Silane-containing branched polymer

Abstract

The present invention relates to a silane-containing branched polymer having an average of at least 2.1 silane groups per molecule obtained from the reaction of at least one amino-, mercapto-, or hydroxysilane with at least one amino-, mercapto-, or hydroxysilane, in a stoichiometric ratio of at least 1 amino-, mercapto-, or hydroxysilane per molar equivalent of isocyanate groups, (i) an isocyanate group-containing polymer having an NCO content in the range of 0.7 wt% to 4 wt% obtained from the reaction of at least one polyether polyol and at least one monomeric diisocyanate in an NCO / OH molar ratio of at least 1.5 / 1, and (ii) at least one amino-, mercapto-, or hydroxysilane. The silane group-containing polymer is a storage-stable liquid at room temperature, is easy to handle, and allows for a curable composition having excellent processability, rapid curing, high strength combined with good elongation, and surprisingly good thermal stability. The above polymer is particularly suitable as a component of moisture-curable sealants, adhesives, or coatings, and particularly includes additional, particularly linear, silane group-containing polymers.

Description

Technology Field

[0001] The present invention relates to curable compositions, in particular to silane group-containing polymers in moisture-curable adhesives, sealants or coatings, and to the use thereof. Background Technology

[0002] Silane-containing polymers, also known as silane-functional group or silane-terminal polymers, are known as components of moisture-curing adhesives, sealants, or coatings.

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

[0004] The latter is of greatest interest regarding mechanical properties, particularly good strength associated with high extensibility. Polymers containing isocyanate groups that serve as starting materials for their production are prepared, for example, by reacting a monomeric diisocyanate with a polyether diol at an NCO / OH ratio of about 2 / 1 as described in US 6,545,087 or US 9,790,315. These contain a significant amount of monomeric diisocyanate and a chain-extending polymer, wherein two or more polyether diols are suspended through the monomeric diisocyanate. Due to these secondary components, the silane-containing polymers obtained from them have high viscosity, and consequently, they are typically diluted with a small amount of plasticizer to facilitate handling at room temperature. However, compositions containing these silane-containing polymers exhibit poor thermal stability after curing, particularly at temperatures above 80 or 90°C.

[0005] In addition, silane group-containing polymers from the reaction of polyether triols and isocyanatosilanes are known, for example, from US 2014 / 187705. These polymers are considerably less viscous but have significantly lower strength and elongation, and their thermal stability after curing is also unsatisfactory.

[0006] Accordingly, the object of the present invention is to provide a silane group-containing polymer that allows for improved thermal stability after curing, along with high strength and good elongation.

[0007] The present object is achieved by a branched polymer containing silane groups as claimed in claim 1. This is obtained from the reaction of an isocyanate group-containing polymer prepared from a polyether triol with an amino-, mercapto-, or hydroxysilane in a stoichiometric ratio of at least 1 / 1 to the isocyanate groups. The silane group-containing polymer of the present invention is free of isocyanate groups. It is branched and has an average of more than 2 silane groups per molecule. This is preferably used in curable compositions comprising at least one additional linear polymer containing, in particular, silane. Surprisingly, this significantly improves the thermal stability of the composition without any notable loss of strength and elongation in the composition.

[0008] In a preferred embodiment, the monomer diisocyanate is IPDI. Thus, a polymer having particularly low viscosity is provided that can be easily manipulated at room temperature even without a very excess amount of NCO and subsequent monomer removal. These enable good processability and improved thermal stability, particularly after curing.

[0009] In a further preferred embodiment, the monomer diisocyanate is 4,4'-MDI, the NCO / OH ratio is at least 3 / 1, and subsequently, a polymer containing isocyanate groups is produced from which the unreacted monomer diisocyanate is removed. This branched polymer containing silane groups is considerably more viscous but still easy to handle at room temperature, and when used in a curable composition having a linear polymer containing silane groups, it allows for significantly increased strength as well as improved thermal stability without loss of elongation.

[0010] The silane group-containing polymer of the present invention is a storage-stable liquid at room temperature and allows for a curable composition that is easy to handle and possesses excellent processability, rapid curing, high strength combined with good elongation, and surprisingly good thermal stability. This is particularly suitable as a component of moisture-curing sealants, adhesives, or coatings, and furthermore, more specifically, comprises linear silane group-containing polymers.

[0011] Further aspects of the present invention are the subject of additional independent claims. Particularly preferred embodiments of the present invention are the subject of dependent claims. Specific details for implementing the invention

[0012] The present invention relates to a stoichiometric ratio of at least 1 mol of amino-, mercapto-, or hydroxysilane per molar equivalent of isocyanate group,

[0013] (i) an isocyanate group-containing polymer having an NCO content in the range of 0.7 wt% to 4 wt%, obtained from the reaction of at least one polyether triol having an average OH functional group in the range of 2.2 to 3 and an OH value in the range of 15 to 58 mg KOH / g with an NCO / OH molar ratio of at least 1.5 / 1, and at least one monomer diisocyanate, and

[0014] (ii) at least one amino-, mercapto-, or hydroxysilane

[0015] A branched polymer containing silane groups is provided from the reaction.

[0016] "Monomer diisocyanate" refers to an organic compound having two isocyanate groups separated by a divalent hydrocarbon radical having 4 to 15 carbon atoms.

[0017] "NCO content" refers to the weight % content of isocyanate groups.

[0018] "Organic silane" or simply "silane" refers to an organic compound having at least one silane group.

[0019] "Alkoxysilane group" or simply "silane group" refers to a silyl group that is bonded to an organic radical and has 1 to 3, particularly 2 or 3, hydrolyzable alkoxy radicals on a silicon atom.

[0020] "Aminosilane," "mercaptosilane," or "hydroxysilane" each refer to an organosilane having an amino, mercapto, or hydroxyl group on an organic radical in addition to the silane group.

[0021] "Molecular weight" refers to the molecular weight (grams per mole) of a molecule or molecular residue. "Average molecular weight" refers to the number-average molecular weight (M) of a polydisperse mixture of oligomer or polymer molecules or molecular residues. n It refers to ). This is determined by gel-permeation chromatography (GPC) for polystyrene as a standard.

[0022] In relation to reactors, the term "molar ratio" refers to the ratio of the number of molar equivalents of corresponding reactors.

[0023] In each case, the dashed line in the chemical formula represents the bond between the substituent and the corresponding molecular radical.

[0024] "Plasticizer" refers to a non-volatile substance that is not chemically incorporated into the polymer during the curing process and exerts a plasticizing effect on the cured polymer.

