Polymers containing silane groups

Abstract

The present invention relates to (i) a polymer containing isocyanate groups, having an NCO content in the range of 0.3 wt% to 4 wt% and a monomeric diisocyanate content of up to 0.3 wt%, obtained by reacting at least one monomeric diisocyanate with at least one polyether polyol in an NCO / OH molar ratio of at least 3 / 1 and subsequently removing most of the unconverted monomeric diisocyanate by a suitable separation method, and (ii) a silane group-containing polymer obtained by reacting at least one amino-, mercapto-, or hydroxysilane in a stoichiometric ratio of at least 1 mole of amino-, mercapto-, or hydroxysilane per molar equivalent of isocyanate groups. The present silane-containing polymer provides a curable composition that is storage-stable, easy to handle at room temperature without dilution with plasticizers or solvents, and possesses excellent processability, rapid curing, high strength along with excellent elongation, and, in a preferred embodiment, improved thermal stability. This is particularly suitable as a component of moisture-curable sealants, adhesives, or coatings.

Description

Technology Field

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

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

[0003] There are various known routes for polymers containing silane groups. 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 polyol; and finally, there is a polymer containing an isocyanate group obtained from the reaction of a polyether polyol with a monomeric diisocyanate and a polymer containing a silane group obtained from the reaction of an amino- or hydroxysilane.

[0004] The latter is of the greatest interest in relation to mechanical properties, particularly excellent strength along with high elongation. Polymers containing isocyanate groups that serve as starting materials for their manufacture are prepared by reacting a monomeric diisocyanate and a polyether diol at an NCO / OH ratio of about 2 / 1, as described in, for example, US 6,545,087 or US 9,790,315. These contain a significant amount of monomeric diisocyanate and a chain-extending polymer in which two or more polyether diols are added through the monomeric diisocyanate. Due to these secondary components, the silane-containing polymers obtained therefrom have high viscosity, and consequently, they must generally be diluted with a significant amount of plasticizer to ensure they are sufficiently free-flowing at room temperature for efficient handling. However, consequently, the freedom of formulation for moisture-curing adhesives, sealants, or coatings is limited in relation to the plasticizer content. In particular, for sealing porous substrates and bonding plastics, sealants and adhesives with very low plasticizer content are required to prevent the risk of substrate damage caused by plasticizer migration. Furthermore, known polymers containing such silane groups still require improvement in terms of curing speed, strength, and thermal stability.

[0005] EP 1,237,967, US 6,884,904, or EP 1,553,118 describe a polymer containing isocyanate groups in which a monomeric diisocyanate is reacted with a polyether polyol at an NCO / OH ratio well greater than 2 / 1, and then the unconverted monomeric diisocyanate is removed by distillation. This provides advantages regarding the viscosity and EHS classification of the obtained polymer containing isocyanate groups.

[0006] The object of the present invention is to provide a polymer containing silane groups that can be efficiently handled at room temperature without dilution with a plasticizer or solvent and enables faster curing and / or higher strength along with excellent elongation and elasticity and / or improved thermal stability.

[0007] This objective is achieved by a polymer containing silane groups as claimed in claim 1. This is achieved by reacting an amino-, mercapto-, or hydroxysilane in a stoichiometric ratio of at least 1 / 1 with respect to the isocyanate groups with a polymer containing isocyanate groups, previously obtained by reacting a monomeric diisocyanate and a polyether polyol in an NCO / OH ratio of at least 3 / 1 and subsequently removing most of the unconverted monomeric diisocyanate. The polymer of the present invention containing silane groups is free of isocyanate groups, contains almost no silane adducts of the monomeric diisocyanate, and contains only a low level of chain-extended polymer components. As a result, it enables a moisture-curing composition having particularly low viscosity at room temperature and excellent processability. Surprisingly, the polymer of the present invention exhibits particularly rapid curing and, to some extent, particularly high strength (tensile strength and / or elastic modulus and / or Shore hardness). The polymer of the present invention can be used to produce sealants, adhesives, or coatings that are particularly storage-stable and highly processable, with low or completely free levels of plasticizers or solvents, of a kind that cannot be obtained from conventional polymers containing silane groups based on polymers containing isocyanate groups.

