Catalyst containing guanidine groups

Abstract

The use of a catalyst of the formula (I) for the crosslinking of a curable composition. The catalyst of the formula (I) contains at least one aliphatic guanidine group. It is substantially odorless and nonvolatile at room temperature and accelerates the crosslinking of curable compositions very efficiently, without impairing the storage stability thereof. It is particularly suitable for compositions based on polymers containing silane groups, where it has very good compatibility, as a result of which such compositions do not have a tendency to separation or migration or evaporation of the catalyst.

Claims

1. A method of crosslinking a curable composition, comprising crosslinking the curable composition with a catalyst of formula (I) ##STR00041## formed from a reaction of a group L-Q.sub.p+r and p (HX-A-Z) groups where p is an integer from 1 to 6 and r is an integer from 0 to 5, where (p+r) is an integer from 1 to 6, L is a (p+r)-valent hydrocarbyl radical having a mean molecular weight in the range from 14 to 20,000 g/mol, optionally having heteroatoms, or is a (p+r+1)-valent hydrocarbyl radical having 4 to 12 carbon atoms, which together with Q forms an optionally substituted 5- or 6-membered ring, or is a covalent bond, or is a hydrogen radical, Q is a reactive group selected from epoxide, aziridine, carbonate, carboxylic anhydride, carboxylic acid, carboxylic ester, lactone, carbonyl chloride, ketone, aldehyde, 1,3-diketone, 1,3-keto ester, 1,3-keto amide, cyanate, thiocyanate, isocyanate, isothiocyanate, (meth)acrylate, (meth)acrylamide, (meth)acrylonitrile, maleate, maleamide, maleimide, fumarate, fumaramide, itaconate, itaconamide, crotonate and crotonamide, Q is a di- or trivalent connecting unit residue formed from the reaction of Q with HX, Y is N or X, where X is O or S or NR.sup.3 where R.sup.3 is a hydrogen radical or is an alkyl or cycloalkyl or aralkyl radical which has 1 to 8 carbon atoms and optionally contains a tertiary amino group or a guanidine group, A is a divalent hydrocarbyl radical which has 2 to 30 carbon atoms and optionally contains unsaturated components and optionally ether oxygen or secondary or tertiary amine nitrogen, where A together with R.sup.3 may also be a trivalent hydrocarbyl radical which has 5 to 10 carbon atoms and optionally contains a tertiary amine nitrogen, and Z is a guanidine group which is bonded via a nitrogen atom and does not contain any nitrogen atom which is bonded directly to an aromatic ring or is part of a heteroaromatic ring system.

2. The method as claimed in claim 1, wherein A is either selected from the group consisting of 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,3-pentylene, 1,1-dimethyl-1,2-ethyl, 1,5-pentylene, 2-methyl-1,5-pentylene, 1,6-hexylene, 2,2(4),4-trimethyl-1,6-hexamethylene, 1,8-octylene, 1,10-decylene, 1,12-dodecylene, (1,5,5-trimethylcyclohexan-1-yl)methane-1,3, 1,3-cyclohexylenebis(methylene), 1,4-cyclohexylene-bis(methylene), 1,3-phenylenebis(methylene), 2- and/or 4-methyl-1,3-cyclohexylene, N-methyl-4-aza-1,7-heptylene, 3-oxa-1,5-pentylene, 3,6-dioxa-1,8-octylene, 4,7-dioxa-1,10-decylene and a polyoxypropylene radical having a mean molecular weight in the range from about 200 to 250 g/mol, or A together with R.sup.3 including the nitrogen atom of X is a radical selected from the group consisting of piperidin-4-ylmethyl, 2-(piperidin-4-yl)ethyl and 2-piperazinoethyl.

3. The method as claimed in claim 1, wherein Z is ##STR00042## where R.sup.0 and R.sup.1 are independently a hydrogen radical or an alkyl or cycloalkyl or aralkyl radical having 1 to 8 carbon atoms, R.sup.2 is a hydrogen radical or an alkyl, cycloalkyl or aralkyl radical which has 1 to 18 carbon atoms and optionally contains ether oxygen or tertiary amine nitrogen, R.sup.4 and R.sup.5 are each independently a hydrogen radical or an alkyl, cycloalkyl or aralkyl radical which has 1 to 18 carbon atoms and optionally contains an ether oxygen or a tertiary amine nitrogen, where R.sup.2 and R.sup.0 together may also be an alkylene radical which has 3 to 6 carbon atoms and optionally contains an ether oxygen or a tertiary amine nitrogen, R.sup.4 and R.sup.5 together may also be an alkylene radical which has 4 to 7 carbon atoms and optionally contains an ether oxygen or a tertiary amine nitrogen, and R.sup.2 and R.sup.5 together may also be an alkylene radical having 2 to 12 carbon atoms.

4. The method as claimed in claim 3, wherein Z is ##STR00043##

5. The method as claimed in claim 1, wherein Q is selected from the group consisting of ##STR00044## where D is O or S, W is O or NR.sup.6 where R.sup.6 is a hydrogen radical or is a monovalent hydrocarbyl radical having 1 to 8 carbon atoms, E.sup.0 is a hydrogen radical or is a methyl radical, E.sup.1 is a carboxyl-substituted alkylene, alkenediyl or phenylene radical having 2 to 8 carbon atoms, E.sup.2 is a hydroxyalkylene radical having 2 to 5 carbon atoms or is an O-bonded hydroxyalkyleneoxy radical having 2 or 3 carbon atoms, E.sup.3 is a hydrogen radical or is a monovalent hydrocarbyl radical which has 1 to 6 carbon atoms and optionally has heteroatoms in the form of ether, ester, amino or amide groups, or together with L is an optionally substituted 1,4-butylene or 1,5-pentylene radical, E.sup.4 is a hydrogen or methyl or alkoxycarbonylmethyl radical having 2 to 9 carbon atoms, E.sup.5 is an alkoxycarbonyl radical having 1 to 8 carbon atoms or is a methyl radical, E.sup.6 is a hydrogen radical or is an alkyl radical having 1 to 8 carbon atoms, E.sup.7 is a monovalent hydrocarbyl radical having 1 to 6 carbon atoms, E.sup.8 is a hydrogen radical or is a monovalent hydrocarbyl radical having 1 to 6 carbon atoms, and d is 0 or 1.

6. The method as claimed in claim 1, wherein p is 1 or 2 or 3 and r is 0.

7. The method as claimed in claim 1, wherein the curable composition is an epoxy resin composition or a polyurethane composition or an epoxy resin/polyurethane composition or a cyanate ester resin composition or a composition containing silane groups.

8. The method as claimed in claim 1, wherein the curable composition is a composition based on polymers containing silane groups.

9. The method as claimed in claim 8, wherein the polymer containing silane groups is selected from the group consisting of polyorganosiloxanes having terminal silane groups and organic polymers containing silane groups.

