METHOD FOR PRODUCING ORGANYLOXYSILANE-TERMINATED POLYMERS

Abstract

The invention provides a process for preparing a mixture (M) which comprises silane-terminated polymers (SP1) of the general formula (I)

Y.sup.1—[O—C(═O)—NH—(CR.sup.1.sub.2).sub.b—SiR.sub.a(OR.sup.2).sub.3-a].sub.x  (I),

optionally silane-terminated polymers (SP2) of the general formula (II)

Y.sup.2—[O—C(═O)—NH—(CR.sup.1.sub.2).sub.b—SiR.sub.a(OR.sup.2).sub.3-a].sub.z  (II) and hydroxy-functional polymers (SP3) of the general formula (III)

Y.sup.2—[O—C(═O)—NH—(CR.sup.1.sub.2).sub.b—SiR.sub.a(OR.sup.2).sub.3-a].sub.z-z1(OH).sub.z1  (III) where Y.sup.1 and Y.sup.2 are polymer radicals and R, R.sup.1, R.sup.2, x, z, z1, a and b have the definitions indicated in claim 1, wherein, in a first process step, at least one polymer (HP1) of the general formula (IV)

Y.sup.1—[OH].sub.x  (IV) reacts with at least one isocyanate-functional silane (S) of the general formula (V)

O═C═N—(CR.sup.1.sub.2).sub.b—SiR.sub.a(OR.sup.2).sub.3-a  (V) to give silane-terminated polymers (SP1), and, in a second process step, the unreacted isocyanate groups of the isocyanate-functional silane (S) of the general formula (V) are reacted with at least one oligomer or polymer (HP2) of the general formula (VI)

Y.sup.2(OH).sub.z  (VI); polymer mixtures (M) preparable by the process; and use of the polymer mixtures (M) for producing adhesives and sealants and also coatings.

Claims

1-12. (canceled)

13. A process for preparing a mixture (M), comprising: providing silane-terminated polymers (SP1) of the general formula (I)
Y.sup.1—[O—C(═O)—NH—(CR.sup.1.sub.2).sub.b—SiR.sub.a(OR.sup.2).sub.3-a].sub.x  (I), optionally silane-terminated polymers (SP2) of the general formula (II)
Y.sup.2—[O—C(═O)—NH—(CR.sup.1.sub.2).sub.b—SiR.sub.a(OR.sup.2).sub.3-a].sub.z  (II) and hydroxy-functional polymers (SP3) of the general formula (III)
Y.sup.2—[O—C(═O)—NH—(CR.sup.1.sub.2).sub.b—SiR.sub.a(OR.sup.2).sub.3-a].sub.z-z1(OH).sub.z1  (III) wherein Y.sup.1 is an x-valent polymer radical having a numerical average molar mass M.sub.n of at least 2000 g/mol; wherein Y.sup.2 is a z-valent oligomer or polymer radical having at least 3 identical repeating units which contain at least 2 carbon atoms and at least 1 heteroatom; wherein R may be identical or different and is a monovalent, optionally substituted hydrocarbon radical; wherein R.sup.1 may be identical or different and is hydrogen atom or a monovalent, optionally substituted hydrocarbon radical; wherein R.sup.2 may be identical or different and is hydrogen atom or a monovalent, optionally substituted hydrocarbon radical; wherein x is an integer from 2 to 50; wherein z is an integer from 1 to 50; wherein z1 is less than or equal to z and is an integer from 1 to 50, wherein a may be identical or different and is 0, 1 or 2; and wherein b may be identical or different and is an integer from 1 to 10; wherein, in a first process step, at least one polymer (HP1) of the general formula (IV)
Y.sup.1—[OH].sub.x  (IV) reacts with at least one isocyanate-functional silane (S) of the general formula (V)
O═C═N—(CR.sup.1.sub.2).sub.b—SiR.sub.a(OR.sup.2).sub.3-a  (V) to give silane-terminated polymers (SP1); wherein the isocyanate-functional silane (S) of the general formula (V) is used in an amount such that there are at least 1.1 isocyanate groups of the isocyanate-functional silane (S) of the general formula (V) to each hydroxyl group in the compounds (HP1) of the general formula (IV); wherein in a subsequent second process step, all unreacted isocyanate groups of the isocyanate-functional silane (S) of the general formula (V) are reacted with at least one oligomer or polymer (HP2) of the general formula (VI)
Y.sup.2(OH).sub.z  (VI), and the compound (HP2) of the general formula (VI) is used in an amount such that there are at least 1.1 hydroxyl groups in the compounds (HP2) of the general formula (IV) to each isocyanate group still present in the reaction mixture after the first process step; and wherein either z and z1 in the general formulae (II), (III) and (VI) possess a value of 1, there are silane-terminated polymers (SP2) of the general formula (II) in the mixture (M), and the polymers (SP3) likewise present in the mixture (M) correspond to the polymers (HP2) used in the second reaction step, or z in the general formulae (II), (III) and (VI) possesses a value of more than 1, Y.sup.2 is a z-valent oligomer or polymer radical having a numerical average molar mass M.sub.n of at most 1500 g/mol, and the mixture (M) comprises hydroxy-functional polymers (SP3) in which z1 is less than z.

