Silane group-containing branched polymer

Abstract

The present invention provides a stoichiometric ratio of at least one mole of amino-, mercapto-, or hydroxysilane per mole equivalent of isocyanate groups. (i) an isocyanate group-containing polymer having an NCO content in the range of 0.7 to 4 wt. % obtained from the reaction of at least one diisocyanate monomer with at least one polyether polyol in an NCO:OH molar ratio of at least 1.5:1; (ii) at least one amino-, mercapto-, or hydroxysilane; The present invention relates to a silane group-containing branched polymer having an average of at least 2.1 silane groups per molecule, obtained by the reaction of: (a) (b) (c) (d) (e) (f) (g) (h) (i) (i) (i) (ii) (iii) (iv) (v) (v) (vi) (vii) (v ...

Description

Technical Field

[0001] The present invention relates to polymers containing silane groups and to their use in curable compositions, especially moisture-curable adhesives, sealants or coatings.

Background Art

[0002] Polymers containing silane groups, also called silane-functional or silane-terminated polymers, are known as components of moisture-curable adhesives, sealants or coatings.

[0003] There are various known routes to polymers containing silane groups. First, there is what is called an MS polymer obtained by hydrosilylation of allyl ether-terminated polyether polyols; there is also what is called a SPUR polymer obtained from the reaction of isocyanatosilane and polyether polyol; and finally there are polymers containing silane groups from the reaction of amino- or hydroxysilane with a polymer containing isocyanate groups from the reaction of polyether polyol and diisocyanate monomer.

[0004] The latter are very interesting with regard to mechanical properties, especially good strength combined with high extensibility. Polymers containing isocyanate groups serving as starting materials for their preparation are prepared, for example, by reacting a diisocyanate monomer with a polyether diol at an NCO / OH ratio of about 2 / 1 as described in U.S. Patent No. 6,545,087 or U.S. Patent No. 9,790,315. They contain a significant amount of diisocyanate monomer and a chain-extended polymer to which two or more polyether diols are added by the diisocyanate monomer. Due to these second components, the polymers containing silane groups obtained from them have a high viscosity, and as a result, they are typically diluted with a small amount of plasticizer for easier handling at room temperature. However, compositions containing these polymers containing silane groups exhibit insufficient thermal stability after curing, especially at temperatures of 80 °C or 90 °C or above.

[0005] Polymers containing silane groups from the reaction of a polyether triol and an isocyanatosilane are also known, for example, from U.S. Patent Application Publication No. 2014 / 187705. These polymers are significantly less viscous but have considerably lower strength and extensibility, and likewise, their thermal stability after curing is unsatisfactory. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0006] Therefore, it is an object of the present invention to provide a polymer containing silane groups that enables improved thermal stability after curing, together with high strength and good extensibility. MEANS FOR SOLVING THE PROBLEM

[0007] This object is achieved by a branched polymer containing silane groups as claimed in claim 1. It is obtained from the reaction of an amino-, mercapto- or hydroxysilane with a polymer containing isocyanate groups prepared from a polyether triol, in a stoichiometric ratio of at least 1 / 1 with respect to the isocyanate groups. The polymer according to the invention containing silane groups does not contain isocyanate groups. It is branched and has on average more than 2 silane groups per molecule. It is preferably used in a curable composition which further comprises at least one further, in particular linear, polymer containing silane groups. Surprisingly, it significantly improves the thermal stability of the composition without causing any perceivable loss of strength and elongation in the composition.

[0008] In a preferred embodiment, the diisocyanate monomer is IPDI. Thus, there are polymers with a particularly low viscosity which can be easily handled even at room temperature without a large excess of NCO and subsequent removal of the monomer. They enable particularly good processability and improved thermal stability after curing.

[0009] In a more preferred embodiment, the diisocyanate monomer is 4,4'-MDI and the polymer containing isocyanate groups is produced at an NCO / OH ratio of at least 3 / 1 and with subsequent removal of the unreacted diisocyanate monomer. Such a branched polymer containing silane groups is significantly more viscous, yet still easy to handle at room temperature and, when used in a curable composition together with a linear polymer containing silane groups, enables not only improved thermal stability but also significantly improved strength without loss of elongation.

[0010] The polymer of the present invention containing a silane group is stable in storage, liquid at room temperature, and easy to handle, and enables a curable composition having excellent processability, fast curing, good elongation, high strength, and surprisingly good thermal stability. It is particularly suitable as a component of a moisture-curable sealant, adhesive or coating, especially further containing a linear silane group-containing polymer thereon.

[0011] A further aspect of the present invention is the subject matter of further independent claims. Particularly preferred embodiments of the present invention are the subject matter of the dependent claims.

Mode for Carrying Out the Invention

[0012] The present invention provides a polymer containing an isocyanate group and having an NCO content in the range of 0.7% to 4% by weight, obtained from the reaction of (i) at least one diisocyanate monomer at an NCO / OH molar ratio of at least 1.5 / 1 and at least one polyether triol having an average OH functionality in the range of 2.2 to 3 and an OH value in the range of 15 to 58 mg KOH / g, (ii) at least one amino-, mercapto-, or hydroxy silane and a branched polymer containing a silane group from the reaction thereof.

[0013] "Diisocyanate monomer" refers to an organic compound having two isocyanate groups separated by a divalent hydrocarbyl group having 4 to 15 carbon atoms.

[0014] "NCO content" refers to the content of isocyanate groups in weight%.

[0015] "Organosilane" or simply "silane" refers to an organic compound having at least one silane group.

[0016] The "alkoxysilane group" or, for short, the "silane group" refers to a silyl group having, on a silicon atom, one to three, especially two or three, hydrolyzable alkoxy groups bonded to an organic group.

[0017] "Aminosilane", "mercaptosilane" or "hydroxysilane" each refer to an organosilane having an amino, mercapto or hydroxyl group, respectively, on an organic group in addition to a silane group.

[0018] "Molecular weight" refers to the molar mass of a molecule or molecular residue (in grams per molecule). "Average molecular weight" refers to the number average molecular weight (M n ) of a polydisperse mixture of oligomer or polymer molecules or molecular acid groups. It is measured by gel permeation chromatography (GPC) relative to polystyrene as a standard.

[0019] In relation to reactive groups, the term "molar ratio" relates to the ratio of the number of molar equivalents of the corresponding reactive groups.

[0020] In each case, the dashed line in the formula represents the bond between the substituent and the corresponding molecular group.

[0021] "Plasticizer" refers to a non-volatile substance that is not chemically incorporated into the polymer during the curing process and that exerts a plasticizing effect on the cured polymer.

[0022] A substance or composition is said to be "stable in storage" or "storable" if it can be stored at room temperature for a long period, typically at least three months, up to six months or more, in a suitable container without causing any change in its coating or use properties to the extent relevant to its use.

[0023] "Room temperature" refers to a temperature of 23°C.