10. A process for preparing a catalyst of formula (I): ##STR00045## formed from a reaction of a group L-Q.sub.p+r and p (HX-A-Z) groups where p is an integer from 1 to 6 and r is an integer from 0 to 5, where (p+r) is an integer from 1 to 6, L is a (p+r)-valent hydrocarbyl radical having a mean molecular weight in the range from 14 to 20000 g/mol, optionally having heteroatoms, or is a (p+r+1)-valent hydrocarbyl radical having 4 to 12 carbon atoms, which together with Q forms an optionally substituted 5- or 6-membered ring, or is a covalent bond, or is a hydrogen radical, Q is a reactive group selected from epoxide, aziridine, carbonate, carboxylic anhydride, carboxylic acid, carboxylic ester, lactone, carbonyl chloride, ketone, aldehyde, 1,3-diketone, 1,3-keto ester, 1,3-keto amide, cyanate, thiocyanate, isocyanate, isothiocyanate, (meth)acrylate, (meth)acrylamide, (meth)acrylonitrile, maleate, maleamide, maleimide, fumarate, fumaramide, itaconate, itaconamide, crotonate and crotonamide, Q is a di- or trivalent connecting unit residue formed from the reaction of Q with HX, Y is N or X, where X is O or S or NR.sup.3 where R.sup.3 is a hydrogen radical or is an alkyl or cycloalkyl or aralkyl radical which has 1 to 8 carbon atoms and optionally contains a tertiary amino group or a guanidine group, A is a divalent hydrocarbyl radical which has 2 to 30 carbon atoms and optionally contains unsaturated components and optionally ether oxygen or secondary or tertiary amine nitrogen, where A together with R.sup.3 may also be a trivalent hydrocarbyl radical which has 5 to 10 carbon atoms and optionally contains a tertiary amine nitrogen, and Z is a guanidine group which is bonded via a nitrogen atom and does not contain any nitrogen atom which is bonded directly to an aromatic ring or is part of a heteroaromatic ring system, the process comprising reacting at least one guanidine of the formula (II)
HX-A-Z(II) with at least one functional compound having at least one reactive group selected from epoxide, aziridine, carbonate, carboxylic anhydride, carboxylic acid, carboxylic ester, lactone, carbonyl chloride, ketone, aldehyde, 1,3-diketone, 1,3-keto ester, 1,3-keto amide, cyanate, thiocyanate, isocyanate, isothiocyanate, (meth)acrylate, (meth)acrylamide, (meth)acrylonitrile, maleate, maleamide, maleimide, fumarate, fumaramide, itaconate, itaconamide, crotonate and crotonamide.

11. A curable composition comprising at least one catalyst of formula (I) ##STR00046## formed from a reaction of a group L-Q.sub.p+r and p (HX-A-Z) groups where p is an integer from 1 to 6 and r is an integer from 0 to 5, where (p+r) is an integer from 1 to 6, L is a (p+r)-valent hydrocarbyl radical having a mean molecular weight in the range from 14 to 20000 g/mol, optionally having heteroatoms, or is a (p+r+1)-valent hydrocarbyl radical having 4 to 12 carbon atoms, which together with Q forms an optionally substituted 5- or 6-membered ring, or is a covalent bond, or is a hydrogen radical, Q is a reactive group selected from epoxide, aziridine, carbonate, carboxylic anhydride, carboxylic acid, carboxylic ester, lactone, carbonyl chloride, ketone, aldehyde, 1,3-diketone, 1,3-keto ester, 1,3-keto amide, cyanate, thiocyanate, isocyanate, isothiocyanate, (meth)acrylate, (meth)acrylamide, (meth)acrylonitrile, maleate, maleamide, maleimide, fumarate, fumaramide, itaconate, itaconamide, crotonate and crotonamide, Q is a di- or trivalent connecting unit residue formed from the reaction of Q with HX, Y is N or X, where X is O or S or NR.sup.3 where R.sup.3 is a hydrogen radical or is an alkyl or cycloalkyl or aralkyl radical which has 1 to 8 carbon atoms and optionally contains a tertiary amino group or a guanidine group, A is a divalent hydrocarbyl radical which has 2 to 30 carbon atoms and optionally contains unsaturated components and optionally ether oxygen or secondary or tertiary amine nitrogen, where A together with R.sup.3 may also be a trivalent hydrocarbyl radical which has 5 to 10 carbon atoms and optionally contains a tertiary amine nitrogen, and Z is a guanidine group which is bonded via a nitrogen atom and does not contain any nitrogen atom which is bonded directly to an aromatic ring or is part of a heteroaromatic ring system.

12. The composition as claimed in claim 11, further comprising at least one polymer containing silane groups.

13. The composition as claimed in claim 12, wherein the polymer containing silane groups is a polyorganosiloxane having terminal silane groups.

14. The composition as claimed in claim 12, wherein the polymer containing silane groups is an organic polymer containing silane groups.

15. The composition as claimed claim 11, wherein it is an adhesive or a sealant or a coating.

Description

EXAMPLES

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

(2) Standard climatic conditions refer to a temperature of 231 C. and a relative air humidity of 505%.

(3) EEW stands for epoxy equivalent weight.

(4) .sup.1H NMR spectra were measured on a spectrometer of the Bruker Ascend 400 type at 400.14 MHz; the chemical shifts are reported in ppm relative to tetramethylsilane (TMS). Coupling constants J are reported in Hz. No distinction was made between true coupling and pseudo-coupling patterns.

(5) Infrared spectra (FT-IR) were measured on a Nicolet iS5 FT-IR instrument from Thermo Scientific equipped with a horizontal ATR measurement unit with a diamond crystal. Liquid samples were applied undiluted as films; solid samples were dissolved in CH.sub.2Cl.sub.2. The absorption bands are reported in wavenumbers (cm.sup.1) (measurement window: 4000-650 cm.sup.1).

(6) Gas chromatograms (GC) were measured within the temperature range of 60 to 320 C. with a heating rate of 15 C./min and a run time of 10 min at 320 C. The injector temperature was 250 C. A Zebron ZB-5 column was used (L=30 m, ID=0.25 mm, dj=0.5 m) with a gas flow rate of 1.5 ml/min. Detection was effected by means of flame ionization (FID), with evaluation of the signals via the area percent method.

(7) The skin time (ST) was determined by applying a few grams of the composition to cardboard in a layer thickness of about 2 mm and measuring, 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.

(8) The characteristics of the surface were tested by touch.

(9) The mechanical properties of tensile strength, elongation at break and modulus of elasticity (at 0-5% and at 0-50% or 0-100% elongation) were measured in accordance with DIN EN 53504 at a pulling speed of 200 mm/min.

