0, n is 2, R.sup.1a is a methyl radical or is an n-butyl radical, and R.sup.1b, R.sup.1c and R.sup.1d are each a hydrogen atom.

6. The polymer formulation as claimed in claim 1, wherein m is 1, n is 1, R.sup.1a is a methyl radical, and R.sup.1b, R.sup.1c and R.sup.1d are each a hydrogen atom.

7. The polymer formulation as claimed in claim 1, wherein the further silane end group is an end group of the formula (II) ##STR00011## where R.sup.6 is a linear or branched alkylene or cycloalkylene radical having 1 to 20 carbon atoms, optionally having aromatic components, R.sup.7 is an alkyl radical having 1 to 8 carbon atoms, R.sup.8 is an alkyl radical which has 1 to 10 carbon atoms and optionally contains ether groups, and y is 0 or 1 or 2.

8. The polymer formulation as claimed in claim 1, wherein the further silane end group is an end group of the formula (III) ##STR00012## where R.sup.9 is a methyl radical or an ethyl radical and z is 0 or 1 or 2.

9. The polymer formulation as claimed in claim 1, wherein the silane-functional polymers overall have a ratio between the number of end groups of the formula (I) and the number of further silane end groups in the range from 99/1 to 5/95.

10. A process for producing the polymer formulation as claimed in claim 1, comprising the steps of providing a polymer containing at least one hydroxyl group and at least one silane end group which does not correspond to the formula (I) as first intermediate; reacting the first intermediate with at least one diisocyanate at an NCO/OH ratio of more than 1 to give a second intermediate; and reacting the second intermediate with at least one hydroxysilane of the formula (VI) at an NCO/OH ratio of not more than 1 ##STR00013##

11. The process as claimed in claim 10, wherein the first intermediate is prepared by reacting at least one polyol with at least one isocyanatosilane of the formula (IV) at an NCO/OH ratio of less than 1 ##STR00014## or at least one polyol having allyl groups with at least one hydrosilane of the formula (V) with hydrosilylation of the allyl groups ##STR00015##

12. A composition comprising at least one polymer formulation as claimed in claim 1.

13. The composition as claimed in claim 12, wherein it has a content of silane-functional polymers in the range from 5% to 95% by weight.

14. The method of using a composition as claimed in claim 12 as an elastic adhesive or sealant or as an elastic coating.

15. A method of lowering the viscosity of a polymer having at least one end group of the formula (I) by introducing at least one further silane end group that does not correspond to the formula (I) ##STR00016## where R.sup.1a, R.sup.1b, R.sup.1c and R.sup.1d are each independently a hydrogen atom or a monovalent hydrocarbyl radical having 1 to 12 carbon atoms, or in pairs are each 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 components, and optionally having one or more heteroatoms, especially nitrogen atoms, 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, x is 0 or 1 or 2, m is 0 or 1, and n is 0 or 1 or 2 or 3 or 4 or 5, where n, if m is 1, is 1 or 2 or 3 or 4.

Description

EXAMPLES

[0194] Detailed hereinafter are working examples which are intended to illustrate the invention described in detail. Of course, the invention is not restricted to these described working examples.

[0195] “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”.

[0196] “TFT” stands for “tack-free time”.

[0197] Viscosities were determined on a Rheotec RC30 thermostatted cone-plate viscometer (cone diameter 50 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 10 s.sup.−1) at a temperature of 20° C.

[0198] The compositions identified by “(Ref)” in tables 1 to 7 are comparative examples.

1. Starting Materials Used and Abbreviations Therefor:

[0199] Acclaim® 12200 polyoxypropylenediol with a low level of unsaturation, OH number 11.0 mg KOH/g (from Bayer MaterialScience) [0200] Acclaim® 4200 polyoxypropylenediol with a low level of unsaturation, OH number 28.0 mg KOH/g (from Bayer MaterialScience) [0201] Acclaim® 6300 polyoxypropylenetriol with a low level of unsaturation, OH number 28.0 mg KOH/g (from Bayer MaterialScience) [0202] Lupranol® 4003/1 EO-endcapped polyoxypropylenetriol with 45% by weight of grafted SAN polymer, OH number 20.0 mg KOH/g (from BASF) [0203] Synalox® 100-150B butanol-started polyoxypropylenemonool, molecular weight 2200 g/mol (from Dow) [0204] Polyvest® EP HT hydroxyl-terminated polybutadiene, OH number 48 mg KOH/g, functionality about 2.5 (from Evonik Industries) [0205] UCON® Hydrolube polyoxypropylene monoallyl ether, OH number 70 mg [0206] APPG-800R KOH/g, 3.5% by weight of allyl, molecular weight about 800 g/mol, (from Dow) [0207] IPDI isophorone diisocyanate, Vestanat® IPDI (from Evonik) [0208] TDI tolylene 2,4-diisocyanate, Desmodur® T-100 (from Bayer MaterialScience) [0209] DIDP diisodecyl phthalate [0210] Tyzor® IBAY bis(ethylacetoacetato)diisobutoxytitanium(IV) (from Dorf Ketal) [0211] Tyzor® AA bis(acetylacetonato)diisopropoxytitanium(IV) (from Dorf Ketal) [0212] VTEO vinyltriethoxysilane [0213] VTMO vinyltrimethoxysilane [0214] PCC precipitated calcium carbonate, Socal® U1 S2 (from Solvay) [0215] GCC ground calcium carbonate, Omyacarb® 5 GU (from Omya) [0216] DBU 1,8-diazabicyclo[5.4.0]undec-7-ene [0217] Geniosil® GF 94 3-(2-aminoethyl)aminopropyltriethoxysilane