[0024] All industry standards and specifications described in this document relate to the valid version as of the filing date of the initial application.

[0025] The weight percentage, abbreviated as wt%, refers to the mass ratio of the components or molecules of the composition based on the total composition or the total molecule, unless otherwise specified. The terms "mass" and "weight" are used synonymously in this document.

[0026] The polymer of the present invention containing a silane group does not contain an isocyanate group.

[0027] It is particularly liquid at room temperature.

[0028] The branched polymer containing a silane group preferably has only a low content of plasticizer. It contains, in particular, less than 15 wt%, preferably less than 12 wt%, of plasticizer. Most preferably, it contains no plasticizer at all. Such polymers allow a high degree of freedom regarding how much and which plasticizers the composition should contain when used in curable compositions.

[0029] The branched polymer containing a silane group preferably has a silane group of the following formula (I): [Chemical formula] (In the formula, b is 0, 1 or 2, especially 0 or 1, R 1 is an alkyl group optionally containing an ether group and having 1 to 10 carbon atoms, R 2 is a divalent hydrocarbyl group having 1 to 12 carbon atoms optionally having a cyclic and / or aromatic moiety and optionally having one or more heteroatoms, especially an amide, carbamate, or morpholino group, and X is O, S, or NR 3 wherein R 3 is H, or a monovalent hydrocarbyl group having 1 to 20 carbon atoms optionally having a heteroatom in the form of an alkoxysilyl, ether or carboxylic acid ester group).

[0030] Preferably, R 1 is methyl or ethyl or isopropyl.

[0031] More preferably, R 1 is methyl. This kind of polymer containing a silane group is particularly highly reactive.

[0032] Similarly more preferably, R 1 is ethyl. Such a polymer containing a silane group is particularly stable in storage and is toxicologically advantageous.

[0033] Preferably, X is O or NR 3 is.

[0034] Preferably, R 3 is H, ethyl, butyl, phenyl or an aliphatic hydrocarbyl group having 6 to 20 carbon atoms optionally having an ether or carboxylic acid group.

[0035] Most preferably, X is NR 3 is, and R 3 is

Chemical formula

[0036] X = NR 3 In the case of, R 2 is preferably 1,3 - propylene, 1,3 - butylene or 1,4 - butylene (wherein the butylene may be substituted with one or two methyl groups), more preferably 1,3 - propylene.

[0037] When X = O, R 2 is preferably a divalent hydrocarbyl group having 6 to 12 carbon atoms having an amide, carbamate or morpholino, especially the formula

Chemical formula

[0038] The preferred silane group of formula (I) enables high strength combined with high extensibility.

[0039] Apart from the silane group of formula (I), the branched polymer containing a silane group preferably has no further silane groups that do not correspond to formula (I). In particular, it has no isocyanate groups directly bonded to the polyether triol by isocyanatosilane. Such silane groups bonded by isocyanatosilane reduce the strength and thermal stability after curing.

[0040] Preferably, the branched polymer containing a silane group has an average of 2.1 to 4, more preferably 2.2 to 3.5 silane groups per molecule.

[0041] Preferably, the branched polymer containing a silane group has an average molecular weight M in the range of 5000 to 30,000 g / mol, preferably 6000 to 20,000 g / mol, especially 7000 to 15,000 g / mol. n has.

[0042] The polymer containing an isocyanate group derived from the branched polymer containing a silane group preferably has an NCO content in the range of 0.8 wt% to 3.5 wt%, more preferably 1 wt% to 3 wt%, especially 1.2 wt% to 2.5 wt%.

[0043] Suitable diisocyanate monomers are commercially available aromatic or aliphatic diisocyanates, especially diphenylmethane 4,4'-diisocyanate, tolylene 2,4-diisocyanate or a mixture thereof with tolylene 2,6-diisocyanate (TDI), phenylene 1,4-diisocyanate (PDI), naphthalene 1,5-diisocyanate (NDI), hexane 1,6-diisocyanate (HDI), 2,2(4),4-tetramethylhexamethylene 1,6-diisocyanate (TMDI), cyclohexane 1,3- or 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI), perhydrodiphenylmethane 2,4'- or 4,4'-diisocyanate (HMDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, m- or p-xylylene diisocyanate (XDI), m-tetramethylxylylene diisocyanate (TMXDI), or mixtures thereof, optionally containing a few percentages of diphenylmethane 2,4'- and / or 2,2'-diisocyanate (MDI).

[0044] More preferably, the diisocyanate monomer is selected from the group consisting of MDI, TDI, HDI and IPDI.

[0045] Among these, IPDI is particularly preferred. The polymer containing a silane group thus obtained enables a composition having particularly low viscosity, particularly good processability, high extensibility, and particularly good light stability.

[0046] Among these, MDI, especially diphenylmethane 4,4'-diisocyanate (4,4'-MDI), is also particularly preferred. The polymer containing a silane group obtained using it enables a composition having particularly high strength.

[0047] Suitable polyether triols are commercially available triols that are preferably liquid at room temperature.

[0048] The polyether triol has an average OH functionality in the range of 2.2 to 3. As a result of their production, commercially available polyether triols have a specific content of monoalcohol, and as a result, their average OH functionality is typically somewhat below 3. They thus typically contain trifunctional and monofunctional components.

[0049] The repeating units present in the polyether triol are preferably 1,2-ethyleneoxy, 1,2-propyleneoxy, 1,3-propyleneoxy, 1,2-butyleneoxy or 1,4-butyleneoxy groups, especially 1,2-ethyleneoxy and / or 1,2-propyleneoxy groups.

[0050] More preferably, the repeating units present in the polyether triol are mainly or exclusively 1,2-propyleneoxy groups. More specifically, the polyether triol contains 80 wt% to 100 wt% of 1,2-propyleneoxy groups and 0 wt% to 20 wt% of 1,2-ethyleneoxy groups, based on all repeating units.

[0051] The polyether triol preferably starts from trimethylolpropane or glycerol.

[0052] The polyether triol has an OH number in the range of 15 to 58 mg KOH / g. It preferably has an OH number in the range of 20 to 40 mg KOH / g. Such a polyether triol has an average molecular weight M in the range of especially 3000 to 10,000 g / mol, preferably 4000 to 9000 g / mol. n It has.

[0053] The reaction between the diisocyanate monomer and the polyether triol is preferably carried out with the exclusion of moisture at a temperature in the range of 20 to 160 °C, especially 40 to 140 °C, optionally in the presence of a suitable catalyst.

[0054] In this reaction, the OH groups of the polyether polyol react with the isocyanate groups of the diisocyanate monomer. This also results in a reaction of the OH groups and / or isocyanate groups of the product of the reaction between the polyol and the diisocyanate monomer, giving rise to what is called a chain extension reaction. The higher the selected NCO / OH molar ratio, the lower the level of the chain extension reaction that occurs, and the lower the polydispersity of the resulting polymer. The measure of the chain extension reaction is the average molecular weight of the polymer, or the width and distribution of the peaks in GPC analysis. A further measure is the effective NCO content of the polymer excluding monomers relative to the theoretical NCO content calculated from the reaction of all OH groups with the diisocyanate monomer.