[0008] The product obtained from the polymer of the present invention surprisingly possesses advantageous properties, such as particularly high strength, along with improved thermal stability and / or particularly high elongation, even after curing.

[0009] 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

[0010] The present invention is,

[0011] (i) a polymer containing isocyanate groups, having an NCO content in the range of 0.3 wt% to 4 wt% and a monomeric diisocyanate content of 0.3 wt% or less, obtained from the reaction of at least one monomeric diisocyanate with at least one polyether polyol at an NCO / OH molar ratio of at least 3 / 1, and the subsequent removal of most of the unconverted monomeric diisocyanate by a suitable separation method, and

[0012] (ii) obtained by reacting at least one amino-, mercapto-, or hydroxysilane in a stoichiometric ratio of at least 1 mole of amino-, mercapto-, or hydroxysilane per molar equivalent of isocyanate group,

[0013] A polymer containing silane groups is provided.

[0014] "Monomeric diisocyanate" refers to an organic compound having two isocyanate groups separated by a divalent hydrocarbyl radical having 4 to 15 carbon atoms.

[0015] "NCO content" refers to the content of isocyanate groups in weight percent.

[0016] "Organosilane," or "silane" for short, refers to an organic compound having at least one silane group.

[0017] "Alkoxysilane group" or, in short, "silane group" refers to a silyl group that is bonded to an organic radical and has one to three, particularly two or three, hydrolyzable alkoxy radicals on a silicon atom.

[0018] "Aminosilane," "mercaptosilane," or "hydroxysilane" each refer to an organic silane having an amino, mercapto, or hydroxyl group on an organic radical in addition to a silane group.

[0019] "Molecular weight" refers to the molar mass (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) on polystyrene as a standard.

[0020] In relation to reactors, the term "molar ratio" refers to the ratio of the number of molar equivalents of the corresponding reactor.

[0021] In the formula for each case, the dotted line represents the bond between the substituent and the corresponding molecular radical.

[0022] A "plasticizer" refers to a non-volatile substance that exerts a plasticizing effect on a cured polymer without being chemically incorporated into the polymer during the curing process.

[0023] A “substance” or “composition” is referred to as “storage-stable” or “storable” when it can be stored in a suitable container at room temperature for a long period, generally from at least 3 months to a maximum of 6 months, without any change in its application or use characteristics to the extent related to use as a result of storage.

[0024] "Room temperature" indicates a temperature of 23℃.

[0025] All industry standards and norms mentioned in this specification relate to the versions valid on the date of the first filing.

[0026] Weight percentage (wt%), abbreviated as wt%, refers to the mass ratio of a component of a composition or molecule relative to the total composition or total molecule, unless otherwise noted. The terms "mass" and "weight" are used synonyms in this document.

[0027] The polymer of the present invention containing silane groups does not have isocyanate groups.

[0028] This is a liquid with low viscosity, especially at room temperature. In particular, it can be handled efficiently at room temperature without dilution with plasticizers or solvents.

[0029] Polymers containing silane groups are preferably essentially free of plasticizers and solvents. In particular, they contain less than 1 weight percent of a plasticizer. When used in curable compositions, such polymers allow complete freedom regarding whether the composition must contain a plasticizer, how much, and what kind of plasticizer.

[0030] A polymer containing a silane group preferably has a silane group of formula (I):

[0031]

[0032] In the above formula,

[0033] b is 0, 1, or 2, specifically 0 or 1, and

[0034] R 1 is an alkyl radical having 1 to 10 carbon atoms and optionally containing an ether group, and

[0035] R 2 is a divalent hydrocarbyl radical having 1 to 12 carbon atoms having optionally a cyclic and / or aromatic moiety and optionally one or more heteroatoms, in particular an amido, carbamate, or morpholino group, and

[0036] X is O, S, or NR 3 and, here R 3It is a monovalent hydrocarbyl radical having 1 to 20 carbon atoms, optionally having a heteroatom in the form of H or an alkoxysilyl, ether, or carboxylic acid ester group.