(10) Reagents Used:

(11) DCC N,N-dicyclohexylcarbodiimide (Sigma-Aldrich)

(12) DIC N,N-diisopropylcarbodiimide (Sigma-Aldrich)

(13) Functional Compounds Used: TMPTA 1,1,1-trimethylolpropane triacrylate (Sartomer SR-351, from Sartomer) Polymer-NCO-1 reaction product of 500 g of Acclaim 4200 polyol (polyoxypropylenediol with a low level of unsaturation, from Bayer; OH number 28.0 mg KOH/g) and 2000 g of Caradol MD34-02 polyol (polyoxypropylenepolyoxyethylenetriol, from Shell; OH number 35.0 mg KOH/g) with 253 g of tolylene diisocyanate (Desmodur T80 P, from Bayer); NCO content: 2.06% by weight Polymer-HEA-1 reaction product of 169.47 g of polymer NCO-1 with 9.60 g of 2-hydroxyethyl acrylate (HEA) and 0.2 g of bismuth neodecanoate at 80 C. for 3 h (until complete conversion of the isocyanate band at 2277 cm.sup.1 in the FT-IR spectrum) Polymer-NCO-2 reaction product of 3.2 kg of Acclaim 12200 polyol (polyoxypropylenediol with a low level of unsaturation, from Bayer; OH number 11.0 mg KOH/g) with 149.4 g of isophorone diisocyanate (Vestanat IPDI, from Evonik) and 0.5 g of bismuth tris(neodecanoate); NCO content: 0.88% by weight EHGE 2-ethylhexyl glycidyl ether (D.E.R. 728, from Dow, EEW about 210 g/eq) DY-E monoglycidyl ether of C.sub.12-C.sub.14 alcohols (Araldite DY-E, from Huntsman, EEW about 282 g/eq) DY-K o-cresyl glycidyl ether (Araldite DY-E, from Huntsman, EEW about 282 g/eq) BADGE bisphenol A diglycidyl ether (Araldite MY 790, from Huntsman, EEW about 186 g/eq) DY-F polypropylene glycol diglycidyl ether (Araldite DY-F, from Huntsman, EEW about 510 g/eq)

(14) 2,2-dimethyl-3-lauroyloxypropanal (prepared as in U.S. Pat. No. 7,625,993, aldehyde A1)

(15) 2,2-dimethyl-3-(N-morpholino)propanal (prepared as in U.S. Pat. No. 8,252,859)

(16) 1,2-propylene carbonate (Sigma-Aldrich)

(17) pentane-2,4-dione (Sigma-Aldrich)

(18) N,N-diethylacetoacetamide (Sigma-Aldrich)

Preparation of Guanidines of the Formula (II)

Compound G-1: 1-(3-aminopropyl)-2,3-dicyclohexylguanidine

(19) In a round-bottom flask, 2.50 g of 1,3-diaminopropane and 6.89 g of DCC were mixed and heated to 120 C. while stirring. After 1 hour, the carbodiimide band at about 2120 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. Thereafter, the reaction mixture was freed of the volatile constituents under reduced pressure. This gave 9.36 g of a pale yellow oil of low odor, which solidified after a few days to give a solid mass.

(20) .sup.1H-NMR (CDCl.sub.3): 1.05-1.2 and 1.25-1.40 (2m, 10H), 1.54-1.78 (m, 10H), 1.88-2.0 (m, 4H), 2.73 (m, 2H), 3.12 (m, 2H), 3.22 (br s, 2H).

(21) FT-IR: 3371 (NH), 2921, 2849, 1627 (CN), 1502, 1447, 1324, 1238, 1147, 1111, 888, 713.

Compound G-2: 1-(2-aminopropyl)-2,3-dicyclohexylguanidine and 1-(3-aminoprop-2-yl)-2,3-dicyclohexylguanidine

(22) In a round-bottom flask, 7.78 g of 1,2-diaminopropane and 20.63 g of DCC were mixed and heated to 120 C. while stirring. After 3 hours, the carbodiimide band at about 2120 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. Thereafter, the reaction mixture was freed of the volatile constituents under reduced pressure. This gave 28.0 g of a pale yellow oil of low odor.

(23) FT-IR: 3270 (NH), 2922, 2849, 1626 (CN), 1497, 1447, 1363, 1336, 1285, 1237, 1189, 1146, 1112, 1091, 1073, 1050, 1027, 977, 888, 860, 804, 715.

Compound G-3: 1-(6-amino-3,3(5),5-trimethylhexyl)-2,3-dicyclohexylguanidine and 1-(6-amino-2,2(4),4-trimethylhexyl)-2,3-dicyclohexylguanidine

(24) In a round-bottom flask, 16.62 g of Vestamin TMD (mixture of 2,2,4- and 2,4,4-trimethylhexamethylene-1,6-diamine, from Evonik) and 20.63 g of DCC were mixed and heated to 120 C. while stirring. After 3 hours, the carbodiimide band at about 2120 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. Thereafter, the reaction mixture was freed of the volatile constituents under reduced pressure. This gave 36.5 g of a pale yellow oil of low odor.

(25) FT-IR: 3281 (NH), 2923, 2850, 1635 (CN), 1496, 1463, 1448, 1362, 1325, 1284, 1237, 1188, 1146, 1112, 1090, 1071, 1051, 1027, 977, 888, 860, 845, 804, 785, 714.

Compound G-4: 1-(3-cyclohexylaminopropyl)-2,3-diisopropylguanidine

(26) In a round-bottom flask, 34.38 g of 3-(cyclohexylamino)propylamine (from BASF) and 25.24 g of DIC were mixed and heated to 120 C. while stirring. After 2 hours, the carbodiimide band at about 2120 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. Thereafter, the reaction mixture was freed of the volatile constituents under reduced pressure. This gave 56.50 g of a pale yellow oil of low odor.

(27) FT-IR: 3292 (NH), 2960, 2924, 2852, 1633 (CN), 1505, 1448, 1361, 1329, 1176, 1125, 889, 714.

Compound G-5: 1-(2-(2-hydroxyethoxy)ethyl)-2,3-dicyclohexylguanidine

(28) In a round-bottom flask, 3.55 g of 2-(2-aminoethoxy)ethanol (Diglycolamine Agent, from Huntsman) and 6.81 g of DCC were mixed and heated to 120 C. while stirring. After 24 hours, the carbodiimide band at about 2120 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. This gave a pale yellow oil of low odor.

(29) .sup.1H-NMR (CDCl.sub.3): 1.05-1.3 and 1.3-1.45 (2m, 10H, CH.sub.2), 1.54-1.78 (m, 8H), 1.88-2.0 (m, 4H), 3.13 (t, 2H, CH.sub.2N), 3.69 (m, 4H, CH.sub.2O), 3.81 (t, 2H, OCH.sub.2CH.sub.2N).

(30) FT-IR: 3355 (OH), 2922, 2849, 1617 (CN), 1520, 1447, 1340, 1257, 1240, 1117, 1066, 888, 717.

Compound G-6: 1-(2-(2-hydroxyethoxy)ethyl)-2,3-diisopropylguanidine

(31) In a round-bottom flask, 23.14 g of 2-(2-aminoethoxy)ethanol (Diglycolamine Agent, from Huntsman) and 25.24 g of DIC were mixed and heated to 120 C. while stirring. After 24 hours, the carbodiimide band at about 2120 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. Thereafter, the reaction mixture was freed of the volatile constituents under reduced pressure. This gave 56.50 g of a mobile, pale yellow oil of low odor.