[0055] In a preferred embodiment of the present invention, the NCO / OH molar ratio in this reaction is preferably in the range of 1.6 / 1 to 2.5 / 1, more preferably in the range of 1.8 / 1 to 2.3 / 1, and particularly in the range of 1.9 / 1 to 2.2 / 1.

[0056] Such polymers containing isocyanate groups are particularly easy to prepare. It contains a certain proportion, typically about 0.5 wt% to 3.5 wt% of unreacted diisocyanate monomer, and a certain proportion of chain-extended components. As a result, its viscosity is somewhat higher.

[0057] Regarding the reaction at an NCO / OH molar ratio within the range of 1.5 / 1 to 2.5 / 1, the diisocyanate monomer is preferably TDI or IPDI, particularly IPDI. The polymers produced in this way have particularly low viscosities and are easy to handle at room temperature.

[0058] In a further preferred embodiment of the present invention, the NCO / OH molar ratio in the reaction is at least 3 / 1, preferably in the range of 3 / 1 to 20 / 1, more preferably in the range of 4 / 1 to 15 / 1, and particularly in the range of 5 / 1 to 13 / 1. After the reaction, most of the unreacted diisocyanate monomer is removed using a suitable method of separation.

[0059] Such polymers containing isocyanate groups have a particularly low content of diisocyanate monomers and a particularly low content of chain extension components.

[0060] It preferably has a diisocyanate monomer content of 0.3% by weight or less, preferably 0.25% by weight or less.

[0061] Such polymers containing isocyanate groups have a particularly low viscosity. In particular, this production process also allows the use of diisocyanate monomers, such as especially MDI, which would otherwise not be very suitable for reaction with polyether triols, since it is possible for undesirably high viscosities to occur during preparation up to the gelling point.

[0062] As a separation method, a distillation method, especially thin-film distillation or short-path distillation, preferably with the application of reduced pressure, is preferred.

[0063] A multi-stage process in which the diisocyanate monomer is removed in a short-path evaporator at a jacket temperature in the range of 120 - 200 °C and a pressure of 0.001 - 0.5 mbar is particularly preferred.

[0064] In the case of preferably 4,4'-MDI, distillative removal is a special challenge. For example, it is necessary to ensure that the condensate does not solidify and block the system. It is preferred to operate at a jacket temperature in the range of 160 - 200 °C, at 0.001 - 0.5 mbar, and to condense the removed diisocyanate monomer at a temperature in the range of 40 - 60 °C.

[0065] It is preferred to react the diisocyanate monomer with the polyether polyol and then remove most of the diisocyanate monomer remaining in the reaction mixture without the use of a solvent or azeotropic agent.

[0066] Preferably, the diisocyanate monomer removed after the reaction is subsequently reused, i.e., reused again for the preparation of a polymer containing isocyanate groups.

[0067] For the subsequent removal of most of the diisocyanate monomer using a suitable method of reaction and separation at an NCO / OH molar ratio of at least 3 / 1, the diisocyanate monomer is preferably IPDI or MDI.

[0068] For this purpose, MDI, especially 4,4'-MDI, is very particularly preferred. Polymers containing silane groups from the reaction of polyether triol and 4,4'-MDI enable particularly high strength combined with high thermal stability. However, their preparation is also a special challenge. In the conventional route, such polymers containing isocyanate groups typically become very viscous, so they are difficult to handle without dilution with large amounts of plasticizer or solvent. Such polymers often gel already during preparation.

[0069] Polymers containing isocyanate groups are very stable in storage by excluding moisture.

[0070] It is reacted with at least one amino-, mercapto- or hydroxysilane in a stoichiometric ratio of at least 1 mole of amino-, mercapto- or hydroxysilane per mole equivalent of isocyanate groups, which gives the branched polymer of the invention containing silane groups.

[0071] The amino-, mercapto- or hydroxysilane for reaction with the polymer containing isocyanate groups is preferably a silane of formula (II)

Chemical formula

[0072] Preferred silanes of formula (II) are selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 4-aminobutyltrimethoxysilane, 4-amino-3-methylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, N-ethyl-3-amino-(2-methylpropyl)trimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, diethyl N-(3-trimethoxysilylpropyl)aminosuccinate, diethyl N-(3-dimethoxymethylsilylpropyl)aminosuccinate, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, N-(3-trimethoxysilylpropyl)-2-hydroxypropanamide, N-(3-trimethoxysilylpropyl)-4-hydroxypentanamide, N-(3-trimethoxysilylpropyl)-4-hydroxyoctanamide, N-(3-trimethoxysilylpropyl)-5-hydroxydecanoamide, N-(3-trimethoxysilylpropyl)-2-hydroxypropylcarbamate, 2-morpholino-4(5)-(2-trimethoxysilylethyl)cyclohexan-1-ol, 2-morpholino-4(5)-(2-trimethoxysilylethyl)cyclohexan-1-ol, 1-morpholino-3-(3-(triethoxysilyl)propoxy)propan-2-ol, and the corresponding analogs having an ethoxy group instead of a methoxy group on silicon.

[0073] Particularly preferred silanes of formula (II) are diethyl N-(3-trimethoxysilylpropyl)aminosuccinate, diethyl N-(3-triethoxysilylpropyl)aminosuccinate, diethyl N-(3-dimethoxymethylsilylpropyl)aminosuccinate, diethyl N-(3-diethoxymethylsilylpropyl)aminosuccinate, N-(3-trimethoxysilylpropyl)-2-hydroxypropanamide, N-(3-triethoxysilylpropyl)-2-hydroxypropanamide, N-(3-dimethoxymethylsilylpropyl)-2-hydroxypropanamide or N-(3-diethoxymethylsilylpropyl)-2-hydroxypropanamide.

[0074] Very particularly preferred silanes of formula (II) are diethyl N-(3-trimethoxysilylpropyl)aminosuccinate, diethyl N-(3-triethoxysilylpropyl)aminosuccinate, diethyl N-(3-dimethoxymethylsilylpropyl)aminosuccinate or diethyl N-(3-diethoxymethylsilylpropyl)aminosuccinate.

[0075] Amino-, mercapto- or hydroxy-silanes are reacted with a polymer containing isocyanate groups in a stoichiometric ratio of at least 1 mole of amino-, mercapto- or hydroxy-silane per mole equivalent of isocyanate groups.

[0076] A stoichiometry of amino-, mercapto- or hydroxy-silane in the range of 1 to 1.3, preferably 1 to 1.2, especially 1 to 1.1 moles per mole equivalent of isocyanate groups is preferred.