[0025] A substance or composition is referred to as "storage-stable" or "storable" when it is stored in a suitable container at room temperature for a long period, typically from at least 3 months to a maximum of 6 months or longer, and such storage does not cause any change in its application properties or use properties to an extent suitable for its use.

[0026] "Room temperature" refers to a temperature of 23℃.

[0027] All industry standards and criteria mentioned in this specification relate to forms valid on the first filing date.

[0028] Weight percentage (wt%) is abbreviated as wt% and, unless otherwise noted, refers to the ratio of the mass of a composition or molecular component to the total composition or total molecule. The terms "mass" and "weight" are used synonyms in this document.

[0029] The silane-containing polymer of the present invention does not have isocyanate groups.

[0030] This is a liquid, especially at room temperature.

[0031] Branched polymers containing silane groups preferably have only a small amount of plasticizer. In particular, they contain less than 15% by weight of plasticizer, preferably less than 12%. More preferably, they are completely free of plasticizer. When used in curable compositions, such polymers allow a high degree of freedom depending on whether a plasticizer is contained in the composition, how much is contained, and what type of plasticizer is contained.

[0032] A branched polymer containing a silane group preferably has a silane group of the following formula (I):

[0033]

[0034] During the meal,

[0035] b is 0, 1, or 2, specifically 0 or 1, and

[0036] R 1 is an alkyl radical having 1 to 10 carbon atoms and optionally containing an ether group, and

[0037] R 2 is a divalent hydrocarbyl radical having 1 to 12 carbon atoms having optionally cyclic and / or aromatic moiety and optionally one or more heteroatoms, in particular, an amido, carbamate, or morpholino group, and,

[0038] X is O, S, or NR 3 and, here, R 3 It is a monovalent hydrocarbyl radical having 1 to 20 carbon atoms having a heteroatom in the form of an alkoxysilyl, ether, or carboxylic acid ester group, or H.

[0039] Preferably, R 1 It is methyl, ethyl, or isopropyl.

[0040] More preferably, R 1 It is methyl. This type of polymer containing silane groups is particularly reactive.

[0041] Also, more preferably, R 1 It is ethyl. These polymers containing silane groups are particularly storage-stable and toxicologically advantageous.

[0042] Preferably, X is O or NR 3 am.

[0043] Preferably, R 3 It is an aliphatic hydrocarbyl radical having 6 to 20 carbon atoms, which is H, ethyl, butyl, phenyl, or optionally an ether or carboxylic acid group.

[0044] Most preferably, X is NR 3 and R 3 silver and, here, R 4 It is methyl or ethyl, especially ethyl.

[0045] X = NR 3 When, R 2 is preferably 1,3-propylene, 1,3-butylene or 1,4-butylene, where butylene can be substituted by one or two methyl groups, more preferably by 1,3-propylene.

[0046] When X = O, R 2 is preferably an amido, carbamate, or morpholino group, particularly of the chemical formula It is a divalent hydrocarbyl radical having 6 to 12 carbon atoms.

[0047] The desirable silane group of chemical formula (I) allows for high strength combined with high elongation.

[0048] In addition to the silane group of formula (I), the branched polymer containing the silane group preferably does not have additional silane groups that do not correspond to formula (I). In particular, it does not have isocyanate groups directly attached to the polyether triol via isocyanatosilane. Such silane groups attached via isocyanatosilane reduce strength and thermal stability after curing.

[0049] Preferably, the branched polymer containing silane groups has an average of 2.1 to 4, more preferably 2.2 to 3.5 silane groups per molecule.

[0050] Preferably, the branched polymer containing silane groups has an average molecular weight M in the range of 5,000 to 30,000 g / mol, preferably 6,000 to 20,000 g / mol, and particularly 7,000 to 15,000 g / mol. n has

[0051] A polymer containing isocyanate groups derived from a branched polymer containing silane groups preferably has an NCO content in the range of 0.8% to 3.5% by weight, more preferably 1% to 3% by weight, and particularly 1.2% to 2.5% by weight.

[0052] Suitable monomeric diisocyanates are commercial aromatic or aliphatic diisocyanates, in particular diphenylmethane 4,4'-diisocyanate, and optionally diphenylmethane 2,4'- and / or 2,2'-diisocyanate (MDI), tolylene 2,4-diisocyanate or mixtures thereof and tolylene 2,6-diisocyanate (TDI), phenylene 1,4-diisocyanate (PDI), naphthalene 1,5-diisocyanate (NDI), hexane 1,6-diisocyanate (HDI), 2,2(4),4-trimethylhexamethylene 1,6-diisocyanate (TMDI), cyclohexane 1,3- or 1,4-diisocyanate, It contains a portion of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI), perhydro-diphenylmethane 2,4'- or 4,4'-diisocyanate (HMDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, m- or p-xylene diisocyanate (XDI), m-tetramethylxylene diisocyanate (TMXDI), or a mixture thereof.

[0053] More preferably, the monomer diisocyanate is selected from the group consisting of MDI, TDI, HDI, and IPDI.

[0054] Among these, IPDI is particularly preferred. The silane group-containing polymer obtained in this way has particularly low viscosity and allows for compositions having particularly good processability, high elongation, and particularly good photostability.

[0055] In addition, among these, MDI, particularly diphenylmethane 4,4'-diisocyanate (4,4'-MDI), is particularly preferred. The silane group-containing polymer obtained together allows for compositions having particularly high strength.

[0056] Suitable polyether triols are preferably commercial triols that are liquid at room temperature.

[0057] Polyether triols have an average of OH functional groups within the range of 2.2 to 3. As a result of their production, commercial polyether triols have a specific amount of monool, and as a result, their average of OH functional groups is typically slightly less than 3. Therefore, they typically contain 3-functional and 1-functional group components.

[0058] The repeating unit present in the polyether triol is preferably a 1,2-ethyleneoxy, 1,2-propyleneoxy, 1,3-propyleneoxy, 1,2-butyleneoxy, or 1,4-butyleneoxy group, in particular a 1,2-ethyleneoxy and / or 1,2-propyleneoxy group.

[0059] More preferably, the repeating unit present in the polyether triol is mainly or exclusively a 1,2-propyleneoxy group. More specifically, 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.

[0060] Polyether triols were preferably started using trimethylolpropane or glycerol.

[0061] Polyether triols have an OH value in the range of 15 to 58 mg KOH / g. Preferably, they have an OH value in the range of 20 to 40 mg KOH / g. These polyether triols have an average molecular weight M, particularly in the range of 3,000 to 10,000 g / mol, preferably 4,000 to 9,000 g / mol. n has

[0062] The reaction between the monomer diisocyanate and the polyether triol is preferably carried out in the range of 20 to 160°C, particularly at a temperature within 40 to 140°C, optionally in the presence of a suitable catalyst, excluding moisture.