Hydroxysilanes:

Hydroxysilane 1: N-(3-Triethoxysilylpropyl)-2-hydroxypropanamide

[0218] In a round-bottom flask, 20.00 g (90.4 mmol) of 3-aminopropyltriethoxysilane and 6.71 g (46.6 mmol) of L-lactide were stirred under a nitrogen atmosphere at 80° C. for 3 h until no further progress in the reaction was detected by means of IR spectroscopy. The crude product was aftertreated at 60° C. and about 10 mbar for 15 min. A colorless liquid product was obtained.

Hydroxysilane 2: N-(3-Triethoxysilylpropyl)-4-hydroxypentanamide

[0219] In a round-bottom flask, 20.00 g (90.4 mmol) of 3-aminopropyltriethoxysilane and 10.86 g (108.5 mmol) of γ-valerolactone were stirred under a nitrogen atmosphere at 135° C. for 6 h until no further progress in the reaction was detected by means of IR spectroscopy. The crude product was aftertreated at 80° C. and about 2 mbar for 30 min. A colorless liquid product was obtained.

Hydroxysilane 3: Mixture comprising 2-hydroxypropyl N-(3-triethoxysilylpropyl)carbamate and 1-hydroxyprop-2-yl N-(3-triethoxysilylpropyl)carbamate

[0220] In a round-bottom flask, 20.00 g (90.4 mmol) of 3-aminopropyltriethoxysilane and 9.51 g (93.1 mmol) of 1,2-propylene carbonate were stirred under a nitrogen atmosphere at 80° C. for 5 h until no further progress in the reaction was detected by means of IR spectroscopy. The crude product was aftertreated at 60° C. and about 10 mbar for 10 min. A colorless liquid product was obtained.

Hydroxysilane 4: N-(3-Diethoxymethylsilylpropyl)-2-hydroxypropanamide

[0221] In a round-bottom flask, 17.30 g (90.4 mmol) of 3-aminopropyldiethoxymethylsilane (Dynasylan® 1505 from Evonik Industries) and 6.71 g (46.6 mmol) of L-lactide were stirred under a nitrogen atmosphere at 80° C. for 3 h until no further progress in the reaction was detected by means of IR spectroscopy. The crude product was aftertreated at 60° C. and about 10 mbar for 15 min. A colorless liquid product was obtained.

Hydroxysilane 5: N-(3-Trimethoxysilylpropyl)-2-hydroxypropanamide

[0222] In a round-bottom flask, 16.21 g (90.4 mmol) of 3-aminopropyltrimethoxysilane and 6.71 g (46.6 mmol) of L-lactide were stirred under a nitrogen atmosphere at 80° C. for 3 h until no further progress in the reaction was detected by means of IR spectroscopy. The crude product was aftertreated at 60° C. and about 10 mbar for 15 min. A colorless liquid product was obtained.

Hydroxysilane 6: N-(3-Dimethoxymethylsilylpropyl)-2-hydroxypropanamide

[0223] In a round-bottom flask, 14.76 g (90.4 mmol) of 3-aminopropyldimethoxymethylsilane (Silquest® A-21 10 from Momentive) and 6.71 g (46.6 mmol) of L-lactide were stirred under a nitrogen atmosphere at 80° C. for 3 h until no further progress in the reaction was detected by means of IR spectroscopy. The crude product was aftertreated at 60° C. and about 10 mbar for 15 min. A colorless liquid product was obtained.

Hydroxysilane 7: N-(2,2-Dimethyl-4-dimethoxymethylsilylbutyl)-2-hydroxypropanamide

[0224] In a round-bottom flask, 18.57 g (90.4 mmol) of 4-amino-3,3-dimethylbutyldimethoxymethylsilane (Silquest® A-2639 from Momentive) and 6.71 g (46.6 mmol) of L-lactide were stirred under a nitrogen atmosphere at 80° C. for 3 h until no further progress in the reaction was detected by means of IR spectroscopy. The crude product was aftertreated at 60° C. and about 10 mbar for 15 min. A colorless liquid product was obtained.

Hydroxysilane 8: N-(2,2-Dimethyl-4-trimethoxysilylbutyl)-2-hydroxypropanamide

[0225] In a round-bottom flask, 20.01 g (90.4 mmol) of 4-amino-3,3-dimethylbutyltrimethoxysilane (Silquest® A-1637 from Momentive) and 6.71 g (46.6 mmol) of L-lactide were stirred under a nitrogen atmosphere at 80° C. for 3 h until no further progress in the reaction was detected by means of IR spectroscopy. The crude product was aftertreated at 60° C. and about 10 mbar for 15 min. A colorless liquid product was obtained.