[0077] The reaction is carried out at a temperature in the range of 20 to 160 °C, especially 60 to 120 °C. Catalysts, especially tertiary amines or metal compounds, especially bismuth(III), zinc(II), zirconium(IV) or tin(II) compounds or organotin(IV) compounds, are optionally used here.

[0078] Particularly preferred branched polymers containing silane groups are derived from IPDI as the diisocyanate monomer. It thus has, inter alia, the silane groups of formula (Ia) or (Ib) [Chemical formula] (wherein R 1 , R 2 , X, and b are as defined previously) Such polymers enable high extensibility and particularly high light stability, combined with good thermal stability.

[0079] It is preferably prepared at an NCO / OH molar ratio in the range of 1.5 / 1 to 2.5 / 1 without subsequent removal of the diisocyanate monomer, or at an NCO / OH ratio of at least 3 / 1 and with subsequent removal of most of the diisocyanate monomer using a suitable method of separation. More preferably, it is prepared at an NCO / OH molar ratio in the range of 1.5 / 1 to 2.5 / 1 without subsequent removal of the diisocyanate monomer.

[0080] Another particularly preferred branched polymer containing silane groups is derived from 4,4'-MDI as the diisocyanate monomer. It thus has, inter alia, the silane groups of formula (Ic) [Chemical formula] (wherein R 1 , R 2 , X, and b are as defined previously) Such polymers enable compositions having particularly high strength and good thermal stability.

[0081] It is preferably prepared at an NCO / OH molar ratio of at least 3 / 1 and with subsequent removal of most of the diisocyanate monomer using a suitable method of separation.

[0082] The branched polymer containing a silane group excludes moisture and is stable in storage. When it comes into contact with moisture, the silane group undergoes hydrolysis. This results in the formation of silanol groups (Si-OH groups) and then, through subsequent condensation reactions, siloxane groups (Si-O-Si groups). As a result of these reactions, the polymer cures to give a cross-linked plastic. The moisture for curing can be derived from air (the humidity of the air) or the polymer can come into contact with a water-containing component, for example, by painting, spraying or mixing. During curing, the silanol groups can condense, for example, with the hydroxyl groups of the substrate on which the polymer is applied, and as a result, an additional improvement in adhesion to the substrate is possible during cross-linking.

[0083] The present invention further provides a method for preparing a branched polymer containing a silane group, characterized in that: (a) reacting at least one diisocyanate monomer with at least one polyether triol having an average OH functionality in the range of 2.2 to 3 and an OH value in the range of 15 to 58 mg KOH / g at an NCO / OH molar ratio of at least 1.5 / 1; (b) then optionally removing most of the unreacted diisocyanate monomer using a suitable separation method, especially when an NCO / OH molar ratio of at least 3 / 1 is present; and (c) then reacting the resulting polymer containing isocyanate groups with at least one amino-, mercapto-, or hydroxy-silane in a stoichiometric ratio of at least 1 mole of amino-, mercapto-, or hydroxy-silane per mole equivalent of isocyanate groups.

[0084] In a preferred embodiment of the present invention, at least one polyether diol is present in step (a) in addition to the polyether triol. This results in the in-situ formation of a mixture of the branched polymer of the invention containing a silane group and a linear polymer not of the invention containing a silane group.

[0085] The weight ratio between the polyether triol and the polyether diol is here preferably in the range of 10 / 90 to 70 / 30, especially 15 / 85 to 60 / 40.

[0086] Suitable polyether diols for this purpose have an OH number especially in the range of 5 to 40 mg KOH / g, preferably 6 to 20 mg KOH / g, especially 7 to 15 mg KOH / g.

[0087] It preferably contains, based on its repeating units, 80% to 100% by weight of 1,2 - propyleneoxy groups and 0% to 20% by weight of 1,2 - ethyleneoxy groups.

[0088] Such linear polymers containing silane groups enable compositions with particularly high extensibility and elasticity.

[0089] The present invention further provides a reaction product from the method of the present invention.

[0090] The present invention further provides a curable composition comprising a branched polymer of the present invention containing silane groups and at least one further component selected from the group consisting of a catalyst, a cross - linking agent, an adhesion promoter, a desiccant, a plasticizer, and a filler.

[0091] Suitable catalysts are metal catalysts and / or nitrogen compounds that accelerate the cross - linking of polymers containing silane groups.

[0092] Suitable metal catalysts are especially titanium, zirconium, aluminum, or tin, especially organotin compounds, organic titanates, organic zirconates or organic aluminates, and these compounds especially have an alkoxy group, an aminoalkoxy group, a sulfonate group, a carboxyl group, a 1,3 - diketonate group, a 1,3 - ketoester group, a dialkyl phosphate group or a dialkyl pyrophosphate group.

[0093] Particularly preferred organotin compounds are dialkyltin oxides, dialkyltin dichlorides, dialkyltin dicarboxylates, and dialkyltin diketonates, especially dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diacetylacetonate, dioctyltin oxide, dioctyltin dichloride, dioctyltin diacetate, dioctyltin dilaurate or dioctyltin diacetylacetonate, or alkyltin thioesters.

[0094] Particularly preferred organotitanates are bis(ethylacetoacetato)diisobutoxytitanium(IV), bis(ethylacetoacetato)diisopropoxytitanium(IV), bis(acetylacetonato)diisopropoxytitanium(IV), bis(acetylacetonato)diisobutoxytitanium(IV), tris(oxyethyl)amine isopropoxytitanium(IV), bis[tris(oxyethyl)amine]diisopropoxytitanium(IV), bis(2-ethylhexane-1,3-dioxy)titanium(IV), tris[2-((2-aminoethyl)amino)ethoxy]ethoxytitanium(IV), bis(neopentyl(diallyl)oxy)-diethoxytitanium(IV), titanium(IV) tetrabutoxide, tetra(2-ethylhexyloxy)titanate, tetra(isopropoxy)titanate or polybutyl titanate. Commercially available products Tyzor® AA, GBA, GBO, AA-75, AA-65, AA-105, DC, BEAT, BTP, TE, TnBT, KTM, TOT, TPT or IBAY (all from Dorf Ketal); Tytan PBT, TET, X85, TAA, ET, S2, S4 or S6 (all from Borica Company Ltd.) and Ken-React® KR® TTS, 7, 9QS, 12, 26S, 33DS, 38S, 39DS, 44, 134S, 138S, 133DS, 158FS or LICA® 44 (all from Kenrich Petrochemicals) are particularly suitable.

[0095] Particularly preferred organozirconates are the commercially available products Ken-React® NZ® 38J, KZ® TPPJ, KZ® TPP, NZ® 01, 09, 12, 38, 44 or 97 (all manufactured by Kenrich Petrochemicals) or Snapcure® 3020, 3030, 1020 (all manufactured by Johnson Matthey & Brandenberger).