(32) FT-IR: 3354 (OH), 2963, 2921, 2865, 1616 (CN), 1524, 1465, 1362, 1337, 1178, 1121, 1066, 884, 829, 715.

Preparation of Amine Intermediates

Compound A-1: N-(2,2-dimethyl-3-lauroyloxypropylidene)-1,3-diaminopropane

(33) In a round-bottom flask, 3.82 g of 1,3-diaminopropane and 14.21 g of 2,2-dimethyl-3-lauroyloxypropanal were mixed and heated to 60 C. while stirring. After 30 minutes, the volatile constituents were removed by means of reduced pressure at 80 C. This gave 16.96 g of a yellowish oil.

(34) FT-IR: 3308, 2922, 2853, 1733, 1668, 1556, 1466, 1432, 1394, 1376, 1350, 1316, 1235, 1165, 1134, 1108, 1048, 1031, 1005, 946, 902, 877, 854, 798, 767, 722.

Compound A-2: N-(2,2-dimethyl-3-lauroyloxypropylidene)-1,2-diaminopropane

(35) In a round-bottom flask, 3.81 g of 1,2-diaminopropane and 14.25 g of 2,2-dimethyl-3-lauroyloxypropanal were mixed and heated to 60 C. while stirring. After 20 minutes, the volatile constituents were removed by means of reduced pressure at 80 C. This gave 16.97 g of a colorless oil.

(36) FT-IR: 3353, 2956, 2923, 2853, 1733, 1667, 1632, 1466, 1418, 1391, 1376, 1301, 1253, 1161, 1112, 1076, 1056, 1001, 934, 883, 826, 722.

Compound A-3: N-(2,2-dimethyl-3-(N-morpholino)propylidene)-1,3-diaminopropane

(37) In a round-bottom flask, 3.16 g of 1,3-diaminopropane and 6.87 g of 2,2-dimethyl-3-(N-morpholino)propanal were mixed and heated to 80 C. while stirring. After 40 minutes, the volatile constituents were removed by means of reduced pressure at 80 C. This gave 8.67 g of a yellowish oil.

(38) FT-IR: 3286, 2934, 2848, 2800, 1665, 1573, 1455, 1430, 1375, 1349, 1313, 1282, 1263, 1203, 1133, 1115, 1070, 1337, 1010, 983, 923, 863, 803, 767.

Preparation of Catalysts of the Formula (I)

Catalyst K-1: 1,1,1-trimethylolpropane tris(3-(3-(2,3-dicyclohexylguanidino)propylamino)propionate)

(39) In a round-bottom flask, 28.05 g of the previously prepared compound G-1 were mixed with 9.88 g of TMPTA and heated to 120 C. After 4 hours, the acrylate band at about 809 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. Thereafter, the reaction mixture was freed of the volatile constituents under reduced pressure. This gave 37.93 g of a highly viscous, odorless oil.

(40) FT-IR: 3291 (NH), 2923, 2850, 1732 (CO), 1628 (CN), 1515, 1448, 1381, 1362, 1343, 1254, 1170, 1113, 1051, 1025, 888, 843, 782, 707.

Catalyst K-2: 1,1,1-trimethylolpropane tris(3-(N-cyclohexyl-3-(2,3-diisopropylguanidino)propylamino)propionate)

(41) In a round-bottom flask, 28.25 g of the previously prepared compound G-4 were mixed with 9.88 g of TMPTA and heated to 120 C. After 24 hours, the acrylate band at about 809 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. Thereafter, the reaction mixture was freed of the volatile constituents under reduced pressure. This gave 38.10 g of a highly viscous, odorless oil.

(42) FT-IR: 2961, 2925, 2852, 1735 (CO), 1627 (CN), 1449, 1362, 1346, 1305, 1250, 1163, 1125, 1055, 889, 718.

Catalyst K-3

(43) To an initial charge of 179.27 g of polymer HEA-1 in a round-bottom flask were added 23.45 g of the previously prepared compound G-4, and the reaction mixture was heated to 100 C. After 3 hours, the acrylate band at about 815 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. This gave an odorless oil of moderate viscosity.

(44) FT-IR: 2969, 2929, 2866, 1720 (CO), 1644 (CN), 1525, 1452, 1372, 1343, 1296, 1096, 1013, 925, 866, 832, 700.

Catalyst K-4

(45) To an initial charge of 179.27 g of polymer HEA-1 in a round-bottom flask were added 23.19 g of the previously prepared compound G-2, and the reaction mixture was heated to 100 C. After 2 hours, the acrylate band at about 815 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. This gave an odorless oil of moderate viscosity.

(46) FT-IR: 3305, 1969, 2928, 2864, 1730 (CO), 1682, 1621 (CN), 1533, 1450, 1372, 1344, 1296, 1226, 1096, 1013, 926, 866, 825, 768, 718.

Catalyst K-5

(47) To an initial charge of 179.27 g of polymer HEA-1 in a round-bottom flask were added 30.15 g of the previously prepared compound G-3, and the reaction mixture was heated to 100 C. After 2 hours, the acrylate band at about 815 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. This gave an odorless oil of moderate viscosity.

(48) FT-IR: 3312, 2969, 2928, 2865, 1728 (CO), 1682, 1629 (CN), 1538, 1450, 1372, 1344, 1296, 1226, 1097, 1013, 926, 865, 825, 767, 714.

Catalyst K-6

(49) To an initial charge of 179.27 g of polymer HEA-1 in a round-bottom flask were added 24.40 g of the previously prepared compound G-1, and the reaction mixture was heated to 100 C. After 2 hours, the acrylate band at about 815 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. This gave an odorless oil of moderate viscosity.

(50) FT-IR: 3309, 2970, 2930, 2867, 1730 (CO), 1620 (CN), 1601, 1533, 1452, 1408, 1372, 1344, 1296, 1225, 1180, 1093, 1013, 926, 867, 811, 768.

Catalyst K-7

(51) An initial charge of 282.2 g of polymer NCO-2 in a round-bottom flask was mixed with 17.79 g of the previously prepared compound G-5 under reduced pressure and heated to 50 C. After 1 hour, the isocyanate band at about 2263 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. Then 1.5 g of vinyltrimethoxysilane were added. This gave an odorless oil of moderate viscosity.

(52) FT-IR: 2969, 2929, 2866, 1720 (CO), 1644 (CN), 1525, 1452, 1372, 1343, 1296, 1096, 1013, 925, 866, 832, 700.

Catalyst K-8

(53) An initial charge of 282.2 g of polymer NCO-2 in a round-bottom flask was mixed with 13.21 g of the previously prepared compound G-6 under reduced pressure and heated to 50 C. After 5 minutes, the isocyanate band at about 2263 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. Then 1.5 g of vinyltrimethoxysilane were added. This gave an odorless oil of moderate viscosity.

(54) FT-IR: 2969, 2930, 2867, 1720 (CO), 1675, 1644 (CN), 1525, 1454, 1372, 1343, 1296, 1096, 1013, 925, 867, 831.