2. Preparation of Silane-Functional Polymers:

Inventive Polymer Formulations:

Polymer M-1:

[0226] With exclusion of moisture, 50.000 g of Acclaim® 12200 and 0.05 g of vinyltriethoxysilane were stirred under reduced pressure at 80° C. for 30 min. Subsequently, 0.050 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 0.124 g of isocyanatopropyltriethoxysilane were added and the reaction mixture was stirred at 80° C. under reduced pressure for 2 h until no isocyanate groups were detectable any longer by means of IR spectroscopy. Then 2.175 g of IPDI were added and the mixture was stirred at 80° C. under reduced pressure for 2 h. Subsequently, 3.206 g of hydroxysilane 1 were added and the mixture was stirred at 80° C. under reduced pressure for 90 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was clear and, the day after the preparation, had a viscosity of 149 Pa.Math.s (20° C.).

Polymer M-2:

[0227] Polymer M-2 was prepared and stored as described for polymer M-1, except using 0.247 g of isocyanatopropyltriethoxysilane, 2.061 g of IPDI and 3.037 g of hydroxysilane 1. It was clear and, the day after the preparation, had a viscosity of 132 Pa.Math.s (20° C.).

Polymer M-3:

[0228] Polymer M-3 was prepared and stored as described for polymer M-1, except using 0.742 g of isocyanatopropyltriethoxysilane, 1.603 g of IPDI and 2.362 g of hydroxysilane 1. It was clear and, the day after the preparation, had a viscosity of 75 Pa.Math.s (20° C.).

Polymer M-4:

[0229] Polymer M-4 was prepared and stored as described for polymer M-1, except using 1.237 g of isocyanatopropyltriethoxysilane, 1.145 g of IPDI and 1.687 g of hydroxysilane 1. It was clear and, the day after the preparation, had a viscosity of 38 Pa.Math.s (20° C.).

Polymer M-5:

[0230] Polymer M-5 was prepared and stored as described for polymer M-1, except using 1.732 g of isocyanatopropyltriethoxysilane, 0.687 g of IPDI and 1.012 g of hydroxysilane 1. It was clear and, the day after the preparation, had a viscosity of 22 Pa.Math.s (20° C.).

Polymer M-6:

[0231] Polymer M-6 was prepared and stored as described for polymer M-1, except using 1.979 g of isocyanatopropyltriethoxysilane, 0.458 g of IPDI and 0.675 g of hydroxysilane 1. It was clear and, the day after the preparation, had a viscosity of 17 Pa.Math.s (20° C.).

Polymer M-7:

[0232] Polymer M-7 was prepared and stored as described for polymer M-1, except using 2.226 g of isocyanatopropyltriethoxysilane, 0.229 g of IPDI and 0.337 g of hydroxysilane 1. It was clear and, the day after the preparation, had a viscosity of 13 Pa.Math.s (20° C.).

Polymer M-8:

[0233] Polymer M-8 was prepared and stored as described for polymer M-1, except using 2.350 g of isocyanatopropyltriethoxysilane, 0.114 g of IPDI and 0.169 g of hydroxysilane 1. It was clear and, the day after the preparation, had a viscosity of 11 Pa.Math.s (20° C.).

Polymer M-10:

[0234] With exclusion of moisture, 250.00 g of Acclaim® 12200 and 0.25 g of vinyltriethoxysilane were stirred under reduced pressure at 80° C. for 30 min. Subsequently, 0.25 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 6.43 g of isocyanatopropyltriethoxysilane were added and the reaction mixture was stirred at 80° C. under reduced pressure for 2 h until no isocyanate groups were detectable any longer by means of IR spectroscopy. Then 5.78 g of IPDI were added and the mixture was stirred at 80° C. under reduced pressure for 2 h. Subsequently, 8.80 g of hydroxysilane 1 were added and the mixture was stirred at 80° C. under reduced pressure for 90 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was clear and, the day after the preparation, had a viscosity of 43.1 Pa.Math.s (20° C.).

Polymer M-11:

[0235] Polymer M-11 was prepared and stored as described for polymer M-10, except using 9.64 g of hydroxysilane 2 rather than the hydroxysilane 1. The resultant silane-functional polymer was slightly cloudy and, the day after the preparation, had a viscosity of 50.1 Pa.Math.s (20° C.).

Polymer M-12:

[0236] Polymer M-12 was prepared and stored as described for polymer M-10, except using 9.71 g of hydroxysilane 3 rather than the hydroxysilane 1. However, isocyanate groups were still present by means of IR spectroscopy after the process described, and then a further 0.97 g of hydroxysilane 3 were added and the mixture was stirred at 80° C. under reduced pressure for 60 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. The resultant silane-functional polymer was slightly cloudy and, the day after the preparation, had a viscosity of 33.2 Pa.Math.s (20° C.).

Polymer M-13:

[0237] Polymer M-13 was prepared and stored as described for polymer M-10, except using 4.53 g of TDI rather than IPDI. The resultant silane-functional polymer was clear and, the day after the preparation, had a viscosity of 28.8 Pa.Math.s (20° C.).