14. The process of claim 13, wherein z possesses a value of at least 2 and wherein Y.sup.2 is a z-valent oligomer or polymer radical having a numerical average molar mass M.sub.n of at most 1000 g/mol.

15. The process of claim 13, wherein x is a value of 2 or 3.

16. The process of claim 13, wherein z is a value of 1 or 2.

17. The process of claim 13, wherein z1 is a value of 1 or 2.

18. The process of claim 13, wherein b is a value of 1 or 3.

19. The process of claim 13, wherein R is a monovalent hydrocarbon radical having 1 to 6 carbon atoms.

20. The process of claim 13, wherein the polymer radical Y.sup.1 is selected from polyester, polyether, polyurethane, polyalkylene or polyacrylate radicals.

21. The process of claim 13, wherein the polymer radical Y.sup.2 is selected from polyester, polyether, polyurethane, polyalkylene or polyacrylate radicals.

22. The process of claim 13, wherein the first and second process steps are carried out in the presence of a bismuth-containing catalyst (K).

23. The process of claim 13, wherein the mixture produced by the mixture (M) is a polymer mixture.

24. The process of claim 23, wherein the polymer mixture is used as an adhesive, a sealant or a coating.

Description

EXAMPLES

Example 1a: Preparation of a Mixture of Silane-Terminated Polypropylene Glycols

[0091] A 1000 ml reaction vessel with stirring, cooling and heating facilities is charged with 400.0 g (22.2 mmol) of a double-sidedly hydroxy-terminated polypropylene glycol having an average molar mass M.sub.n of 18 000 g/mol (available commercially under the name Acclaim® 18200 from Covestro AG, Leverkusen (DE)) and this initial charge is dried with stirring at 80° C. and 1 mbar for 2 h. Thereafter the vacuum is broken with nitrogen. The entirety of the subsequent reaction is carried out under an inert gas atmosphere of nitrogen.

[0092] To implement the silane termination, the dried polyether is admixed first dropwise at 80° C. with 18.2 g (88.8 mmol) of 3-isocyanatopropyltrimethoxysilane (available commercially under the name GENIOSIL® GF40 from Wacker Chemie AG, Munich (DE)) and then via an Eppendorf pipette with 0.62 g of Borchi catalyst 315 (a catalyst containing bismuth neadecanoate, from Borchers). This corresponds to a value of 150 ppm of catalyst, based on the total weight of the reaction mixture. Directly after the addition of catalyst, the reaction mixture warms up to 82-83° C. This is followed by stirring at a temperature of 80° C.

[0093] After 60 min at unaltered temperature, 266.4 g (53.3 mmol) of a monohydroxy-monobutoxy-terminated polypropylene glycol having an average molar mass M.sub.n of 5000 g/mol (available commercially under the name Preminol® S 1005 at AGC Chemicals Europe, LTD, Amsterdam (NL)) are added. This is followed by stirring for a further 60 min at 80° C. Thereafter a sample is taken from the reaction mixture and is analyzed by IR analysis for the possible presence of remaining isocyanatosilane residues. The sample is isocyanate-free.

Example 1b: Preparation of a Mixture of Silane-Terminated Polypropylene Glycols

[0094] The procedure is the same as in Example 1a, with the following amendments: [0095] In process step 1 (reaction of the Acclaim® 18200 with the isocyanate-functional silane) a smaller silane excess is used, of only 13.7 g (66.8 mmol). [0096] In process step 2 (reaction of the excess isocyanate-functional silane the monofunctional polypropylene glycol), correspondingly less Preminol® S 1005 is added, at 133.2 g (26.6 mmol).