[0063] In the reaction, the OH groups of the polyether polyol react with the isocyanate groups of the monomer diisocyanate. This also results in what is called a chain extension reaction, namely, the reaction of the OH groups and / or isocyanate groups of the reaction product between the polyol and the monomer diisocyanate. The higher the selected NCO / OH molar ratio, the lower the level of the chain extension reaction occurring, and the lower the polydispersity of the resulting polymer. Measures of the chain extension reaction are the average molecular weight of the polymer or the peak width and distribution in GPC analysis. An additional measure is the effective NCO content of the monomer-free polymer compared to the theoretical NCO content calculated from the reaction of all OH groups with the monomer diisocyanate.

[0064] In a preferred embodiment of the present invention, the NCO / OH molar ratio in the reaction is preferably within the range of 1.6 / 1 to 2.5 / 1, more preferably within the range of 1.8 / 1 to 2.3 / 1, and particularly within the range of 1.9 / 1 to 2.2 / 1.

[0065] These polymers containing isocyanate groups are particularly easy to manufacture. They contain a specific proportion of non-reactive monomer diisocyanate, typically within about 0.5% to 3.5% by weight, and a specific proportion of chain-extending components. As a result, their viscosity is slightly higher.

[0066] For reactions at an NCO / OH molar ratio within the range of 1.5 / 1 to 2.5 / 1, the monomer diisocyanate is preferably TDI or IPDI, particularly IPDI. The polymer produced by this method has particularly low viscosity and is easy to handle at room temperature.

[0067] In a further preferred embodiment of the present invention, the NCO / OH molar ratio in the reaction is at least 3 / 1, preferably within the range of 3 / 1 to 20 / 1, more preferably within the range of 4 / 1 to 15 / 1, particularly within the range of 5 / 1 to 13 / 1, and after the reaction, a major portion of the unreacted monomer diisocyanate is removed by a suitable separation method.

[0068] These polymers containing isocyanate groups have particularly low content of monomer diisocyanate and particularly low content of chain extension components.

[0069] This preferably has a monomer diisocyanate content of 0.3% by weight or less, preferably 0.25% by weight or less.

[0070] These polymers containing isocyanate groups have particularly low viscosity. In particular, this production process also enables the use of monomeric diisocyanates that are otherwise less suitable for reaction with polyether triols, such as MDI, particularly because undesirably high viscosity is possible up to the gelation point that occurs during manufacturing.

[0071] As a separation method, distillation methods, particularly thin-film distillation or short-path distillation, are preferred, and preferably, reduced pressure is applied.

[0072] A multi-stage process is particularly preferred in which the monomer diisocyanate is removed in a single-path evaporator, the jacket temperature is within the range of 120 to 200°C, and the pressure is 0.001 to 0.5 mbar.

[0073] In the case of the desirable 4,4'-MDI, the removal of the distillate is particularly problematic. For example, it is necessary to ensure that the condensate does not solidify and does not block the system. It is preferred to operate at a jacket temperature in the range of 160 to 200°C, at 0.001 to 0.5 mbar, and to have the monomer diisocyanate condensed and removed at a temperature in the range of 40 to 60°C.

[0074] It is preferred that the monomer diisocyanate reacts with the polyether polyol and subsequently removes most of the monomer diisocyanate, leaving it in the reaction mixture without the use of a solvent or entraining agent.

[0075] Preferably, the monomer diisocyanate removed after the reaction is subsequently reused, that is, reused for the production of a polymer containing isocyanate groups.

[0076] For the reaction at an NCO / OH molar ratio of at least 3 / 1 and subsequent removal of most of the monomer diisocyanate by a suitable separation method, the monomer diisocyanate is preferably IPDI or MDI.

[0077] MDI, particularly 4,4'-MDI, is highly desirable for this purpose. Silane-containing polymers derived from the reaction of polyether triols with 4,4'- allow for strength accompanied by particularly high thermal stability. However, their manufacture is also particularly problematic. In the conventional route, these polymers containing isocyanate groups are typically very viscous, making it difficult to handle them without diluting with large amounts of plasticizer or solvent. These polymers are often already gels during manufacturing.

[0078] Polymers containing isocyanate groups become significantly storage-stable by the exclusion of moisture.

[0079] This is reacted with at least one amino-, mercapto-, or hydroxysilane in a stoichiometric ratio of at least 1 mol of amino-, mercapto-, or hydroxysilane per molar equivalent of isocyanate group to obtain a branched polymer containing silane groups according to the present invention.

[0080] For reaction with a polymer containing an isocyanate group, the amino-, mercapto-, or hydroxysilane is preferably a silane of the following formula (II):

[0081]

[0082] During the meal, R 1 , R 2 , X and b are as previously defined.

[0083] The preferred silane of formula (II) is 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, It is selected from the group consisting of N-(3-trimethoxysilylpropyl)-4-hydroxypentanamide, N-(3-trimethoxysilylpropyl)-4-hydroxyoctanamide, N-(3-trimethoxysilylpropyl)-5-hydroxydecaneamide, N-(3-trimethoxysilylpropyl)-2-hydroxypropyl carbamate, 2-morpholino-4(5)-(2-trimethoxysilylethyl)cyclohexane-1-ol, 2-morpholino-4(5)-(2-trimethoxysilylethyl)cyclohexane-1-ol, 1-morpholino-3-(3-(triethoxysilyl)propoxy)propan-2-ol and corresponding analogs having an ethoxy group instead of a methoxy group on silicon.

[0084] 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.

[0085] A very particularly preferred silane of formula (II) is diethyl N-(3-trimethoxysilylpropyl)aminosuccinate, diethyl N-(3-triethoxysilylpropyl)aminosuccinate, diethyl N-(3-dimethoxymethylsilylpropyl)aminosuccinate, or diethyl N-(3-diethoxymethylsilylpropyl)aminosuccinate.

[0086] Amino-, mercapto-, or hydroxysilane is reacted with a polymer containing an isocyanate group in a stoichiometric ratio of at least 1 mol of amino-, mercapto-, or hydroxysilane per molar equivalent of the isocyanate group.

[0087] A stoichiometry of amino-, mercapto-, or hydroxysilane is preferred within the range of 1 to 1.3 molar equivalents of isocyanate groups, preferably 1 to 1.2, particularly 1 or 1.1 mol.