Polymer M-14:

[0238] With exclusion of moisture, 250.00 g of Acclaim® 12200 and 0.25 g of vinyltriethoxysilane were stirred under reduced pressure at 80° C. for 30 min. Subsequently, 0.25 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 4.95 g of isocyanatopropyltriethoxysilane were added and the reaction mixture was stirred at 80° C. under reduced pressure for 2 h until no isocyanate groups were detectable any longer by means of IR spectroscopy. Then 5.56 g of IPDI were added and the mixture was stirred at 80° C. under reduced pressure for 2 h. Subsequently, 6.75 g of hydroxysilane 1 were added and the mixture was stirred at 80° C. under reduced pressure for 90 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was clear and, the day after the preparation, had a viscosity of 60.3 Pa.Math.s (20° C.).

Polymer M-15:

[0239] With exclusion of moisture, 210.00 g of Acclaim® 12200 and 0.25 g of vinyltriethoxysilane were stirred under reduced pressure at 80° C. for 30 min. Subsequently, 0.25 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 3.96 g of isocyanatopropyltriethoxysilane were added and the reaction mixture was stirred at 80° C. under reduced pressure for 2 h until no isocyanate groups were detectable any longer by means of IR spectroscopy. Then 28.00 g of Acclaim® 4200 and 7.11 g of IPDI were added and the mixture was stirred at 80° C. under reduced pressure for 2 h. Subsequently, 8.10 g of hydroxysilane 1 were added and the mixture was stirred at 80° C. under reduced pressure for 90 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was clear and, the day after the preparation, had a viscosity of 104.0 Pa.Math.s (20° C.).

Polymer M-16:

[0240] Polymer M-16 was prepared and stored as described for polymer M-10, except using 7.90 g of hydroxysilane 4 rather than the hydroxysilane 1. The resultant silane-functional polymer was clear and, the day after the preparation, had a viscosity of 47.0 Pa.Math.s (20° C.).

Polymer M-17:

[0241] With exclusion of moisture, 250.00 g of Acclaim® 12200 and 0.25 g of vinyltrimethoxysilane were stirred under reduced pressure at 80° C. for 30 min. Subsequently, 0.25 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 5.34 g of isocyanatopropyltrimethoxysilane were added and the reaction mixture was stirred at 80° C. without reduced pressure for 45 min, then at 80° C. under reduced pressure for 45 min, until no isocyanate groups were detectable any longer by means of IR spectroscopy. Then 5.78 g of IPDI were added and the mixture was stirred at 80° C. under reduced pressure for 2 h. Subsequently, 7.54 g of hydroxysilane 5 were added and the mixture was stirred at 80° C. under reduced pressure for 90 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was clear and, the day after the preparation, had a viscosity of 37.9 Pa.Math.s (20° C.).

Polymer M-18:

[0242] Polymer M-18 was prepared and stored as described for polymer M-17, except using 7.06 g of hydroxysilane 6 rather than the hydroxysilane 5. The resultant silane-functional polymer was clear and, the day after the preparation, had a viscosity of 68.0 Pa.Math.s (20° C.).

Polymer M-19:

[0243] Polymer M-19 was prepared and stored as described for polymer M-17, except using 8.32 g of hydroxysilane 7 rather than the hydroxysilane 5. The resultant silane-functional polymer was clear and, the day after the preparation, had a viscosity of 72.0 Pa.Math.s (20° C.).

Polymer M-20:

[0244] Polymer M-20 was prepared and stored as described for polymer M-17, except using 8.80 g of hydroxysilane 8 rather than the hydroxysilane 5. The resultant silane-functional polymer was clear and, the day after the preparation, had a viscosity of 70.0 Pa.Math.s (20° C.).

Polymer M-21:

[0245] With exclusion of moisture, 250.00 g of Acclaim® 12200 and 0.25 g of vinyltriethoxysilane were stirred under reduced pressure at 80° C. for 30 min. Then 0.25 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 3.71 g of isocyanatopropyltriethoxysilane were added and the reaction mixture was stirred at 80° C. under reduced pressure for 60 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. Subsequently, 8.23 g of IPDI were added and the mixture was stirred at 80° C. under reduced pressure for 2 h. Finally, 10.27 g of hydroxysilane 1 were added, the mixture was stirred at 80° C. under reduced pressure for 90 min, then 3.94 g of diethyl N-(3-triethoxysilylpropyl)aspartate were added and the mixture was stirred at 80° C. under reduced pressure for another 30 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was clear and, the day after the preparation, had a viscosity of 72.2 Pa.Math.s (20° C.).

Polymer M-22:

[0246] With exclusion of moisture, 200.00 g of Acclaim® 4200 and 0.25 g of vinyltriethoxysilane were stirred under reduced pressure at 80° C. for 30 min. Then 0.25 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 7.41 g of IPDI were added and the reaction mixture was stirred at 80° C. under reduced pressure for 1 h until no isocyanate groups were detectable any longer by means of IR spectroscopy. Then 4.21 g of isocyanatopropyltriethoxysilane were added and the reaction mixture was stirred at 80° C. under reduced pressure for 1 h until no isocyanate groups were detectable any longer by means of IR spectroscopy. Then 3.83 g of IPDI were added and the mixture was stirred at 80° C. under reduced pressure for 2 h. Then 6.07 g of hydroxysilane 1 were added and the mixture was stirred at 80° C. under reduced pressure for 90 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was clear and, the day after the preparation, had a viscosity of 153 Pa.Math.s (20° C.).