[0097] Here again an isocyanate-free polymer mixture is obtained.

Comparative Example 1c: Preparation of a Non-Inventive Silane-Terminated Polypropylene Glycol

[0098] The procedure is the same as in Example 1a, with the following amendments: [0099] In process step 1 (reaction of the Acclaim® 18200 with the isocyanate-functional silane) an even smaller silane excess is used, of only 10.9 g (53.3 mmol). [0100] In process step 2 no Preminol® S 1005 is added. Instead, the excess isocyanatosilane is destroyed by addition of 0.43 g (13.4 mmol) of methanol. In contrast to Example 1a, the reaction temperature is lowered to 60° C. at the start of process step 2, i.e. directly before addition of the methanol, and after the addition of methanol stirring is continued at this temperature for 60 min.

[0101] The polymer obtained is isocyanate-free.

Example 2a: Production of an Adhesive Formulation

[0102] 40.0 g of the polymer mixture from Example 1a are mixed in a laboratory planetary mixer from PC-Laborsystem, fitted with a beam mixer and a dissolver, with 20 g of diisononyl phthalate (available commercially from companies including Merck KGaA, Darmstadt (DE)), 4.0 g of vinyltrimethoxysilane (available commercially under the name GENIOSIL® XL 10 from Wacker Chemie AG, Munich (DE)), 1.0 g of a stabilizer mixture (mixture of 20% Irganox® 1135 (CAS No. 125643-61-0), 40% Tinuvin® 571 (CAS No. 23328-53-2) and 40% Tinuvin® 765 (CAS No. 41556-26-7), available commercially under the name TINUVIN® B 75 from BASF SE, Germany), 24.2 g of a calcium carbonate coated with stearic acid and having an average particle diameter (D50%) of around 2.0 □m (available commercially under the name Omyabond 520 from Omya, Cologne (DE)) and 72.6 g of a precipitated calcium carbonate coated with fatty acid and having an average particle diameter (D50%) of around 0.07 □m (available commercially under the name Hakuenka CCR S10 from Shiraishi Omya GmbH, Gummem (AT)), and the solids are stirred in with the beam mixer at 200 rpm for one minute. Stirring continues thereafter for 5 min at 600 rpm with the beam mixer and 1000 rpm with the dissolver.

[0103] A further 30 g of diisononyl phthalate, 6.0 g of a hydrophobic pyrogenic silica having a BET surface area of around 200 m.sup.2/g (available commercially under the name HDK® H.sub.18 from Wacker Chemie AG, Munich (DE)), 0.2 g of dioctyltin dilaurate (available commercially under the name TIB KAT 216 from TIB Chemicals AG, Mannheim (DE)) and 2 g of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (available commercially under the name GENIOSIL® GF 9 from Wacker Chemie AG, Munich (DE)) are added and are stirred in for one minute at 600 rpm with the beam mixer and at 1000 rpm with the dissolver. This is followed by homogenization and bubble-free stirring under a partial vacuum (around 100 mbar) for 1 minute with the beam mixer at 600 rpm and for 1 minute at 200 rpm.

[0104] The composition obtained accordingly is dispensed into 310 ml PE cartridges and stored at 20° C. for 24 hours prior to analysis.

Example 2b: Production of an Adhesive Formulation

[0105] The procedure is as in Example 2a, replacing the polymer mixture from Example 1a with an identical amount of the polymer mixture from Example 1b.

Comparative Example 2c: Production of an Adhesive Formulation (not Inventive)

[0106] The procedure is as in Example 1a, replacing the polymer mixture from Example 1a with an identical amount of the polymer from comparative example 1c.

Example 3: Determination of Property Profiles of the Adhesive Formulations Produced

[0107] The adhesives obtained in Examples 1a to 1c are caused to crosslink and then studied for their skinning, their mechanical properties, and their adhesion to various substrates. The results are found in Table 1.