[0088] The reaction is carried out at a temperature within the range of 20 to 160°C, particularly 60 to 120°C. Catalysts, particularly tertiary amines or metal compounds, particularly bismuth (III), zinc (II), zirconium (IV) or tin (II) compounds or organotin (IV) compounds are used herein.

[0089] Particularly desirable branched polymers containing silane groups are derived from IPDI as monomeric diisocyanates. Thus, they particularly have silane groups of the following chemical formulas (Ia) or (Ib):

[0090]

[0091] During the meal, R 1 , R 2 , X and b are as previously defined. These polymers allow for high elongation and, in particular, high photostability combined with good thermal stability.

[0092] This is preferably produced by having an NCO / OH molar ratio within the range of 1.5 / 1 to 2.5 / 1 without subsequent removal of monomer diisocyanate, or by having an NCO / OH ratio of at least 3 / 1 and subsequently removing most of the monomer diisocyanate by a suitable separation method. More preferably, it is produced with an NCO / OH molar ratio within the range of 1.5 / 1 to 2.5 / 1 without subsequent removal of monomer diisocyanate.

[0093] Another particularly desirable branched polymer containing a silane group is derived from 4,4'-MDI as a monomeric diisocyanate. Thus, it specifically has a silane group of the following chemical formula (Ic):

[0094]

[0095] During the meal, R 1 , R 2 , X and b are as previously defined. This allows for a composition having particularly high strength and good thermal stability.

[0096] Preferably, it is produced by an NCO / OH molar ratio of at least 3 / 1 and subsequent removal of most monomer diisocyanate by a suitable separation method.

[0097] Branched polymers containing silane groups become storage-stable by excluding moisture. Upon contact with moisture, the silane groups hydrolyze. This leads to the formation of silanol groups (Si-OH groups) and, through subsequent condensation reactions, the formation of siloxane groups (Si-O-Si groups). As a result of these reactions, the polymer cures to provide a cross-linked plastic. For curing, moisture may originate from air (air humidity), or the polymer may come into contact with a water-containing component, for example, by painting, spraying, or mixing. During curing, the silanol groups may condense, for example, with the hydroxyl groups of the substrate to which the polymer is applied, thereby enabling further improvement in adhesion to the substrate in the cross-linking process.

[0098] The present invention is,

[0099] (a) At least one monomer diisocyanate is reacted with at least one polyether triol having an average OH functional group 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

[0100] (b) Subsequently, the majority of unreacted monomer diisocyanates are selectively removed by a suitable separation method, particularly when an NCO / OH molar ratio of at least 3 / 1 is present, and

[0101] (c) Subsequently, the obtained polymer containing isocyanate groups is reacted with at least one amino-, mercapto-, or hydroxysilane in a stoichiometric ratio of at least 1 mol of amino-, mercapto-, or hydroxysilane per molar equivalent of isocyanate groups.

[0102] A process for manufacturing a branched polymer containing silane groups characterized by [specific feature] is further provided.

[0103] In a preferred aspect of the present invention, at least one polyether diol is additionally provided to the polyether triol in step a). This results in the in situ formation of a mixture of the branched polymer containing silane groups of the present invention and the linear polymer not of the present invention containing silane groups.

[0104] The weight ratio between the polyether triol and the polyether diol is preferably in the range of 10 / 90 to 70 / 30, particularly within 15 / 85 to 60 / 40 in this specification.

[0105] Polyether diols suitable for this purpose have an OH value in the range of 5 to 40 mg KOH / g, preferably 6 to 20 mg KOH / g, particularly 7 to 15 mg KOH / g.

[0106] Based on its repeating unit, it preferably contains 80% to 100% by weight of 1,2-propylene oxygen groups and 0% to 20% by weight of 1,2-ethylene oxygen groups.

[0107] These linear polymers containing silane groups allow for compositions with particularly high elongation and elasticity.

[0108] The present invention further provides a reaction product from the process of the present invention.

[0109] The present invention further provides a curable composition comprising at least one additional component selected from the group consisting of a branched polymer containing a silane group according to the present invention and a catalyst, a crosslinking agent, an adhesion promoter, a drying agent, a plasticizer, and a filler.

[0110] Suitable catalysts are metal catalysts and / or nitrogen compounds that accelerate the crosslinking of silane-containing polymers.

[0111] Suitable metal catalysts are particularly titanium, zirconium, aluminum or tin, particularly organotin compounds, organic titanoic acid, organic zirconic acid or organic aluminate acid compounds, and these compounds particularly have an alkoxy group, an aminoalkoxy group, a sulfonic acid group, a carboxyl group, a 1,3-diketonate group, a 1,3-ketoesterate group, a dialkyl phosphate group or a dialkyl pyrophosphate group.

[0112] Particularly suitable organotin compounds are dialkyltin oxide, dialkyltin dichloride, dialkyltin dicarboxylate and dialkyltin diketonate, in particular dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diacetylacetonate, dioctyltin oxide, dioctyltin dichloride, dioctyltin diacetate, dioctyltin dilaurate or dioctyltin diacetylacetonate or alkyltin thioester.

[0113] Particularly suitable organic titanates 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, It is tetra(isopropoxy) titanate or polybutyl titanate. Commercially available product: Tyzor ® AA, GBA, GBO, AA-75, AA-65, AA-105, DC, BEAT, BTP, TE, TnBT, KTM, TOT, TPT, or IBAY (all manufactured by Dorf Ketal); Tytan PBT, TET, X85, TAA, ET, S2, S4, or S6 (all manufactured by Borica Company Ltd.) and Ken-React ® KR ® TTS, 7, 9QS, 12, 26S, 33DS, 38S, 39DS, 44, 134S, 138S, 133DS, 158FS, or LICA ® 44 (all manufactured by Kenrich Petrochemicals) is particularly suitable.

[0114] Particularly suitable organic zirconic acid is the commercially available product Ken-React ® NZ ® 38J, KZ ® TPPJ, KZ ® TPP, NZ ® 01, 09, 12, 38, 44, or 97 (all from Kenrich Petrochemicals) or Snapcure ®3020, 3030, and 1020 (all made by Johnson Matthey & Brandenberger).

[0115] A particularly suitable organic aluminate is the commercially available product K-Kat 5218 (manufactured by King Industries).