Polymer M-23:

[0247] Polymer M-23 was prepared and stored as described for polymer M-10, except using 200.00 g of Acclaim® 6300 rather than Acclaim® 12200 and 12.86 g of isocyanatopropyltriethoxysilane, 11.56 g of IPDI and 17.54 g of hydroxysilane 1. The resultant silane-functional polymer was clear and, the day after the preparation, had a viscosity of 25.9 Pa.Math.s (20° C.).

Polymer M-24:

[0248] Polymer M-24 was prepared and stored as described for polymer M-10, except using 277.8 g of Lupranol® 4003/1 rather than Acclaim® 12200 and 12.86 g of isocyanatopropyltriethoxysilane, 11.56 g of IPDI and 17.54 g of hydroxysilane 1. The resultant silane-functional polymer was clear and, the day after the preparation, had a viscosity of 94.7 Pa.Math.s (20° C.).

Polymer M-25:

[0249] With exclusion of moisture, 250.00 g of Acclaim® 12200 and 0.25 g of vinyltriethoxysilane were stirred under reduced pressure at 80° C. for 30 min. Then 0.25 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 8.53 g of isocyanatopropyltriethoxysilane were added and the reaction mixture was stirred at 80° C. under reduced pressure for 2 h until no isocyanate groups were detectable any longer by means of IR spectroscopy. Subsequently, 43.86 g of Synalox® 100-150B and 7.78 g of IPDI were added and the mixture was stirred at 80° C. under reduced pressure for 2 h. Then 11.74 g of hydroxysilane 1 were added and the mixture was stirred at 80° C. under reduced pressure for 90 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was clear and, the day after the preparation, had a viscosity of 18.4 Pa.Math.s (20° C.).

Polymer M-26:

[0250] Polymer M-26 was prepared and stored as described for polymer M-10, except using 150.00 g of Polyvest® EP HT rather than Acclaim® 12200 and 16.08 g of isocyanatopropyltriethoxysilane, 14.23 g of IPDI and 20.03 g of hydroxysilane 1. The resultant silane-functional polymer was clear and, the day after the preparation, had a viscosity of 204 Pa.Math.s (20° C.).

Polymer M-27:

[0251] With exclusion of moisture, 250.00 g of NCO polymer 1, the preparation of which is described below, 0.25 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 3.93 g of hydroxysilane 1 were stirred under a nitrogen atmosphere at 80° C. until the isocyanate band in the IR spectrum was constant (about 2 h). Then 11.29 g of diethyl N-(3-triethoxysilylpropyl)aspartate were added and the mixture was stirred at 80° C. under reduced pressure for 90 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was clear and, the day after the preparation, had a viscosity of 109 Pa.Math.s (20° C.).

[0252] The NCO polymer 1 was prepared by heating, with exclusion of moisture, 720.0 g of Acclaim® 12200, 34.5 g of IPDI, 80.0 g of DIDP and 0.1 g of bismuth tris(neodecanoate) (10% by weight in DIDP) to 90° C. while stirring and leaving the mixture at this temperature until the content of free isocyanate groups, determined by titrimetry, had reached a stable value of 0.73% by weight. The polymer having isocyanate groups was cooled down to room temperature and stored with exclusion of moisture. It was clear and, the day after the preparation, had a viscosity of 31 Pa.Math.s (20° C.).

Polymer M-28:

[0253] Polymer M-28 was prepared and stored as described for polymer M-27, except using 8.42 g of hydroxysilane 1 and 5.27 g of diethyl N-(3-triethoxysilylpropyl)aspartate. The resultant silane-functional polymer was clear and, the day after the preparation, had a viscosity of 168 Pa.Math.s (20° C.).

Polymer M-29:

[0254] With exclusion of moisture and under a nitrogen atmosphere, 10.00 g of dried UCON® Hydrolube APPG-800R, 10 μl of Karstedt catalyst and 1.66 g of triethoxysilane were converted at 60° C. for 1 h until no allyl groups were detectable any longer by means of IR spectroscopy. Then the reaction mixture was stirred at 80° C. and 15 mbar for 20 min. Subsequently, 2.29 g of IPDI and 0.05 g of dibutyltin dilaurate were added and the mixture was stirred at 80° C. under reduced pressure for 1 h until the isocyanate band in the IR spectrum was constant. Finally, 3.55 g of hydroxysilane 1 and 0.05 g of Coscat® 83 (Bi(III) neodecanoate, from Vertellus) were added and the mixture was stirred at 80° C. under reduced pressure for 60 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was clear and slightly dark-colored and, the day after the preparation, had a viscosity of 2.8 Pa.Math.s (20° C.).

Polymer M-30:

[0255] Polymer M-30 was prepared and stored as described for polymer M-29, except using 3.89 g of hydroxysilane 2 in place of hydroxysilane 1. The resultant silane-functional polymer had minimal turbidity, was pale yellowish in color and, the day after the preparation, had a viscosity of 3.7 Pa.Math.s (20° C.).