Catalyst K-9: 1-(3-((3-((2-ethylhexyl)oxy)-2-hydroxypropyl)amino)propyl)-2,3-dicyclohexylguanidine

(55) In a round-bottom flask, 2.89 g of the previously prepared compound G-1 were mixed with 1.86 g of EHGE and heated to 50 C. After 24 hours, the epoxide band at about 911 cm.sup.1 (FT-IR spectroscopy) had almost completely disappeared, and then the reaction mixture was stirred at 80 C. for 3 hours. This gave a colorless, odorless oil of moderate viscosity, which solidified to give a wax after a few hours at room temperature.

(56) FT-IR: 2923, 2851, 1627 (CN), 1507, 1448, 1360, 1340, 1256, 1238, 1104, 977, 888, 845, 767, 725.

Catalyst K-10: 1-(3-((3-((C12-14-alkyl)oxy)-2-hydroxypropyl)amino)propyl)-2,3-dicyclohexylguanidine

(57) In a round-bottom flask, 2.89 g of the previously prepared compound G-1 were mixed with 2.82 g of DY-E and heated to 80 C. After 6 hours, the epoxide band at about 912 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. This gave a colorless, odorless oil of moderate viscosity.

(58) FT-IR: 3246, 2921, 2851, 1627 (CN), 1505, 1463, 1449, 1405, 1361, 1344, 1304, 1257, 1239, 1112, 1028, 977, 889, 844, 814, 720.

Catalyst K-11: 1-(3-((3-((2-methylphenyl)oxy)-2-hydroxypropyl)amino)propyl)-2,3-dicyclohexylguanidine

(59) In a round-bottom flask, 2.89 g of the previously prepared compound G-1 were mixed with 1.83 g of DY-K and heated to 80 C. After 6 hours, the epoxide band at about 915 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. This gave a colorless, odorless oil of moderate viscosity.

(60) FT-IR: 3270, 2923, 2849, 1622 (CN), 1602, 1494, 1448, 1360, 1339, 1307, 1287, 1243, 1190, 1147, 1120, 1050, 1034, 977, 924, 888, 940, 747, 712.

Catalyst K-12: 2,2-bis(4-(2-hydroxy-3-(3-(2,3-dicyclohexylguanidino)propyl)aminopropoxy)phenyl)propane

(61) In a round-bottom flask, 2.89 g of the previously prepared compound G-1 were mixed with 1.86 g of BADGE and heated to 80 C. After 6 hours, the epoxide band at about 914 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. This gave a colorless, odorless oil of high viscosity.

(62) FT-IR: 3357 (OH), 2924, 2851, 1606 (CN), 1580, 1507, 1450, 1383, 1343, 1296, 1235, 1181, 1105, 1084, 1033, 967, 915, 826, 757, 737, 726, 668.

Catalyst K-13: ,-bis(2-hydroxy-3-(3-(2,3-dicyclohexylguanidino)propyl)aminopropyl)polypropylene glycol

(63) In a round-bottom flask, 2.89 g of the previously prepared compound G-1 were mixed with 5.10 g of DY-F and heated to 80 C. After 6 hours, the epoxide band at about 907 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. This gave a colorless, odorless oil of moderate viscosity, which took on a pasty consistency after a few hours at room temperature.

(64) FT-IR: 3270, 2969, 2926, 2852, 1623 (CN), 1507, 1449, 1372, 1343, 1298, 1257, 1099, 1014, 926, 889, 862, 836, 712.

Catalyst K-14: 2-hydroxypropyl N-(3-(2,3-dicyclohexylguanidino)propyl)carbamate and 3-hydroxy-2-propyl N-(3-(2,3-dicyclohexylguanidino)propyl)carbamate

(65) In a round-bottom flask, 2.89 g of the previously prepared compound G-1 were mixed with 1.12 g of 1,2-propylene carbonate and heated to 90 C. After 30 minutes, the volatile constituents were removed by means of reduced pressure at 80 C. This gave 4.03 g of a transparent, odorless solid.

(66) FT-IR: 3335, 2925, 2851, 1699, 1621, 1518, 1448, 1361, 1338, 1257, 1145, 1109, 1054, 992, 978, 889, 845, 800, 775, 715.

Catalyst K-15: 1-(3-(3-acetylprop-2-en-2-yl)aminopropyl)-2,3-dicyclohexylguanidine

(67) In a round-bottom flask, 2.89 g of the previously prepared compound G-1 were mixed with 1.10 g of pentane-2,4-dione and, after 10 minutes, the volatile constituents were removed by means of reduced pressure at 80 C. This gave 3.98 g of a yellow, odorless solid.

(68) FT-IR: 3192, 3044, 2925, 2852, 1608, 1570, 1483, 1445, 1360, 1295, 1245, 1237, 1211, 1191, 1173, 1150, 1103, 1074, 1052, 1000, 952, 890, 846, 785, 738.

Catalyst K-16: 1-(3-(3-(N,N-diethylaminocarbonyl)prop-2-en-2-yl)aminopropyl)-2,3-dicyclohexylguanidine

(69) In a round-bottom flask, 2.89 g of the previously prepared compound G-1 were mixed with 1.61 g of N,N-diethylacetoacetamide and, after 10 minutes, the volatile constituents were removed by means of reduced pressure. This gave 3.89 g of a white, odorless solid.

(70) FT-IR: 3197, 2970, 2926, 2852, 1722, 1633, 1591, 1473, 1493, 1476, 1448, 1360, 1347, 1315, 1257, 1231, 1150, 1122, 1069, 999, 980, 954, 913, 890, 843, 827, 772, 710.

Catalyst K-17: 3-((3-(2,3-dicyclohexylguanidino)propyl)imino)-2,2-dimethylpropyl dodecanoate

(71) In a round-bottom flask, 2.89 g of the previously prepared compound G-1 were mixed with 2.97 g of 2,2-dimethyl-3-lauroyloxypropanal, the mixture was stirred at room temperature for 10 minutes and then the volatile constituents were removed by means of reduced pressure at 80 C. This gave 5.72 g of a yellowish, odorless oil of moderate viscosity.

(72) FT-IR: 3202, 2923, 2852, 1739, 1661, 1627, 1564, 1450, 1417, 1392, 1364, 1348, 1288, 1246, 1190, 1151, 1107, 1067, 1028, 999, 890, 845, 800, 720.

Catalyst K-18: 3-((3-(2,3-dicyclohexylguanidino)propyl)imino)-2,2-dimethylpropyl dodecanoate

(73) In a round-bottom flask, 7.06 g of the previously prepared compound A-1 were mixed with 4.05 g of DCC and heated to 110 C. while stirring. After 48 hours, the carbodiimide band at about 2120 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. Thereafter, the reaction mixture was freed of the volatile constituents under reduced pressure. This gave 11.12 g of a yellow, odorless oil of low viscosity.

(74) FT-IR: 3292, 2922, 2851, 1738, 1640, 1543, 1449, 1364, 1315, 1253, 1151, 1110, 1070, 889, 845, 721.