[0108] Skin Time (ST)

[0109] To determine the skin time, the crosslinkable compositions obtained in the examples are applied in a layer 2 mm thick to PE film and stored under standard conditions (23° C. and 50% relative atmospheric humidity). In the course of curing, the formation of a skin is tested every 5 min. This is done by placing a dry laboratory spatula carefully on the surface of the sample and pulling it upwards. If sample remains adhering on the finger, a skin has not yet formed. If sample no longer remains adhering on the finger, a skin has formed and the time is recorded.

[0110] Mechanical Properties

[0111] The compositions are each coated out onto milled Teflon plates with a depth of 2 mm and cured for 2 weeks at 23° C. and 50 relative humidity.

[0112] Shore A hardness is determined according to DIN 53505.

[0113] Tensile strength is determined according to DIN 53504-S1.

[0114] The 100% modulus is determined according to DIN 53504-S1.

[0115] Elongation at break is determined according to DIN 53504-S1.

[0116] Adhesion Profile without Water Storage

[0117] Using the compositions, adhesion tests are conducted in each case on the substrates indicated in Table 1, under the following conditions:

[0118] A bead 5-7 cm thick is applied to the substrate, which is stored in a conditioning cabinet at room temperature and a relative humidity of 50% for 14 days.

[0119] After storage, a peel test is conducted, in which the bead is cut off from the substrate at one end with a sharp knife to a length of around 2 cm. Subsequently, starting from this cut, the remainder of the bead is pulled from the substrate, and the nature of the resulting fracture (cohesive and/or adhesive) is assessed.

[0120] Adhesion Profile with Water Storage

[0121] Using the compositions, adhesion tests are conducted in each case on the substrates indicated in Table 1, under the following conditions:

[0122] A bead 5-7 cm thick is applied to the substrate, which is stored in a conditioning cabinet at room temperature and a relative humidity of 50% for 14 days. The sample is subsequently stored under water at room temperature for a further 14 days.

[0123] The subsequent peel test is again carried out as described above.

TABLE-US-00001 TABLE 1 Composition from Example 2a 2b 2c* (C) Skin time [min]  46  28  32 Shore A hardness  35  45  48 Tensile strength [N/mm.sup.2]  2.0  2.8  2.6 100% modulus  0.8  1.3  1.2 Elongation at break [%] 360 324 268 Adhesion without water storage AIMGSi1 Φ Φ Φ AIMg1 + + + AIMg anodized + + + Stainless steel + + + Copper + + + Cut concrete Rocholl + + + Glass + + + Wood (beech) + + + PMMA − − − PMMA filled + + − ABS − − − PVC flexible + + − PVC rigid, Simona transparent − − − PVC rigid grey Simona CAW − − − PVC rigid white Komadur ES + − − Polycarbonate + − − Polystyrene + − − Adhesion with water storage AIMGSi1 + + + AIMg1 + + + AIMg anodized + + + Stainless steel + − − Copper + + + Cut concrete Rocholl − − − Glass + + + Wood (beech) − − − PMMA − − − PMMA filled + Φ − ABS − − − PVC flexible + − − PVC rigid, Simona transparent + Φ − PVC rigid grey Simona CAW + − − PVC rigid white Komadur ES + − − Polycarbonate − − − Polystyrene + − − (+) good adhesion/cohesive fracture in peel test (Ø) partial adhesion/cohesive and adhesive fracture in peel test (−) no adhesion/adhesive fracture in peel test *not inventive

Example 4a: Preparation of a Mixture of Silane-Terminated Polyethers

[0124] A 1000 ml reaction vessel with stirring, cooling and heating facilities is charged with 400.0 g (33.3 mmol) of a double-sidedly hydroxy-terminated polypropylene glycol having an average molar mass M.sub.n of 12 000 g/mol (available commercially under the name Acclaim® 12200 from Covestro AG, Leverkusen (DE)) and this initial charge is dried with stirring at 80° C. and 1 mbar for 2 h. Thereafter the vacuum is broken with nitrogen. The entirety of the subsequent reaction is carried out under an inert gas atmosphere of nitrogen.

[0125] To implement the silane termination, the dried polyether is admixed first dropwise at 80° C. with 12.9 g (80.0 mmol) of isocyanatomethylmethyldimethoxysilane (available commercially under the name GENIOSIL® XL42 from Wacker Chemie AG, Munich (DE)) and then via an Eppendorf pipette with 0.62 g of Borchi catalyst 315. Directly after the addition of catalyst, the reaction mixture warms up to 83-84° C. This is followed by stirring at a temperature of 80° C.