Silane-Functional Comparative Polymers Having Only End Groups of the Formula (I):

Polymer E-1:

[0256] With exclusion of moisture, 250.00 g of Acclaim® 12200 and 0.25 g of vinyltriethoxysilane were stirred under reduced pressure at 80° C. for 30 min. Subsequently, 0.25 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 11.56 g of IPDI were added and the mixture was stirred at 80° C. under reduced pressure for 2 h. Then 17.32 g of hydroxysilane 1 were added and the mixture was stirred at 80° C. under reduced pressure for 90 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was clear and, the day after the preparation, had a viscosity of 263.5 Pa.Math.s (20° C.).

Polymer E-2:

[0257] With exclusion of moisture, 250.00 g of Acclaim® 12200 and 0.25 g of vinyltriethoxysilane were stirred under reduced pressure at 80° C. for 30 min. Subsequently, 0.25 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 11.56 g of IPDI were added and the mixture was stirred at 80° C. under reduced pressure for 2 h. Then 19.93 g of hydroxysilane 2 were added and the mixture was stirred at 80° C. under reduced pressure for 120 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was cloudy and, the day after the preparation, had a viscosity of 272.9 Pa.Math.s (20° C.).

Polymer E-3:

[0258] With exclusion of moisture, 250.00 g of Acclaim® 12200 and 0.25 g of vinyltriethoxysilane were stirred under reduced pressure at 80° C. for 30 min. Subsequently, 0.25 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 11.56 g of IPDI were added and the mixture was stirred at 80° C. under reduced pressure for 2 min. Then 19.08 g of hydroxysilane 3 were added and the mixture was stirred at 80° C. under reduced pressure for 120 min. Isocyanate groups were still present by means of IR spectroscopy, and then a further 1.91 g of hydroxysilane 3 were added and the mixture was stirred at 80° C. under reduced pressure for 60 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was cloudy and, the day after the preparation, had a viscosity of 169.9 Pa.Math.s (20° C.).

Polymer E-4:

[0259] With exclusion of moisture, 250.00 g of Acclaim® 12200 and 0.25 g of vinyltriethoxysilane were stirred under reduced pressure at 80° C. for 30 min. Subsequently, 0.25 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 9.06 g of TDI were added and the mixture was stirred at 80° C. without reduced pressure for 1 h, then at 80° C. under reduced pressure for 1 h. Subsequently, 17.32 g of hydroxysilane 1 were added and the mixture was stirred at 80° C. under reduced pressure for 90 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was clear and, the day after the preparation, had a viscosity of 85.2 Pa.Math.s (20° C.).

Polymer E-5:

[0260] With exclusion of moisture, 250.00 g of Acclaim® 12200 and 0.25 g of vinyltrimethoxysilane were stirred under reduced pressure at 80° C. for 30 min. Subsequently, 0.25 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 11.56 g of IPDI were added and the mixture was stirred at 80° C. under reduced pressure for 2 h. Then 14.83 g of hydroxysilane 5 were added and the mixture was stirred at 80° C. under reduced pressure for 90 min until no isocyanate groups were detectable any longer by means of IR spectroscopy. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was clear and, the day after the preparation, had a viscosity of 179.1 Pa.Math.s (20° C.).

Silane-Functional Comparative Polymers with Further Silane End Groups:

Polymer R-1:

[0261] With exclusion of moisture, 250.00 g of Acclaim® 12200 and 0.25 g of vinyltriethoxysilane were stirred at 80° C. for 30 min and then 0.25 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 12.49 g of isocyanatopropyltriethoxysilane were added and the reaction mixture was stirred at 80° C. under reduced pressure for 2 h. Subsequently, 1.50 g of ethanol were added and the mixture was stirred without reduced pressure for 15 minutes, then under reduced pressure for a further 15 minutes. No isocyanate band was detected any longer in the FT-IR. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was clear and, the day after the preparation, had a viscosity of 10 Pa.Math.s.

Polymer R-2:

[0262] With exclusion of moisture, 250.00 g of Acclaim® 12200 and 0.25 g of vinyltrimethoxysilane were stirred at 80° C. for 30 min and then 0.25 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 10.37 g of isocyanatopropyltrimethoxysilane were added and the reaction mixture was stirred at 80° C. under reduced pressure for 2 h. Subsequently, 1.50 g of methanol were added and the mixture was stirred without reduced pressure for 15 minutes, then under reduced pressure for a further 15 minutes. No isocyanate band was detected any longer in the FT-IR. The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was clear and, the day after the preparation, had a viscosity of 11 Pa.Math.s.

Polymer R-3:

[0263] Polymer R-3 was prepared and stored as described for polymer M-25, except using 15.74 g of diethyl N-(3-triethoxysilylpropyl)aspartate rather than the hydroxysilane 1. The resultant silane-functional polymer was clear and, the day after the preparation, had a viscosity of 14.2 Pa.Math.s (20° C.).

Polymer R-4:

[0264] With exclusion of moisture, 100.00 g of NCO polymer 1, the preparation of which was described for polymer M-27, 0.06 g of bismuth tris(neodecanoate) (10% by weight in DIDP) and 7.19 g of diethyl N-(3-triethoxysilylpropyl)aspartate were stirred under a nitrogen atmosphere at 80° C. until no isocyanate groups were detectable any longer by means of IR spectroscopy (about 1.5 h). The silane-functional polymer was cooled down to room temperature and stored with exclusion of moisture. It was clear and, the day after the preparation, had a viscosity of 83 Pa.Math.s (20° C.).