[0037] Preferably, R 1 It is methyl, ethyl, or isopropyl.

[0038] More preferably, R 1 It is methyl. This type of polymer containing silane groups is particularly reactive.

[0039] More preferably, also, R 1 It is ethyl. These polymers containing silane groups are particularly stable during storage and toxicologically advantageous.

[0040] Preferably, X is O or NR 3 am.

[0041] Preferably, R 3 is an aliphatic hydrocarbyl radical having H, ethyl, butyl, phenyl, or 6 to 20 carbon atoms, optionally an ether or carboxylic acid group.

[0042] Most preferably, X is NR 3 and R 3 silver and, here R 4 It is methyl or ethyl, especially ethyl.

[0043] X = NR 3 In the case of, R 2 is preferably 1,3-propylene, 1,3-butylene or 1,4-butylene, where butylene can be substituted with one or two methyl groups, and more preferably 1,3-propylene.

[0044] If X = O, R 2 is preferably a divalent hydrocarbyl radical having 6 to 12 carbon atoms and an amido, carbamate, or morpholino group, particularly a chemical formula It is a radical.

[0045] The desirable silane group of chemical formula (I) enables high strength combined with high elongation.

[0046] Polymers containing silane groups have an average of 1.3 to 4, more preferably 1.5 to 3.5, and particularly 1.7 to 3.5 silane groups per molecule.

[0047] A particularly preferred polymer containing silane groups is linear and has an average of 1.7 to 2, preferably 1.8 to 2, and particularly 1.9 to 2 silane groups per molecule. Such a polymer enables particularly high elongation.

[0048] A particularly preferred polymer containing silane groups is branched and has an average of 2.1 to 3, preferably 2.2 to 3, silane groups per molecule.

[0049] The polymer containing silane groups preferably has an average molecular weight M in the range of 3,000 to 30,000 g / mol, preferably 5,000 to 20,000 g / mol. n has

[0050] A polymer containing isocyanate groups from which a polymer containing silane groups is derived preferably has an NCO content in the range of 0.3% to 3.5% by weight, particularly 0.4% to 2.5% by weight.

[0051] The polymer containing isocyanate groups preferably has an average molecular weight M in the range of 2,500 to 30,000 g / mol, preferably 4,000 to 20,000 g / mol. n has

[0052] The polymer containing isocyanate groups preferably has a monomeric diisocyanate content of 0.25 weight% or less, preferably 0.2 weight% or less, and particularly 0.15 weight% or less.

[0053] Suitable monomeric diisocyanates include commercial aromatic or aliphatic diisocyanates, in particular diphenylmethane 4,4'-diisocyanate, tolylene 2,4-diisocyanate or mixtures thereof with tolylene 2,6-diisocyanate (TDI), optionally containing fractions of diphenylmethane 2,4'- and / or 2,2'-diisocyanate (MDI), 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. There are 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-xylylene diisocyanate (XDI), m-tetramethylxylylene diisocyanate (TMXDI), or mixtures thereof.

[0054] More preferably, the monomeric diisocyanate is selected from the group consisting of MDI, TDI, HDI, and IPDI.

[0055] Among these, IPDI is particularly preferred. The silane-containing polymer obtained in this way enables compositions with particularly low viscosity, particularly excellent processability, high elongation, and particularly excellent photostability.

[0056] Among these, MDI, particularly diphenylmethane 4,4'-diisocyanate (4,4'-MDI), is highly preferred. The silane-containing polymer obtained in this way enables compositions with surprisingly low viscosity, excellent processability, particularly high strength, and particularly excellent thermal stability. In contrast, silane-containing polymers prepared from conventional polymers containing isocyanate groups based on MDI have very high viscosity and must be diluted with a large amount of plasticizer or solvent to prevent gelation during preparation.

[0057] Suitable polyether polyols are preferably commercially available polyols that are liquid at room temperature.