[0096] Particularly preferred organoaluminates are the commercially available product K-Kat 5218 (manufactured by King Industries).

[0097] Nitrogen compounds suitable as catalysts include, in particular, N-ethyldiisopropylamine, N,N,N',N'-tetramethylalkylenediamine, polyoxyalkyleneamine, amines such as 1,4-diazabicyclo[2.2.2]octane; in particular, aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-N'-[3-(trimethoxysilyl)propyl]ethylenediamine or their analogs with ethoxy groups instead of methoxy groups on silicon, etc. aminosilanes; in particular, cyclic amidines such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 6-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene; in particular, guanidines such as tetramethylguanidine, 2-guanidinobenzimidazole, acetylacetone guanidine, 1,3-di-o-tolylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, or reaction products of carbodiimide with amines such as polyetheramine or aminosilaneamine; or imidazoles such as N-(3-trimethoxysilylpropyl)-4,5-dihydroimidazole or N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole, in particular.

[0098] Combinations of different catalysts, especially combinations of at least one metal catalyst and at least one nitrogen compound, are also suitable.

[0099] Preferred catalysts are organotin compounds, organic titanates, amines, especially aminosilanes, amidines, guanidines or imidazoles.

[0100] Suitable adhesion promoters and / or crosslinking agents are, inter alia, aminosilanes, mercaptosilanes, epoxysilanes, (meth)acrylosilanes, anhydridosilanes, carbamatosilanes, alkylsilanes or iminosilanes, or oligomeric forms of these silanes, or adducts of primary amines with epoxysilanes or (meth)acrylosilanes or anhydrosilanes. 3-Glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane, N-(2-aminoethyl)-N’-[3-(trimethoxysilyl)propyl]ethylenediamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane or the corresponding silanes having ethoxysilane groups instead of methoxysilane groups on silicon, or oligomeric forms of these silanes are particularly preferred.

[0101] Particularly preferred desiccants are tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, organosilanes having a functional group in the α-position of the silane group, in particular N-(methyldimethoxysilylmethyl)-O-methylcarbamate or (methacryloxymethyl)silane, methoxymethylsilane, orthoformic acid esters, and also calcium oxide or molecular sieves. Vinyltrimethoxysilane or vinyltriethoxysilane is preferred. When the branched polymer containing a silane group has a methoxysilane group, vinyltrimethoxysilane is preferred, while when the branched polymer containing a silane group has an ethoxysilane group, vinyltriethoxysilane is preferred.

[0102] Suitable plasticizers include, inter alia, phthalates, especially diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di(2-propylheptyl) phthalate (DPHP), hydrogenated phthalates, namely cyclohexane-1,2-dicarboxylates, especially hydrogenated diisononyl phthalate, namely diisononyl cyclohexane-1,2-dicarboxylate (DINCH), terephthalates, especially bis(2-ethylhexyl) terephthalate (DOTP) or diisononyl terephthalate (DINT), hydrogenated terephthalates, namely cyclohexane-1,4-dicarboxylates, especially hydrogenated bis(2-ethylhexyl) terephthalate, namely bis(2-ethylhexyl) cyclohexane-1,4-dicarboxylate, or hydrogenated diisononyl terephthalate, namely diisononyl cyclohexane-1,4-dicarboxylate, isophthalates, trimellitates, adipates, especially dioctyl adipate, azelates, sebacates, benzoates and other carboxylic acid esters, polyols, especially polyether polyols or polyester polyols, glycol ethers, glycol esters, especially in the form of acetate groups, polyether monools or polyols having blocked hydroxyl groups, organic phosphoric acid esters or sulfonic acid esters, polybutene or natural fats or oils, also called "biodiesel", especially fatty acid methyl or ethyl esters, or epoxidized soybean oil or linseed oil.

[0103] Suitable fillers include, inter alia, fatty acids, especially stearate-coated, ground or precipitated calcium carbonate, barite, quartz powder, silica sand, dolomite, wollastonite, calcined kaolin, mica or talc, etc., layered silicates, zeolites, aluminum hydroxide, magnesium hydroxide, finely divided silica from a thermal decomposition process, etc., silica, cement, gypsum, fly ash, industrially produced carbon black, graphite, metal powders, such as aluminum, copper, iron, silver or steel, PVC powder or hollow beads. Precipitated, fatty acid-coated calcium carbonate and / or carbon black are preferred.

[0104] Even more preferred constituents are, inter alia, the following auxiliaries and additives: - oligomers or polymers containing a silane group; - solvents; - fibers, in particular polymer fibers such as glass fibers, carbon fibers, metal fibers, ceramic fibers, polyamide fibers or polyethylene fibers, or natural fibers such as wood, cellulose, hemp or sisal; - nanofibers such as graphene or carbon nanotubes; - dyes; - inorganic or organic pigments, in particular titanium dioxide, chromium oxide or iron oxide; - rheology modifiers, in particular thickeners, in particular layered silicates such as bentonite, derivatives of castor oil, hydrogenated castor oil, polyamides, polyamide waxes, polyurethanes, urea compounds, fumed silica, cellulose ethers or hydrophobically modified polyoxyethylene; - stabilizers against oxidation, heat, light or UV radiation; - natural resins, fats or oils such as rosin, shellac, linseed oil, castor oil or soybean oil; - non-reactive polymers, in particular homopolymers or copolymers of unsaturated monomers from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth) acrylates, in particular polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene / vinyl acetate copolymer (EVA) or atactic poly-α-olefin (APAO); - flame retardants, in particular the fillers already mentioned, aluminum hydroxide or magnesium hydroxide, or organic phosphoric esters; - additives, in particular wetting agents, leveling agents, defoamers, degassing agents, stabilizers against oxidation, heat, light or UV radiation, or biocides are.

[0105] It may be advisable for certain constituents to undergo chemical or physical drying before being incorporated into the composition.

[0106] The curable composition preferably contains 5% to 80% by weight, more preferably 10% to 70% by weight, especially 20% to 60% by weight, of a polymer containing a silane group.

[0107] In a preferred embodiment of the present invention, the curable composition contains at least one further polymer not according to the invention containing a silane group.

[0108] In particular, this further polymer containing a silane group is linear. It preferably has on average 1.7 to 2, more preferably 1.8 to 2, especially 1.9 to 2, silane groups per molecule.

[0109] The weight ratio here between the branched polymer of the invention containing a silane group and the further polymer containing a silane group is preferably in the range of 10 / 90 to 70 / 30, especially 15 / 85 to 60 / 40.