3. Moisture-Curing Compositions (Unfilled)

Compositions Z1 to Z18:

[0265] For each composition, the ingredients specified in table 1 were processed in the amounts specified (in parts by weight) in a vacuum mixer at 50° C. with exclusion of moisture for 30 min to give a homogeneous paste, and stored.

[0266] Each composition was tested as follows:

[0267] The viscosity was determined the day after the preparation, with 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) at a temperature of 20° C.

[0268] To determine the tack-free time (TFT), 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.

TABLE-US-00001 TABLE 1 Composition and properties of the compositions Z1 to Z10. Composition Z1 Z10 (Ref) Z2 Z3 Z4 Z5 Z6 Z7 Z8 Z9 (Ref) Polymer E-1 M-1 M-2 M-3 M-4 M-5 M-6 M-7 M-8 R-1 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Tyzor ® IBAY 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 End gr. (I)/others.sup.1 100/0 95/5 90/10 70/30 50/50 30/70 20/80 10/90 5/95 0/100 Viscosity [Pa .Math. s] 258 149 132 75 38 22 17 13 11 9 TFT [min.] 66 72 75 74 78 86 90 90 88 86 .sup.1Ratio of the number of end groups of the formula (I) to the number of other silane groups

TABLE-US-00002 TABLE 2 Composition and properties of the compositions Z1 and Z10 to Z18. Composition Z1 Z11 Z12 Z13 Z14 Z15 Z16 Z17 Z18 Z10 (Ref) (Ref) (Ref) (Ref) (Ref) (Ref) (Ref) (Ref) (Ref) (Ref) Polymer E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 R-1 100.0 95.0 90.0 70.0 50.0 30.0 20.0 10.0 5.0 100.0 R-1 R-1 R-1 R-1 R-1 R-1 R-1 R-1 5.0 10.0 30.0 50.0 70.0 80.0 90.0 95.0 Tyzor ® IBAY 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Viscosity [Pa .Math. s] 258 190 162 90 45 24 17 13 11 9 TFT [min.] 66 69 73 71 71 72 74 79 81 86

4. Moisture-Curing Compositions (Filled)

Compositions Z19 to Z56

[0269] For each composition, the ingredients specified in tables 3 to 7 were processed in the amounts specified (in parts by weight) in a vacuum mixer at 50° C. with exclusion of moisture for 30 min to give a homogeneous paste, and stored.

[0270] Each composition was tested as follows:

[0271] Viscosity and tack-free time were tested as described for composition Z1. Shore A hardness was determined in accordance with DIN 53505 on test specimens which had been cured under standard climatic conditions for 14 days.

[0272] 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, and 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%-5% elongation).

[0273] The results are reported in tables 3 to 7.

[0274] The thickener paste was produced by initially charging a vacuum mixer with 300 g of diisodecyl phthalate and 48 g of 4,4′-methylene diphenyl diisocyanate (Desmodur® 44 MC L; from Bayer), heating them gently and then, while stirring vigorously, gradually adding 27 g of monobutylamine dropwise. The resultant paste was stirred for a further hour under vacuum and while cooling.

TABLE-US-00003 TABLE 3 Composition and properties of the compositions Z19 to Z33. Composition Z19 Z20 Z21 Z23 Z24 (Ref.) (Ref.) (Ref.) Z22 (Ref.) (Ref.) Z25 Polymer R-1 E-1 R-1 M-10 E-2 R-1 M-11 20.0 20.0 10.0 20.0 20.0 10.0 20.0 E-1 E-2 10.0 10.0 DIDP 17.6 17.6 17.6 17.6 17.6 17.6 17.6 Thickener paste 5.9 5.9 5.9 5.9 5.9 5.9 5.9 VTEO 1.0 1.0 1.0 1.0 1.0 1.0 1.0 PCC 10.0 10.0 10.0 10.0 10.0 10.0 10.0 GCC 50.0 50.0 50.0 50.0 50.0 50.0 50.0 Tyzor ® IBAY 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Viscosity [Pa .Math. s] 38.1 96.9 47.7 42.2 114.5 63.8 49.8 TFT [min] 150 60 80 70 70 75 80 Shore A 39 36 39 40 28 37 40 Tensile strength 1.1 1.6 1.5 1.5 0.8 1.0 1.1 [MPa] Elongation at break 171 162 133 147 133 118 121 [%] Modulus of 1.3 1.8 1.8 1.9 0.5 0.8 0.9 elasticity [MPa] Composition Z26 Z27 Z29 (Ref.) (Ref.) Z28 (Ref.) Z30 Z31 Z32 Z33 Polymer E-3 R-1 M-12 E-4 M-13 M-14 M-15 M-16 20.0 10.0 20.0 20.0 20.0 20.0 20.0 20.0 E-3 10.0 DIDP 17.6 17.6 17.6 17.6 17.6 17.6 17.6 17.6 Thickener paste 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 VTEO 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 PCC 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 GCC 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 Tyzor ® IBAY 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Viscosity 78.5 52.5 49.9 69.4 43.8 53.0 72.0 55.2 [Pa .Math. s] TFT [min] 80 85 85 75 70 85 55 120 Shore A 32 36 37 45 47 38 38 39 Tensile 1.0 1.1 1.2 1.5 1.4 1.3 1.4 1.5 strength [MPa] Elongation at 156 146 137 138 129 160 195 185 break [%] Modulus of 0.6 1.1 1.2 1.8 1.8 1.2 1.3 1.6 elasticity [MPa]