[0058] The repeating units present in the polyether polyol are preferably 1,2-ethyleneoxy, 1,2-propyleneoxy, 1,3-propyleneoxy, 1,2-butyleneoxy, or 1,4-butyleneoxy groups. More preferably, they have 1,2-propyleneoxy groups mainly or exclusively. More specifically, they have 80 to 100 weight% of 1,2-propyleneoxy groups and 0 to 20 weight% of 1,2-ethyleneoxy groups based on all repeating units.

[0059] Polyoxyalkylene diols and / or polyoxyalkylene triols, in particular polymer products of ethylene oxide or 1,2-propylene oxide or 1,2- or 2,3-butylene oxide or oxetane or tetrahydrofuran or mixtures thereof are particularly suitable, wherein these are starting molecules having two or more active hydrogen atoms, in particular water, ammonia, or, for example, ethane-1,2-diol, propane-1,2- or -1,3-diol, neopentyl glycol, diethylene glycol, triethylene glycol, isomer dipropylene glycol or tripropylene glycol, isomer butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonandiol, decanediol, undecanediol, cyclohexane-1,3- or -1,4-dimethanol, bisphenol A, hydrogenated bisphenol A, Polymerization can be performed with the help of starter molecules, such as compounds having multiple OH or NH groups, such as 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol or aniline, or mixtures of the aforementioned compounds. Polyoxypropylene diols, polyoxypropylene triols, or ethylene oxide-terminated polyoxypropylene diols or triols are particularly preferred. These are polyoxyethylene / polyoxypropylene copolyols obtained by further alkoxylating the polyoxypropylene diol or triol with ethylene oxide at the end of the polypropoxylation reaction, as a result, they ultimately have primary hydroxyl groups. Polyether polyols having an unsaturated level of less than 0.02 meq / g, particularly less than 0.01 meq / g, are preferred.

[0060] Polyether polyols preferably have an OH value in the range of 5 to 58 mg KOH / g, particularly 6 to 40 mg KOH / g.

[0061] Polyether polyols preferably have an average molecular weight M in the range of 2,000 to 20,000 g / mol. n has

[0062] Polyether polyols preferably have an average OH functionality in the range of 1.7 to 3.

[0063] Polyether polyols are preferably polyether diols. These polymers containing silane groups enable compositions with particularly high elongation. Polyether diols preferably have an average OH functionality in the range of 1.7 to 2, preferably 1.8 to 2, and particularly 1.9 to 2. As a result of their production, commercial polyether diols contain a specific amount of monool, and consequently, their average OH functionality is generally slightly lower than 2. Polyether diols preferably have an OH value in the range of 5 to 58 mg KOH / g, and particularly 6 to 33 mg KOH / g.

[0064] Polyether diols having an OH value in the range of 5 to 20 mg KOH / g, particularly 6 to 15 mg KOH / g, are particularly preferred. Such polymers enable compositions having particularly high elongation and elasticity.

[0065] A polymer containing isocyanate groups made of polyether diol preferably has an NCO content in the range of 0.3% to 3.5% by weight, particularly 0.4% to 2.2% by weight.

[0066] In a preferred embodiment of the present invention, the polyether polyol is a polyether triol having an average OH function in the range of 2.2 to 3. As a result of their production, commercial polyether triols contain a specific amount of monool, and as a result, their average OH function is generally slightly lower than 3. These polymers containing silane groups enable compositions having particularly excellent thermal stability after curing.

[0067] Polyether triols preferably have an OH value in the range of 15 to 58 mg KOH / g, particularly 20 to 40 mg KOH / g.

[0068] A polymer containing isocyanate groups prepared from a polyether triol preferably has an NCO content in the range of 0.8% to 3.5% by weight, particularly 1.2% to 2.5% by weight.

[0069] Polymers containing silane groups derived from 4,4'-MDI as polyether triols and monomeric diisocyanates are highly particularly preferred. Since such polymers gel during the manufacturing process, they cannot be obtained by conventional means without adding large amounts of plasticizers or solvents. When used in proportion to moisture-curing compositions based on polymers containing silane groups, this enables a significant increase in strength along with increased elongation and improved thermal stability.