Catalyst K-19: 3-((3-(2,3-diisopropylguanidino)propyl)imino)-2,2-dimethylpropyl dodecanoate

(75) In a round-bottom flask, 5.79 g of the previously prepared compound A-1 were mixed with 1.96 g of DIC and heated to 110 C. while stirring. After 4 days, the carbodiimide band at about 2120 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. Thereafter, the reaction mixture was freed of the volatile constituents under reduced pressure. This gave 7.75 g of a yellow, odorless oil of low viscosity.

(76) FT-IR: 3290, 2958, 2923, 2853, 1738, 1640, 1538, 1465, 1364, 1258, 1166, 1124, 1012, 933, 721.

Catalyst K-20: 3-((3-(2,3-dicyclohexylguanidino)prop-2-yl)imino)-2,2-dimethylpropyl dodecanoate

(77) In a round-bottom flask, 7.65 g of the previously prepared compound A-2 were mixed with 4.41 g of DCC and heated to 110 C. while stirring. After 7 days, the carbodiimide band at about 2120 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. Thereafter, the reaction mixture was freed of the volatile constituents under reduced pressure. This gave 12.06 g of an orange, odorless oil of low viscosity.

(78) FT-IR: 3304, 2923, 2852, 1738, 1643, 1538, 1463, 1449, 1374, 1345, 1318, 1252, 1237, 1151, 1111, 1072, 1027, 978, 940, 889, 861, 845, 721.

Catalyst K-21: 1-(3-((3-(N-morpholino)-2,2-dimethylpropylidene)amino)propyl)-2,3-dicyclohexylguanidine

(79) In a round-bottom flask, 7.56 g of the previously prepared compound A-3 were mixed with 4.11 g of DCC and heated to 90 C. while stirring. After 7 days, the carbodiimide band at about 2120 cm.sup.1 (FT-IR spectroscopy) had completely disappeared. Thereafter, the reaction mixture was freed of the volatile constituents under reduced pressure. This gave 8.63 g of a yellow, odorless oil of low viscosity.

(80) FT-IR: 3355, 2923, 2849, 2807, 1636, 1504, 1449, 1360, 1345, 1282, 1268, 1257, 1236, 1136, 1116, 1070, 1051, 1012, 978, 929, 888, 864, 802, 713.

Preparation of Polyethers Containing Silane Groups

(81) Polymer STP-1:

(82) With exclusion of moisture, 1000 g of Acclaim 12200 polyol (polyoxy-propylenediol having a low level of unsaturation, from Bayer; OH number 11.0 mg KOH/g), 43.6 g of isophorone diisocyanate (IPDI; 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 up to 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. Subsequently, 63.0 g of diethyl N-(3-trimethoxysilylpropyl)-aminosuccinate (adduct formed from 3-aminopropyltrimethoxysilane and diethyl maleate; prepared according to the details in U.S. Pat. No. 5,364,955) were mixed in and the mixture was stirred at 90 C. until it was no longer possible to detect any free isocyanate by means of FT-IR spectroscopy. The polyether containing trimethoxysilane groups thus obtained, having a silane equivalent weight of about 6880 g/eq (calculated from the amounts used), was cooled down to room temperature and stored with exclusion of moisture.

(83) Polymer STP-2:

(84) With exclusion of moisture, 1000 g of Acclaim 12200 polyol (polyoxy-propylenediol having a low level of unsaturation, from Bayer; OH number 11.0 mg KOH/g), 43.6 g of isophorone diisocyanate (IPDI; 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 up to 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 0.64% by weight. Subsequently, 70.6 g of diethyl N-(3-triethoxysilylpropyl)-aminosuccinate (adduct formed from 3-aminopropyltriethoxysilane and diethyl maleate) were mixed in and the mixture was stirred at 90 C. until it was no longer possible to detect any free isocyanate by means of FT-IR spectroscopy. The polyether containing triethoxysilane groups thus obtained, having a silane equivalent weight of about 6920 g/eq (calculated from the amounts used), was cooled down to room temperature and stored with exclusion of moisture.

(85) Commercial Catalysts Used: DBU 1,8-diazabicyclo[5.4.0]undec-7-ene (Lupragen N 700, from BASF) TMG 1,1,3,3-tetramethylguanidine (from Sigma-Aldrich) IBAY bis(ethylacetoacetato)diisobutoxytitanium(IV) (Tyzor IBAY, from Dorf Ketal)

(86) Compositions Based on Polymers Containing Silane Groups:

(87) Comparative examples in tables 1 to 8 are indicated by (Ref).

(88) Compositions Z1 to Z26:

(89) A composition composed of 96.5 g of polymer STP-1, 0.5 g of vinyltrimethoxy-silane and 3.0 g of 3-aminopropyltrimethoxysilane was blended with various catalysts in the amount specified according to table 1, and the mixture was tested for viscosity and skin time (ST) under standard climatic conditions, before and after storage. The skin time serves as a measure of the activity of the catalyst in relation to the crosslinking reaction of the silane groups, i.e. of the crosslinking rate; the change in viscosity and the skin time after storage are a measure of storage stability. In addition, the mixture applied, after 24 hours under standard climatic conditions, was tested as to whether the surface was dry as desired or whether a greasy film had formed, which is a sign of the exudation of the catalyst owing to poor compatibility with the cured polymer, and/or whether the surface was tacky, which is a sign of incomplete curing. In addition, the mixture was used to produce a film of thickness 2 mm, which was left to cure under standard climatic conditions for 7 days and tested for mechanical properties. The results are shown in tables 1 and 2. Comp. stands for composition.