TABLE-US-00004 TABLE 4 Composition and properties of the compositions Z34 to Z40. Composition Z34 Z35 Z36 (Ref.) (Ref.) (Ref.) Z37 Z38 Z39 Z40 Polymer R-2 E-5 R-2 M-17 M-18 M-19 M-20 20.0 20.0 10.0 20.0 20.0 20.0 20.0 E-5 10.0 DIDP 17.6 17.6 17.6 17.6 17.6 17.6 17.6 Thickener paste 5.9 5.9 5.9 5.9 5.9 5.9 5.9 VTMO 1.0 1.0 1.0 1.0 1.0 1.0 1.0 PCC 10.0 10.0 10.0 10.0 10.0 10.0 10.0 GCC 50.0 50.0 50.0 50.0 50.0 50.0 50.0 Tyzor ® IBAY 1.0 1.0 1.0 1.0 — — — Tyzor ® AA — — — — 1.6 1.6 1.6 Viscosity [Pa .Math. s] 39.1 89.7 54.0 48.8 62.0 60.5 60.6 TFT [min] 20 15 15 15 35 45 30 Shore A 40 22 34 38 35 35 35 Tensile strength 1.2 0.7 1.1 1.2 1.4 1.4 1.5 [MPa] Elongation at break 192 131 158 172 261 292 354 [%] Modulus of elasticity 1.4 0.4 0.9 1.0 1.5 1.5 1.6 [MPa]

TABLE-US-00005 TABLE 5 Composition and properties of the compositions Z41 to Z47. Composition Z47 Z41 Z42 Z43 Z44 Z45 Z46 (Ref.) Polymer M-3 M-21 M-22 M-10 M-10 M-25 R-3 20.0 20.0 20.0 15.0 15.0 20.0 20.0 M-23 M-24 5.0 9.0 DIDP 17.6 17.6 17.6 17.6 17.6 17.6 17.6 Thickener paste 5.9 5.9 5.9 5.9 5.9 5.9 5.9 VTEO 1.0 1.0 1.0 1.0 1.0 1.0 1.0 PCC 10.0 10.0 10.0 10.0 10.0 10.0 10.0 GCC 50.0 50.0 50.0 50.0 50.0 50.0 50.0 Tyzor ® IBAY 1.6 1.6 1.6 — — 1.6 1.6 Tyzor ® AA — — — 2.0 2.0 — — Viscosity [Pa .Math. s] 49.1 49.0 84.1 42.4 47.6 31.9 30.3 TFT [min] 80 110 150 130 140 125 180 Shore A 49 22 28 53 58 40 36 Tensile strength 1.5 1.2 1.2 1.3 1.6 1.2 1.0 [MPa] Elongation at break 139 128 170 125 139 115 122 [%] Modulus of elasticity 1.6 1.0 0.8 2.7 3.4 1.2 0.8 [MPa]

TABLE-US-00006 TABLE 6 Composition and properties of the compositions Z48 to Z53. Composition Z50 Z51 Z48 Z49 (Ref.) (Ref.) Z52 Z53 Polymer M-26 M-10 R-4 E-1 M-27 M-28 20.0 10.0 18.0 18.0 18.0 18.0 M-26 10.0 DIDP 17.6 17.6 19.6 19.6 19.6 19.6 Thickener paste 5.9 5.9 5.9 5.9 5.9 5.9 VTEO 1.0 1.0 1.0 1.0 1.0 1.0 PCC 10.0 10.0 10.0 10.0 10.0 10.0 GCC 50.0 50.0 50.0 50.0 50.0 50.0 Tyzor ® IBAY 1.6 1.6 1.6 1.6 1.6 1.6 Viscosity [Pa .Math. s] 118.0 48.4 55.9 76.0 59.1 76.3 TFT [min] 35 30 >300 50 145 65 Shore A 66 61 20 37 36 37 Tensile strength 2.4 1.9 1.1 1.4 1.1 1.2 [MPa] Elongation at break 62 85 165 174 211 238 [%] Modulus of elasticity 5.3 3.0 0.9 1.5 0.8 1.0 [MPa]

TABLE-US-00007 TABLE 7 Composition and properties of the compositions Z54 to Z56. Composition Z54 Z55 Z56 Polymer M-29 M-29 M-30 18.0 18.0 18.0 DIDP 4.5 4.5 4.5 VTEO 1.5 1.5 1.5 Tyzor ® IBAY 1.5 — 1.5 Fumed silica 0.5 0.5 0.5 Geniosil ® GF 94 — 1.5 — DBU 0.4 0.4 0.4 TFT [min] 400 500 270 Shore A 41 51 10