[0110] The further polymer containing a silane group is preferably - a polymer containing a silane group derived from a polymer containing an isocyanate group from the reaction of a diisocyanate monomer and polyethylene glycol with an NCO / OH molar ratio of at least 1.5 / 1; - especially a polyether containing a silane group obtained from the reaction of an allyl group-containing polyether and a hydrosilane, optionally with chain extension, using a diisocyanate; - especially a polyether containing a silane group obtained from the copolymerization of an alkylene oxide and an epoxy silane, optionally with chain extension, using a diisocyanate; - a polyether containing a silane group obtained from the reaction of a polyether polyol, especially a diol, and an isocyanatosilane, optionally with chain extension, using a diisocyanate selected from the group consisting of.

[0111] The branched polymer of the present invention containing a silane group improves, here, the thermal stability of the composition and optionally the strength and / or elongation.

[0112] As a further polymer containing a silane group, those derived from a polymer containing an isocyanate group from the reaction of a diisocyanate monomer and a polyether diol at an NCO / OH molar ratio of at least 1.5 / 1 are preferred.

[0113] Suitable polyether diols for this purpose have an OH value in the range of 5 to 40 mg KOH / g, preferably 6 to 20 mg KOH / g, especially 7 to 15 mg KOH / g. In particular, it has an average molecular weight M in the range of 3500 to 20,000 g / mol, preferably 5000 to 18,000 g / mol, especially 7500 to 16,000 g / mol. n Such polymers enable compositions having particularly high elongation and elasticity.

[0114] Such a mixture of the branched polymer of the present invention and a non-inventive polymer can also be prepared, in particular, such that the diisocyanate monomer is mixed with a mixture of at least one polyether triol and at least one polyether diol as described at an NCO / OH molar ratio of at least 1.5 / 1 to form a polymer containing an isocyanate group, which is then reacted with at least one amino, mercapto or hydroxy silane as described.

[0115] The curable composition is produced, inter alia, by excluding moisture and stored at ambient temperature in a moisture-proof container. Suitable moisture-proof containers consist, inter alia, of optionally coated metal and / or plastic and are, inter alia, drums, transport boxes, hob boxes, buckets, canisters, cans, bags, tubular bags, cartridges or tubes.

[0116] The curable composition can be in the form of a one-component composition or in the form of a two-component composition.

[0117] The "one-component" composition refers to a composition in which all the constituent components of the composition are mixed and stored together in the same container and can be cured by moisture.

[0118] The "two-component" composition refers to a composition in which the constituent components of the composition are present in two different components stored in separate containers. The two components are not mixed with each other until immediately before or during the application of the composition, and as soon as they are mixed, the mixed composition cures in a state where the curing proceeds or is completed only by the action of moisture.

[0119] The curable composition is preferably a one-component composition. Assuming suitable packaging and storage, it is typically stable in storage for several months, up to one year, or more.

[0120] When the curable composition is applied, the silane groups present come into contact with moisture, which initiates the curing process. The curing proceeds at various rates depending on the temperature, the nature of the contact, the amount of moisture, and the presence of any catalyst. In the case of curing using air humidity, a skin first forms on the surface of the composition. What is called the skin time is a measure of the curing rate.

[0121] This results in the formation of a cured composition.

[0122] In the case of a one-component composition, it is applied as it is and then begins to cure under the influence of moisture or water. For accelerating the curing, an accelerator component containing or releasing water and / or a catalyst and / or a curing agent can be incorporated into the composition at the time of application, or the composition can be brought into contact with such an accelerator component after its application.

[0123] The curable composition is preferably applied at ambient temperature, especially within the range of about -10 to 50 °C, preferably -5 °C to 45 °C, especially within the range of 0 to 40 °C.

[0124] The curing preferably occurs at ambient temperature as well.

[0125] In the hardened state, the present composition has significantly elastic properties, in particular high strength and high elongation, good thermal stability, and good adhesion properties on various substrates. As a result, it is suitable for numerous uses, especially as a sealant, adhesive, coating, covering or paint for construction or industrial applications, for example as a joint sealant, veneer adhesive, secondary adhesive, finishing adhesive, or body sealant, seam sealant or cavity sealant, as a floor covering, floor coating, balcony coating, roof coating or multi-storey car park coating.

[0126] It is preferred to use the curable composition as an elastic adhesive or elastic sealant or elastic coating.

[0127] The curable composition can be formulated to have a paste-like consistency with structurally viscous properties. This type of composition can have an essentially round or triangular cross-section, for example in the form of a bead, and is applied using a suitable device, for example from a commercially available cartridge or drum or hob box.

[0128] The curable composition can also be formulated such that it is fluid and "self-leveling" or slightly thixotropic and can be poured out for application. As a coating, it can then be distributed over an area using, for example, a roller, a slip bar, a spiked applicator or a trowel to give the desired layer thickness. In one operation, layer thicknesses in the range from 0.5 to 3 mm, especially from 1 to 2.5 mm, are typically applied.

[0129] Suitable substrates for bonding or sealing or coating are, inter alia, - natural stones such as glass, glass ceramic, screen-printed ceramic, concrete, mortar, cement screed, fibre cement, especially fibre cement boards, bricks, tiles, plaster, especially plaster boards or anhydrite screed, or granite or marble; - Metals or alloys such as aluminum, copper, iron, steel, non-ferrous metals, etc., including surface finishing metals or alloys such as zinc-plated or chromium-plated metals; - Plastics, especially rigid or flexible PVC, polycarbonate (PC), polyamide (PA), polyester, PMMA, ABS, SAN, epoxy resin, phenolic resin, PUR, POM, TPO, PE, PP, EPM or EPDM (where the surface of the plastic is optionally subjected to plasma, corona or flame treatment); - Paints or varnishes, especially automotive topcoats; - Repair or leveling compounds based on PCC (polymer-modified cement mortar) or ECC (epoxy resin-modified cement mortar); - Asphalt or bitumen; - Resin-bonded wood-based materials, resin-fabric composites or other so-called polymer composites such as leather, fabric, paper, wood, phenolic resin, melamine resin or epoxy resin; - Insulating foams made especially of EPS, XPS, PUR, PIR, rock wool, glass wool or expanded glass is.

[0130] If necessary, the substrate can be pretreated before application, especially by physical and / or chemical cleaning methods or by applying an activator or primer.

[0131] It is possible to join or seal two identical substrates or two different substrates.

[0132] After joining or sealing two substrates, a joined or sealed article is obtained. This article can be a construction structure or a part thereof, especially a ground or underground construction structure, bridge, roof, staircase or facade, or it can be an industrial product or a consumer product, especially a window, pipe, household appliance or a means of transportation such as a car, bus, truck, railway vehicle, ship, aircraft or helicopter, or an installable component thereof.

[0133] The present invention further provides a cured composition obtained from the curable composition after contact with moisture therewith.

[0134] The composition of the present invention excludes moisture, is stable in storage, and can be easily processed. It cures rapidly and, after curing, has high strength combined with good elongation, good adhesion properties, and surprisingly good thermal stability.

Examples

[0135] Examples are presented below in this specification for the purpose of further clarifying the described invention. The present invention is, of course, not limited to these described examples.