(90) TABLE-US-00001 TABLE 1 Viscosity [Pa .Math. s] ST Comp. Catalyst Amount Concentration.sup.1 fresh stored.sup.2 increase fresh stored.sup.2 Z1 K-1.sup.3 0.70 g 1.90 28.1 36.3 29% 16 23 Z2 K-2.sup.3 0.70 g 1.90 30.2 41.8 38% 12 18 Z3 K-3 4.66 g 2.00 26.4 29.5 12% 38 30 Z4 K-4 4.73 g 2.00 34.6 47.2 36% 26 21 Z5 K-5 4.89 g 2.00 32.6 37.6 15% 20 29 Z6 K-6 4.52 g 2.00 29.0 31.0 7% 30 21 Z7 K-7 12.80 g 1.90 32.5 50.8 56% 32 11 Z8 K-8 12.65 g 1.90 26.5 49.3 86% 51 11 Z9 K-9.sup.3 0.85 g 1.90 21.4 26.2 22% 12 21 Z10 K-9.sup.3 0.11 g 0.25 25.2 32.9 31% 44 80 IBAY 0.25 g 0.50 Z11 K-10 1.02 g 1.90 22.0 32.8 49% 10 25 Z12 K-11.sup.3 0.84 g 1.90 19.4 25.5 31% 33 31 Z13 K-12.sup.3 0.85 g 1.90 20.8 26.2 26% 9 22 Z14 K-13.sup.3 1.42 g 1.90 20.1 30.5 52% 14 21 Z15 K-13.sup.3 0.19 g 0.25 27.3 36.3 33% 75 80 IBAY 0.25 g 0.50 Z16 K-14.sup.3 0.70 g 1.90 21.0 32.0 52% 10 11 Z17 K-15.sup.3 0.67 g 1.90 25.0 44.6 78% 14 9 Z18 K-16.sup.3 0.77 g 1.90 27.8 59.6 114% 7 7 Z19 K-17.sup.3 1.00 g 1.90 26.4 43.8 66% 20 13 Z20 K-18.sup.3 1.00 g 1.90 34.5 48.6 41% 21 18 Z21 K-19 1.86 g 1.90 36.2 52.2 44% 23 18 Z22 K-20 1.00 g 1.90 35.4 51.8 46% 25 19 Z23 K-21 0.80 g 1.90 43.3 77.3 79% 14 7 Z24 (Ref) DBU 0.28 g 1.90 27.2 36.9 36% 25 29 Z25 (Ref) TMG 0.21 g 1.90 22.3 24.6 10% 65 75 Z26 (Ref) DBU 0.04 g 0.25 26.9 28.9 7% 54 90 IBAY 0.25 g 0.50 .sup.1mmol of amidine or guanidine groups/metal atoms per 100 g of polyether containing silane groups. .sup.2for 7 days at 60 C. in a closed container. .sup.3as a solution (40% by wt.) in N-ethylpyrrolidone.

(91) TABLE-US-00002 TABLE 2 Surface Tensile Elongation Modulus of elasticity Comp. after 24 h strength at break 0-5% 0-50% Z1 dry 0.74 MPa 123% 1.00 MPa 0.72 MPa Z2 dry 0.67 MPa 104% 1.02 MPa 0.71 MPa Z3 dry 0.82 MPa 133% 0.82 MPa 0.74 MPa Z4 dry 0.76 MPa 124% 1.26 MPa 0.74 MPa Z5 dry 0.81 MPa 139% 1.21 MPa 0.72 MPa Z6 dry 0.79 MPa 126% 1.07 MPa 0.74 MPa Z7 dry 0.73 MPa 136% 0.94 MPa 0.66 MPa Z8 dry 0.70 MPa 115% 1.00 MPa 0.70 MPa Z9 dry 0.72 MPa 97% 1.14 MPa 0.79 MPa Z10 dry 0.66 MPa 88% 0.90 MPa 0.77 MPa Z11 dry 0.73 MPa 106% 1.02 MPa 0.77 MPa Z12 dry 0.69 MPa 95% 0.98 MPa 0.77 MPa Z13 dry 0.96 MPa 140% 1.10 MPa 0.84 MPa Z14 dry 0.68 MPa 95% 1.00 MPa 0.78 MPa Z15 dry 0.75 MPa 116% 0.90 MPa 0.75 MPa Z16 dry 0.59 MPa 71% 0.94 MPa 0.78 MPa Z17 dry 0.68 MPa 91% 1.00 MPa 0.78 MPa Z18 dry 0.60 MPa 77% 0.98 MPa 0.77 MPa Z19 dry 0.61 MPa 79% 0.94 MPa 0.77 MPa Z20 almost dry 0.63 MPa 82% 1.08 MPa 0.80 MPa Z21 almost dry 0.62 MPa 81% 1.14 MPa 0.81 MPa Z22 dry 0.66 MPa 89% 1.10 MPa 0.80 MPa Z23 dry 0.57 MPa 65% 1.25 MPa 0.81 MPa Z24(Ref) greasy 0.58 MPa 72% 1.16 MPa 0.77 MPa Z25(Ref) tacky 0.62 MPa 90% 1.19 MPa 0.75 MPa Z26(Ref) dry 0.66 MPa 91% 0.93 MPa 0.74 MPa

(92) Compositions Z27 to Z37:

(93) A composition composed of 95.9 g of polymer STP-2, 0.4 g of vinyltriethoxy-silane and 3.7 g of N-(2-aminoethyl)-3-aminopropyltriethoxysilane was blended with various catalysts in the amount specified according to table 3, and the mixture was tested as described for composition Z1 for viscosity, skin time (ST), surface characteristics and mechanical properties. The results are shown in tables 3 and 4. Comp. stands for composition.

(94) TABLE-US-00003 TABLE 3 Viscosity [Pa .Math. s] ST Comp. Catalyst Amount Concentration.sup.1 fresh stored.sup.2 increase fresh stored.sup.2 Z27 K-3 9.72 g 4.2 36.4 66.4 82% 4 h 20 1 h 23 Z28 K-4 9.86 g 4.2 40.8 48.9 20% 4 h 29 2 h 24 Z29 K-5 10.20 g 4.2 41.5 47.8 15% 4 h 11 2 h 53 Z30 K-6 9.43 g 4.2 39.2 42.0 7% 4 h 3 h 36 Z31 K-9 1.68 g 3.8 79.6 101.9 28% 1 h 16 1 h 25 Z32 K-10 2.02 g 3.8 76.3 96.6 27% 1 h 49 1 h 51 Z33 K-11.sup.3 1.67 g 3.8 58.4 83.0 42% 1 h 33 1 h 21 Z34 K-12.sup.3 1.68 g 3.8 58.2 97.5 68% 38 33 Z35 K-13 2.83 g 3.8 36.6 61.0 67% 1 h 07 1 h 15 Z36 (Ref) DBU 0.55 g 3.8 48.8 58.1 19% 2 h 7 2 h 35 Z37 (Ref) TMG 0.42 g 3.8 44.5 53.4 20% >12 h >12 h .sup.1mmol of amidine or guanidine groups per 100 g of polyether containing silane groups. .sup.2for 7 days at 60 C. in a closed container. .sup.3as a solution (40% by wt.) in N-ethylpyrrolidone.

(95) TABLE-US-00004 TABLE 4 Surface Tensile Elongation Modulus of elasticity Comp. after 24 h strength at break 0-5% 0-50% Z27 slightly 0.52 MPa 129% 0.39 MPa 0.43 MPa tacky Z28 dry 0.67 MPa 160% 0.86 MPa 0.52 MPa Z29 dry 0.67 MPa 167% 0.81 MPa 0.49 MPa Z30 dry 0.57 MPa 135% 0.67 MPa 0.48 MPa Z31 almost dry 0.59 MPa 241% 0.31 MPa 0.31 MPa Z32 almost dry 0.50 MPa 194% 0.31 MPa 0.30 MPa Z33 almost dry 0.54 MPa 225% 0.30 MPa 0.29 MPa Z34 almost dry 0.60 MPa 233% 0.30 MPa 0.30 MPa Z35 almost dry 0.56 MPa 129% 0.68 MPa 0.50 MPa Z36 (Ref) greasy, 0.43 MPa 157% 0.28 MPa 0.28 MPa highly tacky Z37 (Ref) very n.d. n.d. n.d. n.d. highly tacky n.d. = not determined/not measurable.