[0116] Nitrogen compounds suitable as catalysts are particularly amines, e.g., particularly N-ethyldiisopropylamine, N,N,N',N'-tetramethylalkylenediamine, polyoxyalkyleneamines, 1,4-diazabicyclo[2.2.2]octane; aminosilanes, e.g., particularly 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxylmethylsilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-N'-[3-(trimethoxysilyl)propyl]ethylenediamine or analogs thereof having an ethoxy group instead of a methoxy group on silicon; Cyclic amidines, e.g., particularly, 1,8-diazabicyclo[5.4.0]undec-7-en (DBU), 1,5-diazabicyclo[4.3.0]non-5-en (DBN), 6-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-en; guanidines, e.g., particularly, tetramethylguanidine, 2-guanidinobenzimidazole, acetylacetoneguanidine, 1,3-di-o-tolylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, or reaction products with carbodiimide and amines, e.g., particularly, polyetheramine or aminosilane; or an imidazole, for example, in particular, N-(3-trimethoxysilylpropyl)-4,5-dihydroimidazole or N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0117] In addition, a combination of different catalysts, in particular a combination of at least one metal catalyst and at least one nitrogen compound is suitable.

[0118] Preferred catalysts are organotin compounds, organotitonic acids, amines, particularly aminosilanes, amidines, guanidines, or imidazoles.

[0119] Suitable adhesion promoters and / or crosslinking agents are, in particular, aminosilanes, mercaptosilanes, epoxysilanes, (meth)acrylosilanes, anhydridosilanes, carbamateosilanes, alkylsilanes or iminosilanes, or oligomeric forms of these silanes, or adducts of primary aminosilanes and epoxysilanes or (meth)acrylosilanes or anhydridosilanes. 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane, N-(2-aminoethyl)-N'-[3-(trimethoxysilyl)propyl]ethylenediamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, or corresponding silanes having an ethoxysilane group instead of a methoxysilane group on silicon, or oligomeric forms of these silanes are particularly suitable.

[0120] Particularly suitable drying agents are tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, organosilanes having a functional group at the α-position relative to the silane group, particularly N-(methyldimethoxysilylmethyl)-O-methylcarbamate or (methacryloyloxymethyl)silane, methoxymethylsilane, orthoformic acid esters, and also calcium oxide or molecular sieves. Vinyltrimethoxysilane or vinyltriethoxysilane is preferred. In this specification, vinyltrimethoxysilane is preferred when the branched polymer containing the silane group has a methoxysilane group, whereas vinyltriethoxysilane is preferred when the branched polymer containing the silane group has an ethoxysilane group.

[0121] Suitable plasticizers include, in particular, acetate groups, organophosphate or sulfonic acid esters, polybutene, or plasticizers derived from natural fats or oils also called "biodiesel," in particular fatty acid methyl or ethyl esters, or carboxyl esters in the form of epoxidized soybean or flaxseed oil, e.g., phthalates, in particular diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), or di(2-propylheptyl)phthalate (DPHP), hydrogenated phthalates or cyclohexane-1,2-dicarboxylates, in particular hydrogenated diisononyl phthalate or diisononyl cyclohexane-1,2-dicarboxylate (DINCH), terephthalates, in particular bis(2-ethylhexyl) terephthalate (DOTP) or diisononyl terephthalate (DINT), hydrogenated terephthalates or cyclohexane-1,4-dicarboxylates, in particular hydrogenated It is bis(2-ethylhexyl) terephthalate or bis(2-ethylhexyl) cyclohexane-1,4-dicarboxylate, or hydrogenated diisononyl terephthalate or diisononyl cyclohexane-1,4-dicarboxylate, isophthalate, trimellitate, adipate, in particular dioctyl adipate, azelate, sebacate, benzoate, polyol, in particular polyether polyol or polyester polyol, glycol ether, glycol ester, polyether mono- or polyol having blocked hydroxyl groups.

[0122] Suitable fillers are, in particular, fatty acids, in particular stearates, barites, quartz powder, silica sand, dolomite, wollastonite, calcined kaolin, sheet silicates, e.g., mica or talc zeolite, aluminum hydroxide, magnesium hydroxide, silica (including finely divided silica from a pyrolysis process), cement, gypsum, fly ash, industrially produced carbon black, graphite, metal powders, e.g., aluminum, copper, iron, silver or steel, PVC powder or metal powder in the form of hollow beads, and pulverized or precipitated calcium carbonate, optionally coated with metal powder. Precipitating fatty acid-coated calcium carbonate and / or carbon black is preferred.

[0123] Additional suitable components are, in particular, the following auxiliary agents and additives:

[0124] - Oligomers or polymers containing silane groups;

[0125] - Solvent;

[0126] - Fibers, particularly glass fibers, carbon fibers, metal fibers, ceramic fibers, polymer fibers, e.g., polyamide fibers or polyethylene fibers, or natural fibers, e.g., wood, cellulose, hemp, or sisal;

[0127] - Nanofillers, e.g., graphene or carbon nanotubes;

[0128] - Dye;

[0129] - Inorganic or organic pigments, in particular, titanium dioxide, chromium oxide, or iron oxide;

[0130] - Flow modifiers, particularly thickeners, sheet silicates, e.g., bentonite, derivatives of castor oil, hydrogenated castor oil, polyamides, polyamide waxes, polyurethanes, urea compounds, fumed silica, cellulose ethers, or hydrophobically modified polyoxyethylene;

[0131] - Stabilizer against oxidation, heat, light, or UV radiation;

[0132] - Natural resins, fats, or oils, e.g., pine resin, shellac, linseed oil, castor oil, or soybean oil;

[0133] - Non-reactive polymers from the group comprising, in particular, 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), in particular, homopolymers or copolymers of unsaturated monomers;

[0134] - Flame-retardant materials, in particular the previously mentioned fillers aluminum hydroxide or magnesium hydroxide, or organic phosphate esters;

[0135] - Additives, in particular wetting agents, leveling agents, anti-foaming agents, air separators, stabilizers against oxidation, heat, light or UV radiation or biocides.

[0136] Certain components may be recommended to undergo chemical or physical drying before being mixed into the composition.

[0137] The curable composition preferably contains 5% to 80% by weight, more preferably 10% to 70% by weight, and particularly 20% to 60% by weight of a silane group-containing polymer.

[0138] In a preferred embodiment of the present invention, the curable composition comprises at least one additional, non-inventional silane group-containing polymer.

[0139] In particular, this additional silane group-containing polymer is linear. It preferably has an average of 1.7 to 2 silane groups per molecule, more preferably 1.8 to 2, and particularly 1.9 to 2.

[0140] The weight ratio of the branched polymer containing silane groups according to the present invention and the additional polymer containing silane groups according to the present specification is preferably in the range of 10 / 90 to 70 / 30, particularly within 15 / 85 to 60 / 40.