[0136] “Standard climatic conditions” (“SCC”) refers to a temperature of 23 ± 1 °C and a relative air humidity of 50 ± 5%.

[0137] The chemicals used were from Sigma - Aldrich unless otherwise specified.

[0138] Diisodecyl phthalate was used in the form of Palatinol® 10 - P (manufactured by BASF).

[0139] Viscosity was measured using a Rheotec RC30 cone - plate viscometer at a constant temperature (cone diameter 25 mm, cone angle 1°, cone tip - plate distance 0.05 mm, shear rate 10 s -1 ).

[0140] The diisocyanate monomer content was measured by HPLC (detection by photodiode array; mobile phase: 0.04 M sodium acetate / acetonitrile) after prior derivatization with N - propyl - 4 - nitrobenzylamine.

[0141] Preparation of Isocyanate Group-Containing Polymers Using Polyether Triol Polymer T - 1: (NCO / OH = 2.1 / 1) 190.0 g of ethylene oxide-terminated polyoxypropylene triol (OH value 28 mg KOH / g, Desmophen® 5031 BT, manufactured by Covestro), 27.8 g of diisodecyl phthalate, 22.2 g of IPDI (1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, Vestanat® IPDI, manufactured by Evonik), and 0.12 g of dibutyltin dilaurate were reacted at 90 °C by a known method to give a polymer having an NCO content of 1.75 wt% and a viscosity of 31 Pa·s at 20 °C.

[0142] Polymer T-2: 780.0 g of ethylene oxide-terminated polyoxypropylene triol (OH value 28 mg KOH / g, Desmophen® 5031 BT, manufactured by Covestro) and 220 g of IPDI (1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, Vestanat® IPDI, manufactured by Evonik) were reacted at 80 °C by a known method in the presence of 0.01 g of dibutyltin dilaurate to give a polymer having an NCO content of 6.4 wt%, a viscosity of 4.1 Pa·s at 20 °C, and an IPDI monomer content of about 12 wt%.

[0143] Most of the volatile constituents, especially the IPDI monomer, were then removed by distillation in a short-path evaporator (jacket temperature 160 °C, pressure 0.1 - 0.005 mbar). The polymer thus obtained had an NCO content of 1.9 wt%, a viscosity of 8.2 Pa·s at 20 °C, and an IPDI monomer content of 0.02 wt%.

[0144] Polymer T-3: 725.0 g of propylene oxide-terminated polyoxypropylene triol (OH value 28 mg KOH / g, Desmophen® 5031 BT, manufactured by Covestro) and 275 g of diphenylmethane 4,4'-diisocyanate (Desmodur® 44 MC L, manufactured by Covestro) were reacted at 80 °C by a known method to give a polymer having an NCO content of 7.6% by weight, a viscosity of 6.5 Pa·s at 20 °C, and a diphenylmethane 4,4'-diisocyanate monomer content of approximately 20% by weight.

[0145] Most of the volatile components, in particular the diphenylmethane 4,4'-diisocyanate monomer, were then removed by distillation in a short-path evaporator (jacket temperature 180 °C, pressure 0.1 - 0.005 mbar, condensation temperature 47 °C). The polymer thus obtained had an NCO content of 1.7% by weight, a viscosity of 19 Pa·s at 20 °C, and a diphenylmethane 4,4'-diisocyanate monomer content of 0.04% by weight.

[0146] Polymer T-4: (NCO / OH = 2.1 / 1) 190.0 g of ethylene oxide-terminated polyoxypropylene triol (OH value 28 mg KOH / g, Desmophen® 5031 BT, manufactured by Covestro) and 25.0 g of diphenylmethane 4,4'-diisocyanate (Desmodur® 44 MC L, manufactured by Covestro) were reacted at 80 °C by a known method. The reaction mixture underwent gelation during the reaction and as a result was unsuitable for further use.

[0147] Preparation of Isocyanate Group-Containing Polymers Using Polyether Diol Polymer L-1: (NCO / OH = 2.1 / 1) 1000.0 g of polyoxypropylene diol (OH value 10 mg KOH / g, Acclaim® 12200N, manufactured by Covestro), 122.8 g of diisodecyl phthalate, 41.6 g of IPDI (1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, Vestanat® IPDI, manufactured by Evonik), and 0.12 g of dibutyltin dilaurate were reacted at 90 °C by a known method to yield a polymer having an NCO content of 0.63 wt%, a viscosity of 31 Pa·s at 20 °C, and an IPDI monomer content of about 0.5 wt%.

[0148] Silane of Formula (II) Used Diethyl N-(3-trimethoxysilylpropyl)aminosuccinate (351.5 g / mol), obtained from the reaction of 3-aminopropyltrimethoxysilane and diethyl maleate in a molar ratio of about 1 / 1

[0149] Preparation of Silane Group-Containing Polymers Polymer ST-1: (branched, of the invention) To an initial charge of 240.0 g of Polymer T-1 prepared as described above, 36.2 g of Silane A-1 was added under a nitrogen atmosphere from which moisture had been excluded, and the mixture was stirred at 60 °C until the isocyanate groups could no longer be detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored with moisture excluded. It contained 10 wt% plasticizer (diisodecyl phthalate), was colorless and transparent, and had a viscosity of 97 Pa·s at 20 °C the day after preparation.

[0150] Polymer ST-2: (branched, of the invention) To an initial charge of 221.0 g of Polymer T-2 prepared as described above, 36.2 g of Silane A-1 was added under a nitrogen atmosphere from which moisture had been excluded, and the mixture was stirred at 60 °C until the isocyanate groups could no longer be detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored with moisture excluded. It was colorless and transparent and had a viscosity of 70 Pa·s at 20 °C the day after preparation.

[0151] Polymer ST-3: (branched, of the invention) To an initial charge of 247.0 g of Polymer T-3 prepared as described above, 36.2 g of silane A-1 was added under a nitrogen atmosphere from which moisture had been excluded, and the mixture was stirred at 60 °C until the isocyanate groups could no longer be detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored after excluding moisture. It was colorless and transparent and had a viscosity of 357 Pa·s at 20 °C the day after preparation.

[0152] Polymer SL-1: (linear, not of the invention) To an initial charge of 333.3 g of Polymer L-1 prepared as described above, 18.1 g of silane A-1 was added under a nitrogen atmosphere from which moisture had been excluded, and the mixture was stirred at 60 °C until the isocyanate groups could no longer be detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored after excluding moisture. It contained 10 wt% plasticizer (diisodecyl phthalate), was colorless and transparent, and had a viscosity of 99 Pa·s at 20 °C the day after preparation.