(96) Compositions Z38 to Z42:

(97) In a planetary mixer, 30.8 g of polymer STP-1, 25.7 g of ground chalk (Omyacarb 5 GU, from Omya), 25.7 g of precipitated chalk (Socal U1S2, from Solvay), 15.4 g of diisononyl cyclohexane-1,2-dicarboxylate (Hexamoll DINCH, from BASF), 1.2 g of vinyltrimethoxysilane, 1.2 g of 3-aminopropyltrimethoxysilane and various catalysts in the amount specified according to table 5 were blended, and the mixture was tested as described for composition Z1 for skin time (ST), surface characteristics and mechanical properties. The results are shown in table 5. Comp. stands for composition.

(98) TABLE-US-00005 TABLE 5 Surface Modulus of after Tensile Elongation elasticity [MPa] Comp. Catalyst Amount Concentration.sup.1 ST 24 h strength at break 0-5% 0-100% Z38 K-1.sup.2 0.19 g 0.5 71 dry 2.0 MPa 263% 2.0 1.2 Z39 K-2.sup.2 0.19 g 0.5 29 dry 2.0 MPa 255% 1.9 1.2 Z40 K-7 2.99 g 0.4 23 dry 2.0 MPa 248% 1.9 1.2 Z41 K-8 2.96 g 0.4 22 dry 1.9 MPa 275% 1.9 1.1 Z42 DBU 0.08 g 0.5 35 greasy 2.1 MPa 283% 1.8 1.2 (Ref) .sup.1mmol of amidine or guanidine groups per 100 g of composition. .sup.2as a solution (40% by wt.) in N-ethylpyrrolidone.

(99) Compositions Z43 to Z52:

(100) In a planetary mixer, 36.2 g of polymer STP-1, 60.2 g of ground chalk (Omyacarb 5 GU, from Omya), 1.2 g of thixotropic paste prepared as described below, 1.2 g of vinyltrimethoxysilane, 1.2 g of 3-aminopropyltrimethoxysilane and various catalysts in the amount specified according to table 6 were blended, and the mixture was tested as described for composition Z1 for skin time (ST), surface characteristics and mechanical properties. The results are shown in table 6. Comp. stands for composition. The thixotropic paste was prepared by initially charging a vacuum mixer with 300 g of diisodecyl phthalate (Palatinol Z, from BASF) and 48 g of 4,4-methylene diphenyl diisocyanate (Desmodur 44 MC L, from Bayer), gently heating the initial charge and then slowly adding 27 g of n-butylamine dropwise while stirring vigorously. The resultant paste was stirred for a further hour under reduced pressure while cooling.

(101) TABLE-US-00006 TABLE 6 Surface Modulus of after Tensile Elongation elasticity [MPa] Comp. Catalyst Amount Concentration.sup.1 ST 24 h strength at break 0-5% 0-100% Z43 K-3 4.83 g 2.0 27 dry 2.7 MPa 132% 4.2 2.4 Z44 K-4 4.90 g 2.0 15 dry 2.7 MPa 118% 4.5 2.5 Z45 K-5 5.07 g 2.0 16 dry 2.6 MPa 114% 4.5 2.4 Z46 K-6 4.68 g 2.0 11 dry 3.0 MPa 134% 4.6 2.5 Z47 K-9 0.18 g 0.4 27 dry 2.9 MPa 117% 6.0 2.6 Z48 K-10 0.22 g 0.4 31 dry 2.7 MPa 91% 6.1 Z49 K-11.sup.2 0.18 g 0.4 21 dry 2.4 MPa 69% 6.0 Z50 K-12.sup.2 0.18 g 0.4 33 dry 2.9 MPa 116% 5.9 2.6 Z51 K-13 0.31 g 0.4 25 dry 2.9 MPa 104% 5.9 2.7 Z52 DBU 0.12 g 0.8 25 slightly 2.5 MPa 103% 6.1 2.8 (Ref) greasy .sup.1mmol of amidine or guanidine groups per 100 g of composition. .sup.2as a solution (40% by wt.) in N-ethylpyrrolidone.

(102) Compositions Z53 to Z61:

(103) In a planetary mixer, 36.2 g of polymer STP-2, 60.2 g of ground chalk (Omyacarb 5 GU, from Omya), 1.2 g of thixotropic paste prepared as described for composition Z27, 1.2 g of vinyltriethoxysilane, 1.2 g of 3-aminopropyltriethoxysilane and various catalysts in the amount specified according to table 7 were blended, and the mixture was tested as described for composition Z1 for skin time (ST), surface characteristics and mechanical properties. The results are shown in table 7. Comp. stands for composition.

(104) TABLE-US-00007 TABLE 7 Surface Modulus of after Tensile Elongation elasticity [MPa] Comp. Catalyst Amount Concentration.sup.1 ST 24 h strength at break 0-5% 0-100% Z53 K-4 9.79 g 4.0 169 dry 2.0 MPa 167% 3.1 1.5 Z54 K-5 10.13 g 4.0 69 dry 2.1 MPa 164% 3.6 1.6 Z55 K-6 9.36 g 4.0 125 dry 2.4 MPa 180% 3.1 1.7 Z56 K-9 1.20 g 2.6 67 s. tacky 2.6 MPa 108% 4.9 2.5 Z57 K-10 1.44 g 2.6 83 s. tacky 2.6 MPa 127% 4.6 2.3 Z58 K-11.sup.2 1.19 g 2.6 96 s. tacky 2.9 MPa 145% 5.0 2.4 Z59 K-12.sup.2 1.20 g 2.6 77 s. tacky 2.2 MPa 106% 6.7 1.9 Z60 K-13 2.02 g 2.6 79 s. tacky 2.5 MPa 127% 5.9 2.2 Z61 DBU 0.40 g 2.6 83 slightly 2.5 MPa 155% 4.0 2.0 (Ref) greasy .sup.1mmol of amidine or guanidine groups per 100 g of polyether containing silane groups. .sup.2as a solution (40% by wt.) in N-ethylpyrrolidone. s. stands for slightly.

(105) Compositions Z62 and Z63:

(106) A composition composed of 96.0 g of GENIOSIL STP-E 15 polyether containing silane groups (from Wacker), 0.35 g of vinyltrimethoxysilane and 3.72 g of 3-aminopropyltrimethoxysilane was blended with various catalysts in the amount specified according to table 8, and the mixture was tested as described for composition Z1 for skin time (ST), surface characteristics and mechanical properties. The results are shown in table 8. Comp. stands for composition.

(107) TABLE-US-00008 TABLE 8 Modulus of Surface Tensile Elongation elasticity Comp. Catalyst Amount Concentration.sup.1 ST after 24 h strength at break 0-5% Z62 K-13 1.51 g 1.9 23 dry 0.82 MPa 60% 1.77 MPa Z63 DBU 0.28 g 1.9 60 greasy 0.72 MPa 48% 1.84 MPa (Ref) .sup.1mmol of amidine or guanidine groups per 100 g of polyether containing silane groups.