[0126] After 60 min at unaltered temperature, 4.1 g (20.0 mmol) of methyltriglycol are added. This is followed by stirring for a further 60 min at 80° C. Thereafter a sample is taken from the reaction mixture and is analyzed by IR analysis for the possible presence of remaining isocyanatosilane residues. The sample is isocyanate-free.

Example 4b: Preparation of a Mixture of Silane-Terminated Polyethers

[0127] The procedure is as in Example 4a, but in the second process step, rather than 4.1 g of methyltriglycol, 7.0 g (20 mmol) of a polyglycol monomethyl ether having an average molecular mass M.sub.n of 350 g/mol (available commercially under the name Polyglycol M 350 from Clariant, Basel (CH)) are used.

Example 5a: Production of an Adhesive Formulation

[0128] 58.0 g of the polymer mixture from Example 4a are mixed in a laboratory planetary mixer from PC-Laborsystem, fitted with a beam mixer and a dissolver, with 40 g of diisoundecyl phthalate (available commercially under the name Jayfiex DIUP from ExxonMobil), 4.0 g of vinyltrimethoxysilane and 96.0 g of a ground calcium carbonate coated with stearic acid and having an average particle diameter (D50%) of around 0.4 □m (available commercially under the name Omyabond 302 from Omya, Cologne (DE)), and the calcium carbonate is stirred in with the beam mixer at 200 rpm for one minute. Stirring continues thereafter for 5 min at 600 rpm with the beam mixer and 1000 rpm with the dissolver.

[0129] 2 g of 3-aminopropyltrimethoxysilane (available commercially under the name GENIOSIL® GF 96 from Wacker Chemie AG, Munich (DE)) are added and are stirred in for one minute at 600 rpm with the beam mixer and at 1000 rpm with the dissolver. This is followed by homogenization and bubble-free stirring under a partial vacuum (around 100 mbar) for 1 minute with the beam mixer at 600 rpm and for 1 minute at 200 rpm.

[0130] The composition obtained accordingly is dispensed into 310 ml PE cartridges and stored at 20° C. for 24 hours prior to analysis.

Example 5b: Production of a Sealant Formulation

[0131] The procedure is as in Example 5a, replacing the polymer mixture from Example 4a with an identical amount of the polymer mixture from Example 4b.

Example 6: Determination of Property Profiles of the Sealant Formulations Produced

[0132] The adhesives obtained in Examples 5a and 5b are caused to crosslink and are studied by the methods described in Example 3 in terms of their skinning and their mechanical properties. The results are found in Table 2.

TABLE-US-00002 TABLE 2 Composition from Example 5a 5b Skin time [min] 18 18 Shore A hardness 47 49 Tensile strength [N/mm.sup.2] 2.4 2.4 100% modulus 1.4 1.5 Elongation at break [%] 206 187

Example 7: Preparation of a Mixture of Silane-Terminated Polyethers

[0133] A 1000 ml reaction vessel with stirring, cooling and heating facilities is charged with 400.0 g (22.2 mmol) of a double-sidedly hydroxy-terminated polypropylene glycol having an average molar mass M.sub.n of 18 000 g/mol (available commercially under the name Acclaim® 18200 from Covestro AG, Leverkusen (DE)) and this initial charge is dried with stirring at 80° C. and 1 mbar for 2 h. Thereafter the vacuum is broken with nitrogen. The entirety of the subsequent reaction is carried out under an inert gas atmosphere of nitrogen.

[0134] To implement the silane termination, the dried polyether is admixed first dropwise at 80° C. with 10.9 g (53.3 mmol) of 3-isocyanatopropyltrimethoxysilane and then via an Eppendorf pipette with 0.62 g of Borchi catalyst 315. Directly after the addition of catalyst, the reaction mixture warms up to 82-83° C. This is followed by stirring at a temperature of 80° C.

[0135] After 60 min at unaltered temperature, 4.7 g (13.4 mmol) of a polyglycol monomethyl ether having an average molecular mass M.sub.n of 350 g/mol (available commercially under the name Polyglycol M 350 from Clariant, Basel (CH)) are added. This is followed by stirring for a further 60 min at 80° C. Thereafter a sample is taken from the reaction mixture and is analyzed by IR analysis for the possible presence of remaining isocyanatosilane residues. The sample is isocyanate-free.