[0153] Polymer SPUR-1: (branched, for comparison) 190.0 g of Desmophen® 5031 BT and 19.5 g of 3-isocyanatopropyltrimethoxysilane were reacted at 80 °C by a known method to give a polymer containing silane groups. The resulting polymer was cooled to room temperature and stored after excluding moisture. It was colorless and transparent and had a viscosity of 5 Pa·s at 20 °C the day after preparation

[0154] Moisture-Curable Composition Compositions Z1 to Z9: For each composition, the raw materials specified in Tables 1 to 2 were mixed at the specified amounts (in parts by weight) using a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) at 3000 rpm for 1 minute after excluding moisture, and stored after excluding moisture.

[0155] The composition was tested as follows: As a measure of storage stability, the viscosity was measured after storage in a closed aluminum tube with moisture excluded, after 1 day at room temperature (1d RT) and after 7 days at 60 °C in an air-circulating oven (7d 60 °C).

[0156] As a measure of open time, the skin time (HBZ) was measured. For this purpose, 2 or 3 grams of the composition was applied to cardboard with a layer thickness of approximately 2 mm, and the period under standard climatic conditions was measured on an LDPE pipette used to gently tap the surface of the composition until no further residue remained.

[0157] As a measure of hardness and thermal stability, the Shore A hardness was measured in accordance with DIN 53505 for test specimens cured for 7 days under standard climatic conditions (7d SCC), or for test specimens stored for 7 days under standard climatic conditions and then for a specified period at a specified temperature in an air-circulating oven at 80 °C, 90 °C or 100 °C.

[0158] For the measurement of mechanical properties, the composition was applied to silicone-coated release paper to obtain a film with a thickness of 2 mm, which was stored for 14 days under standard climatic conditions. Thereafter, two or three dumbbells with a test piece length of 30 mm and a test piece width of 4 mm and a length of 75 mm were punched out from the film, and these were tested in accordance with DIN 53504 at a strain rate of 200 mm / min to measure the tensile strength (breaking load), elongation at break, and 5% modulus of elasticity (at 0.5 - 5% elongation).

[0159] The results are reported in Tables 1 - 2.

[0160] The comparative examples are identified by (Ref.).

[0161]

Table 1

[0162]

Table 2

[0163] From Tables 1 and 2, it can be understood that the compositions Z2 to Z4 and Z6 to Z9 of the present invention have good to very good thermal stability, while on the other hand, the comparative compositions Z1 and Z5 have insufficient thermal stability. After storage at 90 °C for 14 days and 100 °C for 7 days, their Shore A hardness test specimens were destroyed to such an extent that measurement was no longer possible. This disclosure includes the following aspects of the invention: <Aspect 1> At a stoichiometric ratio of at least 1 mol of amino-, mercapto-, or hydroxy silane per 1 mol equivalent of isocyanate groups (i) A polymer containing isocyanate groups and having an NCO content in the range of 0.7 wt% to 4 wt%, obtained from the reaction of at least one diisocyanate monomer with at least one polyether triol having an average OH functionality in the range of 2.2 to 3 and an OH value in the range of 15 to 58 mg KOH / g at an NCO / OH molar ratio of at least 1.5 / 1, and (ii) At least one amino-, mercapto-, or hydroxy silane A branched polymer containing silane groups resulting from the reaction. <Aspect 2> A polymer containing silane groups according to Aspect 1, characterized by having silane groups of the following formula (I):

Chemical formula

Claims

1. in a stoichiometric ratio of at least 1 mole of amino-, mercapto-, or hydroxysilane per mole equivalent of isocyanate groups (i) a reaction of at least one diisocyanate monomer at an NCO / OH molar ratio of at least 1.5 / 1 with at least one polyether triol having an average OH functionality in the range of 2.2 to 3 and an OH value in the range of 15 to 58 mg KOH / g, without using a polyol other than the at least one polyether triol, to obtain a polymer containing isocyanate groups and having an NCO content in the range of 0.7% to 4% by weight, and (ii) at least one amino-, mercapto-, or hydroxysilane a branched polymer containing silane groups resulting from the reaction of a polymer containing silane groups, characterized by having a silane group of the following formula (I): 【Chemical 1】 (wherein b is 0, 1, or 2, especially 0 or 1, R 1 is an alkyl group optionally containing an ether group and having 1 to 10 carbon atoms, R 2 is a divalent hydrocarbyl group having 1 to 12 carbon atoms optionally having a cyclic and / or aromatic moiety and optionally having one or more heteroatoms, especially an amide, carbamate, or morpholino group, and X is NR 3, where R 3 is 【Chem.】 (wherein R 4 is methyl or ethyl)).

2. The polymer containing silane groups according to claim 1, characterized by having an average of 2.1 to 4, preferably 2.2 to 3.5, silane groups per molecule.

3. The polymer containing silane groups according to claim 1 or 2, characterized in that the diisocyanate monomer is 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane.

4. The polymer containing silane groups according to claim 1 or 2, characterized in that the diisocyanate monomer is diphenylmethane 4,4-diisocyanate.

5. The polymer containing silane groups according to any one of claims 1 to 4, characterized in that the polyether triol contains 80% to 100% by weight of 1,2-propyleneoxy groups and 0% to 20% by weight of 1,2-ethyleneoxy groups based on all repeating units.

6. The polymer containing a silane group according to any one of claims 1 to 5, wherein the NCO / OH molar ratio in the reaction is in the range of 1.6 / 1 to 2.5 / 1.

7. The polymer containing a silane group according to any one of claims 1 to 5, wherein the NCO / OH molar ratio in the reaction is at least 3 / 1.

8. A method for preparing a polymer containing a silane group according to any one of claims 1 to 7, characterized by the following: (a) Reacting at least one diisocyanate monomer with at least one polyether triol having an average OH functionality in the range of 2.2 to 3 and an OH value in the range of 15 to 58 mg KOH / g at an NCO / OH molar ratio of at least 1.5 / 1, wherein in this reaction, no polyol other than the at least one polyether triol is used. (b) Then, most of the unreacted diisocyanate monomer is optionally removed using a suitable separation method, and (c) Then, the resulting polymer containing isocyanate groups is reacted with at least one amino-, mercapto-, or hydroxysilane in a stoichiometric ratio of at least 1 mole of amino-, mercapto-, or hydroxysilane per mole equivalent of isocyanate groups.

9. The method according to claim 8, characterized in that at least one polyether diol is present in step (a) in addition to the polyether triol.

10. A curable composition comprising the polymer containing at least one silane group according to any one of claims 1 to 7 and at least one additional constituent selected from the group consisting of a catalyst, a crosslinking agent, an adhesion promoter, a desiccant, a plasticizer, and a filler.

11. The curable composition according to claim 10, characterized by comprising at least one additional, particularly linear, polymer containing a silane group that is different from the polymer containing a silane group according to any one of claims 1 to 7.

12. The curable composition according to claim 10 or 11, characterized by being used as an elastic adhesive or an elastic sealant or an elastic coating.

13. A cured composition obtained from the curable composition according to any one of claims 10 to 12 after contact with moisture.

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