[0070] In the preparation of a polymer containing isocyanate groups, the NCO / OH molar ratio is preferably in the range of 3 / 1 to 20 / 1, more preferably in the range of 4 / 1 to 15 / 1, particularly 5 / 1 to 13 / 1.

[0071] The reaction is preferably carried out at a temperature in the range of 20 to 160°C, particularly 40 to 140°C, with moisture excluded in the presence of a suitable catalyst, optionally. After the reaction, the monomeric diisocyanate remaining in the reaction mixture is removed by a suitable separation method to the described residual content.

[0072] A preferred separation method is preferably a distillation method applying reduced pressure, in particular thin-film distillation or short-path distillation.

[0073] A multi-stage method for removing monomeric diisocyanates in a single-path evaporator having a jacket temperature in the range of 120 to 200°C and a pressure of 0.001 to 0.5 mbar is particularly preferred. For 4,4'-MDI, which is preferred as the monomeric diisocyanate, distillation removal is particularly difficult. For example, care must be taken to prevent the condensate from solidifying and clogging the system. It is preferable to perform the process at a jacket temperature in the range of 160 to 200°C at 0.001 to 0.5 mbar and to condense the removed monomeric diisocyanates at a temperature in the range of 40 to 60°C.

[0074] It is desirable to react a monomeric diisocyanate with a polyether polyol and subsequently remove most of the monomeric diisocyanate remaining in the reaction mixture without the use of solvents or entraining agents. It is also desirable to subsequently reuse the monomeric diisocyanate removed after the reaction, that is, to reuse it for the production of polymers containing isocyanate groups.

[0075] In the reaction, the OH groups of the polyether polyol react with the isocyanate groups of the monomeric diisocyanate. This also results in a chain extension reaction, in that there is a reaction between the OH groups and / or isocyanate groups of the reaction product between the polyol and the monomeric diisocyanate. The higher the selected NCO / OH ratio, the lower the level of the chain extension reaction occurring, the lower the polydispersity, and the lower the viscosity of the obtained polymer. Measures of the chain extension reaction are the average molecular weight of the polymer, or the peak width and distribution in GPC analysis. The effective NCO content of the monomer-free polymer is further measured relative to the theoretical NCO content calculated from the reaction of all OH groups with the monomeric diisocyanate.

[0076] The polymer containing isocyanate groups preferably contains only a low content of chain-extending components. The NCO content of the polymer is preferably at least 90%, particularly at least 95%, of the theoretical NCO content calculated from the addition of 1 mole of monomeric diisocyanate per 1 mole of OH groups of the polyether polyol.

[0077] The polymer containing isocyanate groups is in a liquid state, has low viscosity at room temperature, contains a low content of monomeric diisocyanate, and has very high storage stability due to the exclusion of moisture. It reacts with amino-, mercapto-, or hydroxysilane in a stoichiometric ratio of at least 1 amino-, mercapto-, or hydroxysilane per molar equivalent of isocyanate groups, thereby providing the polymer of the present invention containing silane groups.

[0078] The amino-, mercapto-, or hydroxysilane for reaction with a polymer containing an isocyanate group is preferably a silane of formula (II):

[0079]

[0080] In the above equation, R 1 , R 2 , X and b follow the previously given definitions.

[0081] 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)cyclohexan-1-ol, 2-morpholino-4(5)-(2-trimethoxysilylethyl)cyclohexan-1-ol, 1-morpholino-3-(3-(triethoxysilyl)propoxy)propan-2-ol, and corresponding analogs having an ethoxy group instead of a methoxy group of silicon.