Example 8: Production of an Adhesive Formulation and Determination of its Properties

[0136] 58.0 g of the polymer mixture from Example 4a are mixed in a laboratory planetary mixer from PC-Laborsystem, fitted with a beam mixer and a dissolver, with 40 g of diisoundecyl phthalate (available commercially under the name Jayfiex DIUP from ExxonMobil), 4.0 g of vinyltrimethoxysilane and 95.6 g of a ground calcium carbonate coated with stearic acid and having an average particle diameter (D50%) of around 0.4 □m (available commercially under the name Omyabond 302 from Omya, Cologne (DE)), and the calcium carbonate is stirred in with the beam mixer at 200 rpm for one minute. Stirring continues thereafter for 5 min at 600 rpm with the beam mixer and 1000 rpm with the dissolver.

[0137] 2 g of 3-aminopropyltrimethoxysilane and 0.4 g of dioctyltin dilaurate are added and are stirred in for one minute at 600 rpm with the beam mixer and at 1000 rpm with the dissolver. This is followed by homogenization and bubble-free stirring under a partial vacuum (around 100 mbar) for 1 minute with the beam mixer at 600 rpm and for 1 minute at 200 rpm.

[0138] The composition obtained accordingly is dispensed into 310 ml PE cartridges and stored at 20° C. for 24 hours prior to analysis.

[0139] The resulting adhesives are caused to crosslink and investigated by the methods described in Example 3 in terms of its skinning and its mechanical properties. The skin time is 17 min, the Shore A hardness 49, tensile strength 2.6 N/mm.sup.2, the 100% modulus 1.23 N/mm.sup.2 and the elongation at break 209%.

Example 9a: Preparation of a Mixture of Silane-Terminated Polyethers

[0140] A 1000 ml reaction vessel with stirring, cooling and heating facilities is charged with 400.0 g (33.3 mmol) of a double-sidedly hydroxy-terminated polypropylene glycol having an average molar mass M.sub.n of 12 000 g/mol (available commercially under the name Acclaim® 12200 from Covestro AG, Leverkusen (DE)) and this initial charge is dried with stirring at 80° C. and 1 mbar for 2 h. Thereafter the vacuum is broken with nitrogen. The entirety of the subsequent reaction is carried out under an inert gas atmosphere of nitrogen.

[0141] To implement the silane termination, the dried polyether is admixed first dropwise at 80° C. with 21.5 g (133.2 mmol) of isocyanatomethylmethyldimethoxysilane and then via an Eppendorf pipette with 0.62 g of Borchi catalyst 315. Directly after the addition of catalyst, the reaction mixture warms up to around 84° C. This is followed by stirring at a temperature of 80° C.

[0142] After 60 min at unaltered temperature, 12.0 g (40.0 mmol) of a hydroxy-terminated at both ends and having an average molar mass M.sub.n of 300 g/mol (available commercially under the name Polyglycol 300 from Clariant, Basel (CH)) are added. This is followed by stirring for a further 60 min at 80° C. Thereafter a sample is taken from the reaction mixture and is analyzed by IR analysis for the possible presence of remaining isocyanatosilane residues. The sample is isocyanate-free.

Example 9b: Preparation of a Mixture of Silane-Terminated Polyethers

[0143] The procedure is the same as in Example 9a, with the following amendments: [0144] In process step 1 (reaction of the Acclaim® 12200 with the isocyanate-functional silane) a smaller silane excess is used, of only 16.1 g (99.9 mmol). [0145] In process step 2 (reaction of the excess isocyanate-functional silane the difunctional ethylene glycol), correspondingly less Polyglycol 300 is added, at 7.5 g (25.0 mmol).

[0146] Here again an isocyanate-free polymer mixture is obtained.

Comparative Example 9c: Preparation of a Non-Inventive Silane-Terminated Polypropylene Glycol

[0147] The procedure is the same as in Example 9a, with the following amendments: [0148] In process step 1 (reaction of the Acclaim® 12200 with the isocyanate-functional silane) an even smaller silane excess is used, of only 12.9 g (79.9 mmol). [0149] In process step 2 no Polyglycol 300 is added. Instead, the excess isocyanatosilane is destroyed by addition of 0.64 g (20.0 mmol) of methanol. In contrast to Example 9a, the reaction temperature is lowered to 60° C. at the start of process step 2, i.e. directly before addition of the methanol, and after the addition of methanol stirring is continued at this temperature for 60 min.