[0141] An additional polymer containing silane groups is preferably,

[0142] - A silane group-containing polymer derived from a polymer containing isocyanate groups from the reaction of a monomer diisocyanate and a polyether diol at least 1.5 / 1 NCO / OH molar ratio;

[0143] - A silane group-containing polyether obtained from the reaction of an allyl group-containing polyether with a hydrosilane, optionally with a chain extension, in particular, with a diisocyanate;

[0144] - A silane group-containing polyether obtained from the copolymerization of an alkylene oxide with an epoxysilane, optionally copolymerization with a chain extension, particularly copolymerization with a diisocyanate;

[0145] - Silane group-containing polyethers obtained from the reaction of polyether polyols, particularly diols, with isocyanatosilanes, and optionally with chain extensions using diisocyanates

[0146] It is selected from a group consisting of.

[0147] In this specification, the branched polymer containing silane groups of the present invention improves the thermal stability and possibly strength and / or elongation of the composition.

[0148] As an additional silane group-containing polymer, it is preferred to be derived from a polymer containing isocyanate groups from the reaction of a monomer diisocyanate and a polyether diol at an NCO / OH molar ratio of at least 1.5 / 1.

[0149] Polyether diols suitable for this purpose have an OH value particularly in the range of 5 to 40 mg KOH / g, preferably 6 to 20 mg KOH / g, particularly 7 to 15 mg KOH / g. In particular, this has an average molecular weight M in the range of 3,500 to 20,000 g / mol, preferably 5,000 to 18,000 g / mol, particularly within 7,500 to 16,000 g / mol. n These polymers allow for compositions with particularly high elongation and elasticity.

[0150] This mixture of the branched polymer of the present invention and the polymer not of the present invention can also be prepared in particular by mixing the monomer diisocyanate with a mixture of at least one polyether triol and at least one polyether diol as described, in an NCO / OH molar ratio of at least 1.5 / 1, in a polymer containing an isocyanate group, and then reacting with at least one amino, mercapto, or hydroxysilane as described.

[0151] The curable composition is produced in particular by excluding moisture and is stored at ambient temperature in a moisture-proof container. Suitable moisture-proof containers are made of metal and / or plastic, particularly optionally coated, and are drums, transport boxes, hobbocks, buckets, canisters, cans, bags, tubular bags, cartridges, or tubes.

[0152] The curable composition may be in the form of a one-component composition or a two-component composition.

[0153] A "one-component" composition refers to a composition in which all components are mixed together in the same container, stored, and hardened by moisture.

[0154] A "2-component" composition refers to a composition in which the components exist as two different components stored in separate containers. The two components are not mixed with the other until immediately before or during the application of the composition, and as a result, the mixed composition hardens, and the hardening proceeds or is completed only through the action of moisture.

[0155] The curable composition is preferably a one-component composition. If suitable packaging and storage are provided, storage is typically stable for several months to up to one year or longer.

[0156] When a curable composition is applied, the present silane groups come into contact with moisture to initiate the curing process. Curing proceeds at varying rates depending on temperature, contact properties, the amount of moisture, and the presence of any catalyst. In the case of curing by air humidity, a skin is formed first on the surface of the composition. Skin time is a measure of the curing speed.

[0157] This results in the formation of a cured composition.

[0158] In the case of a one-component composition, it is applied as is and then begins to cure under the influence of moisture or water. To accelerate curing, an accelerator component containing water and / or a catalyst and / or a curing agent may be mixed with the composition at the time of application, or the composition may come into contact with such accelerator component after application.

[0159] The curable composition is preferably applied at ambient temperature, particularly in the range of about -10 to 50°C, preferably in the range of -5 to 45°C, particularly in the range of 0 to 40°C.

[0160] Curing preferably occurs at ambient temperature as well.

[0161] In the cured state, the composition exhibits remarkably elastic properties on various substrates, particularly high strength and high elongation, good thermal stability, and good adhesive properties. As a result, it is suitable for a number of applications, particularly as a sealant, adhesive, covering, coating, or paint for construction or industrial applications, for example, as a joint sealant, parquet adhesive, assembly adhesive, glazing adhesive, or body sealant, seam sealant, or cavity sealant, as a floor finish, floor coating, balcony coating, roof coating, or parking lot coating.

[0162] It is preferred to use a curable composition as an elastic adhesive, elastic sealant, or elastic coating.

[0163] A curable composition can be formulated to have a paste-like viscosity having structurally viscous characteristics. This type of composition is applied by a suitable device, for example, from a commercial cartridge, drum, or hop, in the form of beads having a cross-sectional area that is essentially round or triangular.

[0164] The curable composition may also be formulated to be fluid, "self-leveling," or only slightly thixotropic, and pourable for application. As a coating, it can then be distributed over an area, for example, by a roller, slide bar, toothed applicator, or trowel, to achieve a desired layer thickness. In operation, a layer thickness in the range of 0.5 to 3 mm, particularly within 1 to 2.5 mm, is typically applied.

[0165] Substrates suitable for adhesion, sealing, or coating are specifically as follows:

[0166] - Glass, glass ceramics, screen-printed ceramics, concrete, mortar, cement screed, fiber cement, especially fiber cement board, brick, tile, plaster, especially plasterboard or gypsum screed, or natural stone, e.g., granite or marble;

[0167] - Metals or alloys, e.g., aluminum, copper, iron, steel, non-ferrous metals, e.g., surface-finished metals or alloys, e.g., zinc-plated or chrome-plated metals;

[0168] - Plastics, particularly rigid or flexible PVC, polycarbonate (PC), polyamide (PA), polyester, PMMA, ABS, SAN, epoxy resin, phenolic resin, PUR, POM, TPO, PE, PP, EPM, or EPDM (wherein the surface of the plastic is optionally subjected to plasma, corona, or flame treatment);

[0169] - Paints or varnishes, especially automotive topcoats;

[0170] - Repair or smoothing compounds based on PCC (polymer-modified cement mortar) or ECC (epoxy resin-modified cement mortar);

[0171] - Asphalt or bitumen;

[0172] - Leather, fabric, paper, wood, wood-based materials combined with resins such as phenol, melamine, or epoxy resins, resin-fabric composites, or other so-called polymer composites;

[0173] - Foam insulation, particularly made of EPS, XPS, PUR, PIR, rock wool, glass wool, or foamed glass.

[0174] If necessary, the substrate may be pretreated prior to application, particularly by physical and / or chemical cleaning methods or by the application of an activator or primer.

[0175] This can combine or seal two identical or two different materials.

[0176] After the two materials are joined or sealed, a joined or sealed article is obtained. This article may be a building structure or part thereof, particularly an above-ground or underground building structure, a bridge, a roof, a staircase, or a facade, or an industrial product or consumer product, particularly a window, a pipe, a household appliance, or a means of transportation, such as, in particular, an automobile, a bus, a truck, a railway vehicle, a ship, an aircraft, or a helicopter, or an installable part thereof.

[0177] The present invention further provides a cured composition obtained from a curable composition after the curable composition is brought into contact with moisture.

[0178] The composition of the present invention eliminates moisture storage stability and can be easily processed. It cures rapidly and, after curing, possesses high strength combined with good elongation, good adhesive properties, and surprisingly good thermal stability.

[0179] Examples

[0180] Working examples are presented below in this specification, the purpose of which is to further explain the invention. The invention is, of course, not limited to the working examples described herein.

[0181] Standard climatic condition ("SCC") refers to a temperature of 23±1℃ and a relative air humidity of 50±5%.

[0182] The chemicals used were Sigma-Aldrich products unless otherwise noted.

[0183] Diisodecyl phthalate Palatinol ® It is used in the form of 10-P (BASF).

[0184] viscosityThermostated Rheotec RC30 conical plate viscometer (cone diameter 25 mm, cone angle 1°, distance from cone tip to plate 0.05 mm, shear rate 10 s -1 It was measured using ).

[0185] Monomer diisocyanate content It was determined by HPLC (photodiode array; detection via 0.04 M sodium acetate / acetonitrile as mobile phase) after pre-derivation with N-propyl-4-nitrobenzylamine.

[0186] Preparation of isocyanate group-containing polymers using polyether triols:

[0187] Polymer T-1: (NCO / OH = 2.1 / 1)

[0188] 190.0 g of ethylene oxide-terminated polyoxypropylene triol (OH value 28 mg KOH / g, Desmophen ® 5031 BT, Covestro), 27.8g of diisodecyl phthalate, 22.2g of IPDI (1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, Vestanat® IPDI, Evonik) and 0.12g of dibutyltin dilaurate were reacted at 90°C by a known method to obtain a polymer having an NCO content of 1.75 wt% and a viscosity of 31 Pa·s at 20°C.

[0189] Polymer T-2:

[0190] 780.0 g of ethylene oxide-terminated polyoxypropylene triol (OH value 28 mg KOH / g, Desmophen ®5031 BT (Covestro) and 220 g of IPDI (1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, Vestanat® IPDI, Evonik) were reacted at 80°C in the presence of 0.01 g of dibutyltin dilaurate by a known method to obtain a polymer having an NCO content of 6.4 wt%, a viscosity of 4.1 Pa·s at 20°C, and a monomer IPDI content of about 12 wt%.

[0191] Subsequently, volatile components, particularly most monomer IPDI, were removed by distillation in a short-path evaporator (jacket temperature 160°C, pressure 0.1 to 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 a monomer IPDI content of 0.02 wt%.

[0192] Polymer T-3:

[0193] 725.0 g of ethylene oxide-terminated polyoxypropylene triol (OH value 28 mg KOH / g, Desmophen ® 5031 BT, Covestro) and 275g of diphenylmethane 4,4'-diisocyanate (Desmodur ® 44 MC L, Covestro agent) was reacted at 80°C by a known method to obtain a polymer having an NCO content of 7.6 wt%, a viscosity of 6.5 Pa·s at 20°C, and a monomer diphenylmethane 4,4'-diisocyanate content of approximately 20 wt%.

[0194] Subsequently, volatile components, particularly most monomeric diphenylmethane 4,4'-diisocyanate, were removed by distillation in a short-circuit evaporator (jacket temperature 180°C, pressure 0.1 to 0.005 mbar, condensation temperature 47°C). The polymer thus obtained had an NCO content of 1.7 wt%, a viscosity of 19 Pa·s at 20°C, and a monomeric diphenylmethane 4,4'-diisocyanate content of 0.04 wt%.

[0195] Polymer T-4: (NCO / OH = 2.1 / 1)

[0196] 190.0 g of ethylene oxide-terminated polyoxypropylene triol (OH value 28 mg KOH / g, Desmophen ® 5031 BT, Covestro) and 25.0 g of diphenylmethane 4,4'-diisocyanate (Desmodur ® 44 MC L, Covestro agent) was reacted at 80°C by a known method. The reaction mixture gelled during the reaction and consequently was unsuitable for further use.

[0197] Preparation of isocyanate group-containing polymers using polyether diols:

[0198] Polymer L-1: (NCO / OH = 2.1 / 1)

[0199] 1000.0g of polyoxypropylene diol (OH value 10mg KOH / g, Acclaim ® 12200N (Covestro), 122.8g of diisodecyl phthalate, 41.6g of IPDI (1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, Vestanat® IPDI, Evonik) and 0.12g of dibutyltin dilaurate were reacted at 90°C by a known method to obtain a polymer having an NCO content of 0.63 wt%, a viscosity of 31 Pa·s at 20°C, and a monomer IPDI content of about 0.5 wt%.

[0200] Silane of the chemical formula (II) used:

[0201]

[0202] Preparation of silane-containing polymers:

[0203] Polymer ST-1: (The present invention, branched type)

[0204] 240.0g of as stated above Polymer T-1 36.2g of the initial packing under a nitrogen atmosphere with moisture excluded Silan A-1 The mixture was added and stirred at 60°C until isocyanate groups could no longer be detected by FT-IR spectroscopy. The obtained polymer was cooled to room temperature, dehydrated, and stored. It contained 10 wt% of a plasticizer (diisodecyl phthalate), was clear, and had a viscosity of 97 Pa·s at 20°C on the day following preparation.

[0205] Polymer ST-2: (The present invention, branched type)

[0206] 221.0g of as stated above Polymer T-2 36.2g of the initial packing under a nitrogen atmosphere with moisture excluded Silan A-1 ...was added, and the mixture was stirred at 60°C until isocyanate groups could no longer be detected by FT-IR spectroscopy. The obtained polymer was cooled to room temperature, dehydrated, and stored. It was clear and had a viscosity of 70 Pa·s at 20°C on the day following preparation.

[0207] Polymer ST-3: (The present invention, branched type)

[0208] 247.0g of as stated above Polymer T-3 36.2g of the initial packing under a nitrogen atmosphere with moisture excluded Silan A-1 ...was added, and the mixture was stirred at 60°C until isocyanate groups could no longer be detected by FT-IR spectroscopy. The obtained polymer was cooled to room temperature, dehydrated, and stored. It was clear and had a viscosity of 357 Pa·s at 20°C on the day following preparation.