[0150] The polymer obtained is isocyanate-free.

Example 10a: Production of an Adhesive Formulation

[0151] 58.0 g of the polymer mixture from Example 4a are mixed in a laboratory planetary mixer from PC-Laborsystem, fitted with a beam mixer and a dissolver, with 40 g of diisoundecyl phthalate (available commercially under the name Jayflex DIUP from ExxonMobil), 4.0 g of vinyltrimethoxysilane and 96.0 g of a ground calcium carbonate coated with stearic acid and having an average particle diameter (D50%) of around 0.4 □m (available commercially under the name Omyabond 302 from Omya, Cologne (DE)) and the calcium carbonate is stirred in with the beam mixer at 200 rpm for one minute. Stirring continues thereafter for 5 min at 600 rpm with the beam mixer and 1000 rpm with the dissolver.

[0152] 2 g of 3-aminopropyltrimethoxysilane are added and stirred in for one minute at 600 rpm with the beam mixer and at 1000 rpm with the dissolver. This is followed by homogenization and bubble-free stirring under a partial vacuum (around 100 mbar) for 1 minute with the beam mixer at 600 rpm and for 1 minute at 200 rpm.

[0153] The composition obtained accordingly is dispensed into 310 ml PE cartridges and stored at 20° C. for 24 hours prior to analysis.

Example 10b: Production of an Adhesive Formulation

[0154] The procedure is as in Example 10a, replacing the polymer mixture from Example 9a with an identical amount of the polymer mixture from Example 9b.

Comparative Example 10c: Production of an Adhesive Formulation

[0155] The procedure is as in Example 9a, replacing the polymer mixture from Example 9a with an identical amount of the polymer from comparative example 9c.

Example 11: Determination of Property Profiles of the Adhesive Formulations Produced

[0156] The adhesives obtained in Examples 10a to 10c are caused to crosslink and studied by the methods described in Example 3 in terms of their skinning and their mechanical properties. The results are found in Table 3.

TABLE-US-00003 TABLE 3 Composition from Example 10a 10b 10c* (C) Skin time [min] 21 22 25 Shore A hardness 45 47 48 Tensile strength [N/mm.sup.2] 1.9 2.2 2.0 100% modulus 1.2 1.3 1.51 Elongation at break [%] 170 180 150 *not inventive

Example 12: Preparation of a Mixture of Silane-Terminated Polyethers

[0157] A 1000 ml reaction vessel with stirring, cooling and heating facilities is charged with 400.0 g (33.3 mmol) of a double-sidedly hydroxy-terminated polypropylene glycol having an average molar mass M.sub.n of 12 000 g/mol (available commercially under the name Acclaim® 12200 from Covestro AG, Leverkusen (DE)) and this initial charge is dried with stirring at 80° C. and 1 mbar for 2 h. Thereafter the vacuum is broken with nitrogen. The entirety of the subsequent reaction is carried out under an inert gas atmosphere of nitrogen.

[0158] To implement the silane termination, the dried polyether is admixed first dropwise at 80° C. with 12.9 g (80.0 mmol) of isocyanatomethylmethyldimethoxysilane and then via an Eppendorf pipette with 0.62 g of Borchi catalyst 315. Directly after the addition of catalyst, the reaction mixture warms up to 83-84° C. This is followed by stirring at a temperature of 80° C.

[0159] After 60 min at unaltered temperature, 4.0 g (20.0 mmol) of a hydroxy-terminated at both ends and having an average molar mass M.sub.n of 200 g/mol are added. This is followed by stirring for a further 60 min at 80° C. Thereafter a sample is taken from the reaction mixture and is analyzed by IR analysis for the possible presence of remaining isocyanatosilane residues. The sample is isocyanate-free.

Example 13: Production of an Adhesive Formulation and Determination of its Properties

[0160] 58.0 g of the polymer mixture from Example 12 are mixed in a laboratory planetary mixer from PC-Laborsystem, fitted with a beam mixer and a dissolver, with 40 g of diisoundecyl phthalate (available commercially under the name Jayflex DIUP from ExxonMobil), 4.0 g of vinyltrimethoxysilane and 96.0 g of a ground calcium carbonate coated with stearic acid and having an average particle diameter (D50%) of around 0.4 □m (available commercially under the name Omyabond 302 from Omya, Cologne (DE)), and the calcium carbonate is stirred in with the beam mixer at 200 rpm for one minute. Stirring continues thereafter for 5 min at 600 rpm with the beam mixer and 1000 rpm with the dissolver.

[0161] 2 g of 3-aminopropyltrimethoxysilane are added and are stirred in for one minute at 600 rpm with the beam mixer and at 1000 rpm with the dissolver. This is followed by homogenization and bubble-free stirring under a partial vacuum (around 100 mbar) for 1 minute with the beam mixer at 600 rpm and for 1 minute at 200 rpm.

[0162] The composition obtained accordingly is dispensed into 310 ml PE cartridges and stored at 20° C. for 24 hours prior to analysis.

[0163] The resulting adhesives are caused to crosslink and investigated by the methods described in Example 3 in terms of its skinning and its mechanical properties. The skin time is 14 min, the Shore A hardness 44, tensile strength 2.1 N/mm.sup.2, the 100% modulus 1.34 N/mm.sup.2 and the elongation at break 170%.

Example 14: Preparation of a Mixture of Silane-Terminated Polyethers

[0164] A 1000 ml reaction vessel with stirring, cooling and heating facilities is charged with 400.0 g (22.2 mmol) of a double-sidedly hydroxy-terminated polypropylene glycol having an average molar mass M.sub.n of 18 000 g/mol (available commercially under the name Acclaim® 18200 from Covestro AG, Leverkusen (DE)) and this initial charge is dried with stirring at 80° C. and 1 mbar for 2 h. Thereafter the vacuum is broken with nitrogen. The entirety of the subsequent reaction is carried out under an inert gas atmosphere of nitrogen.

[0165] To implement the silane termination, the dried polyether is admixed first dropwise at 80° C. with 8.6 g (53.3 mmol) of 3-isocyanatomethylmethyldimethoxysilane and then via an Eppendorf pipette with 0.62 g of Borchi catalyst 315. Directly after the addition of catalyst, the reaction mixture warms up to 82-83° C. This is followed by stirring at a temperature of 80° C.

[0166] After 60 min at unaltered temperature, 1.3 g (6.5 mmol) of a hydroxy-terminated at both ends and having an average molar mass M.sub.n of 200 g/mol (available commercially under the name Polyglycol 300 from Clariant, Basel (CH)) are added. This is followed by stirring for a further 60 min at 80° C. Thereafter a sample is taken from the reaction mixture and is analyzed by IR analysis for the possible presence of remaining isocyanatosilane residues. The sample is isocyanate-free.

Example 15: Production of an Adhesive Formulation and Determination of its Properties

[0167] 58.0 g of the polymer mixture from Example 14 are mixed in a laboratory planetary mixer from PC-Laborsystem, fitted with a beam mixer and a dissolver, with 40 g of diisoundecyl phthalate (available commercially under the name Jayflex DIUP from ExxonMobil), 4.0 g of vinyltrimethoxysilane and 96 g of a ground calcium carbonate coated with stearic acid and having an average particle diameter (D50%) of around 0.4 □m (available commercially under the name Omyabond 302 from Omya, Cologne (DE)), and the calcium carbonate is stirred in with the beam mixer at 200 rpm for one minute. Stirring continues thereafter for 5 min at 600 rpm with the beam mixer and 1000 rpm with the dissolver.

[0168] 2 g of 3-aminopropyltrimethoxysilane are added and are stirred in for one minute at 600 rpm with the beam mixer and at 1000 rpm with the dissolver. This is followed by homogenization and bubble-free stirring under a partial vacuum (around 100 mbar) for 1 minute with the beam mixer at 600 rpm and for 1 minute at 200 rpm.

[0169] The composition obtained accordingly is dispensed into 310 ml PE cartridges and stored at 20° C. for 24 hours prior to analysis.

[0170] The resulting adhesives are caused to crosslink and investigated by the methods described in Example 3 in terms of its skinning and its mechanical properties. The skin time is 20 min, the Shore A hardness 40, tensile strength 2.5 N/mm.sup.2, the 100% modulus 0.82 N/mm.sup.2 and the elongation at break 317%.