[0209] Polymer SL-1: (Not the present invention, branched type)

[0210] 333.3g of as stated above Polymer L-1 18.1g of the initial packing of under a nitrogen atmosphere with moisture excluded Silan A-1...was added, and the mixture was stirred at 60°C until isocyanate groups could no longer be detected by FT-IR spectroscopy. The obtained polymer was cooled to room temperature, dehydrated, and stored. It contained 10 wt% of a plasticizer (diisodecyl phthalate), was clear, and had a viscosity of 99 Pa·s at 20°C on the day after preparation.

[0211] Polymer SPUR-1: (Comparative example, branched type)

[0212] 190.0g of Desmophen ® 5031 BT and 19.5 g of 3-isocyanatopropyltrimethoxysilane were reacted at 80°C by a known method to obtain a silane group-containing polymer. The obtained polymer was cooled to room temperature, dehydrated, and stored. It was clear and had a viscosity of 5 Pa·s at 20°C on the day following preparation.

[0213] Moisture-curing composition:

[0214] Composition Z1 to Z9:

[0215] For each composition, the ingredients specified in Tables 1 and 2 were mixed in the specified amounts (parts by weight) using a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) at 3000 rpm for 1 minute to remove moisture, and then stored after removing moisture.

[0216] The composition was tested as follows:

[0217] As a measure of storage stability, at room temperature after 1 day ( 1d RT ) After storage with moisture removed in a sealed aluminum tube, and after 7 days, in an air-circulating oven at 60°C ( 7d 60℃ ) viscosity Measured.

[0218] As a measure of open time, skin time ( HBZ) was determined. For this purpose, a few grams of the composition were applied to a cardboard with a layer thickness of about 2 mm and for a period under standard weather conditions, and it was determined that no residue remained on the LDPE pipette used to lightly tap the surface of the composition thereafter.

[0219] As a measure of hardness and thermal stability, Shore A Hardness was determined according to DIN 53505 for test specimens hardened under standard weather conditions (7d SCC) for 7 days, or for test specimens hardened under standard weather conditions for 7 days, followed by being stored for a specified period at a specified temperature of 80°C, 90°C, or 100°C in an air-circulating oven.

[0220] To determine mechanical properties, the composition was applied to a silicon-coated release liner to provide a film with a thickness of 2 mm, which was stored for 14 days under standard air conditions; subsequently, several dumbbells having a length of 75 mm with a bar length of 30 mm and a bar width of 4 mm were punched into the film, and these were tested according to DIN EN 53504 at a strain rate of 200 mm / min. tensile strength (Breaking force), Breaking elongation , and (at an elongation of 0.5 to 5%) 5% elastic modulus Decided.

[0221] The results are reported in Tables 1 and 2.

[0222] Comparative example (reference) Confirmed by.

[0223]

[0224]

[0225] From Tables 1 and 2, the composition of the present invention Z2 inside Z4 and Z6 inside Z9 While has good to very good thermal stability, the comparative composition Z1 and Z5It can be seen that it has unsuitable thermal stability. After storage at 90°C for 14 days and at 100°C for 7 days, Shore A specimen was destroyed to the point where further measurement was no longer possible.

Claims

Claim 1 A silane group-containing branched polymer, characterized by having at least 1 mol of amino-, mercapto-, or hydroxysilane per 1 molar equivalent of an isocyanate group, wherein (i) an isocyanate group-containing polymer having an NCO content in the range of 0.7 wt% to 4 wt% obtained from the reaction of at least one monomer diisocyanate with at least one polyether triol having an average OH functional group 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) a silane group having a silane group of the following chemical formula (I), obtained from the reaction of at least one amino-, mercapto-, or hydroxysilane, wherein the silane group is obtained in a stoichiometric ratio such that at least 1 mol of amino-, mercapto-, or hydroxysilane is present per 1 molar equivalent of an isocyanate group: In the expression, b is 0, 1, or 2, and ,R 1 is an alkyl radical having 1 to 10 carbon atoms, and R 2 is a divalent hydrocarbyl radical having 1 to 12 carbon atoms, and X is NR 3 and, here, R 3 silver and, here R 4 is methyl or ethyl. Claim 2 A silane group-containing branched polymer according to claim 1, characterized by having an average of 2.1 to 4 silane groups per molecule. Claim 3 A silane group-containing branched polymer according to claim 1, characterized in that the monomer diisocyanate is 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane. Claim 4 A silane group-containing branched polymer according to claim 1, characterized in that the monomer diisocyanate is diphenylmethane 4,4'-diisocyanate. Claim 5 A silane group-containing branched polymer according to claim 1, characterized in that the polyether triol contains 80% to 100% by weight of 1,2-propylene oxygen groups and 0% to 20% by weight of 1,2-ethylene oxygen groups based on all repeating units. Claim 6 A silane group-containing branched polymer, characterized in that, in claim 1, the NCO / OH molar ratio in the reaction is within 1.6 / 1 to 2.5 / 1. Claim 7 A silane group-containing branched polymer, characterized in that, in claim 1, the NCO / OH molar ratio in the reaction is at least 3 / 1, and after the reaction, the unreacted monomer diisocyanate is separated and removed. Claim 8 A method for preparing a silane group-containing branched polymer according to any one of claims 1 to 7, wherein (a) at least one monomer diisocyanate is reacted with at least one polyether triol having an OH value in the range of 15 to 58 mg KOH / g and an NCO / OH molar ratio of at least 1.5 / 1 having an average OH functional group in the range of 2.2 to 3, (b) subsequently, the unreacted monomer diisocyanate is separated and removed, and (c) subsequently, the obtained polymer containing isocyanate groups is reacted with at least one amino-, mercapto-, or hydroxysilane in a stoichiometric ratio such that at least 1 mol of amino-, mercapto-, or hydroxysilane is present per 1 molar equivalent of the isocyanate group. Claim 9 A method for preparing a silane group-containing branched polymer, characterized in that, in claim 8, at least one polyether diol is additionally provided to the polyether triol in step a). Claim 10 Reaction product from the method according to paragraph 8. Claim 11 A curable composition comprising at least one silane group-containing polymer according to any one of claims 1 to 7 and at least one additional component selected from the group consisting of a catalyst, a crosslinking agent, an adhesion promoter, a drying agent, a plasticizer, and a filler. Claim 12 A curable composition according to claim 11, further comprising at least one different silane group-containing polymer. Claim 13 A curable composition according to claim 11, characterized in that it is used as an elastic adhesive, an elastic sealant, or an elastic coating. Claim 14 A cured composition obtained from the curable composition after contacting the curable composition according to claim 11 with moisture. Claim 15 delete

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