[0082] 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. Amino-, mercapto-, or hydroxysilane reacts with a polymer containing an isocyanate group in a stoichiometric ratio of at least 1 mole of amino-, mercapto-, or hydroxysilane per molar equivalent of the isocyanate group. A stoichiometric range of 1 to 1.3, preferably 1 to 1.2, and particularly 1 to 1.1 moles per molar equivalent of the isocyanate group is preferred. The reaction is carried out at a temperature in the range of 20 to 160°C, particularly 60 to 120°C. A catalyst, particularly a tertiary amine or metal compound, particularly a bismuth (III), zinc (II), zirconium (IV), or tin (II) compound or an organotin (IV) compound, is optionally used.

[0083] A particularly preferred polymer containing silane groups is derived from a polyether triol, as previously described. This polymer containing silane groups has an average of more than 2 silane groups per molecule, preferably 2.1 to 4, particularly 2.2 to 3.5. This enables a composition having particularly excellent thermal stability after curing. It is preferably used in combination with an additional, preferably linear, polymer containing silane groups, which, together with the polymer of the present invention containing silane groups, enables particularly improved thermal stability.

[0084] A particularly desirable polymer containing a silane group is derived from IPDI as a monomeric diisocyanate. Thus, it has a silane group of formula (Ia) or (Ib) in particular:

[0085]

[0086]

[0087] In the above equation, R 1 , R 2 , X and b are defined according to the definition given earlier. These polymers enable high elongation and particularly high photostability, along with particularly excellent thermal stability.

[0088] Polymers containing silane groups derived from 4,4'-MDI as polyether triols and monomeric diisocyanates are very particularly preferred.

[0089] Therefore, this has a silane group of the chemical formula (Ic) in particular.

[0090]

[0091] In the above equation, R 1 , R 2 , X and b follow the previously given definitions.

[0092] Since these polymers gel during the manufacturing process, they cannot be obtained by conventional means without adding a large amount of plasticizer or solvent. This enables compositions with particularly high strength and particularly excellent thermal stability. More preferably, this is used in combination with additional, preferably linear, polymers containing silane groups, which enables improved strength and improved thermal stability along with very high elongation.

[0093] Polymers containing silane groups are storage-stable as they exclude moisture. Upon contact with moisture, the silane groups hydrolyze. This forms silanol groups (Si-OH groups) and, through a subsequent condensation reaction, forms siloxane groups (Si-O-Si groups). As a result of these reactions, the polymer cures to produce a cross-linked plastic. The moisture for curing can come from the air (air humidity), or the polymer may come into contact with moisture-containing components, for example, through 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 the adhesion of the cross-linked material to the substrate.

[0094] The present invention further provides a method for manufacturing a polymer containing silane groups, and

[0095] (a) at least one monomeric diisocyanate is reacted with at least one polyether polyol having an OH value in the range of 5 to 58 mg KOH / g, particularly 6 to 40 mg KOH / g, at a molar ratio of at least 3 / 1 NCO / OH, and

[0096] (b) Then, most of the unconverted monomeric diisocyanate is removed by an appropriate separation method, and

[0097] (c) The obtained polymer containing isocyanate groups is finally reacted with at least one amino-, mercapto-, or hydroxysilane in a stoichiometric ratio of at least 1 mole of amino-, mercapto-, or hydroxysilane per molar equivalent of isocyanate groups.

[0098] The present invention further provides a curable composition comprising one or more additional components selected from the group consisting of the polymer of the present invention containing silane groups and catalysts, crosslinking agents, adhesion promoters, drying agents, plasticizers, and fillers.

[0099] Suitable catalysts are metal catalysts and / or nitrogen compounds that promote the crosslinking of polymers containing silane groups. Suitable metal catalysts are particularly compounds of titanium, zirconium, aluminum, or tin, particularly organotin compounds, organotitanates, organozirconates, or organaluminates, and these compounds particularly have alkoxy groups, aminoalkoxy groups, sulfonate groups, carboxyl groups, 1,3-diketonate groups, 1,3-ketoesterate groups, dialkyl phosphate groups, or dialkyl pyrophosphate groups.

[0100] Particularly suitable organotin compounds are dialkyltin oxides, dialkyltin dichlorides, dialkyltin dicarboxylates and dialkyltin diketons, 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 thioesters.

[0101] Particularly suitable organic titanates are bis(ethylacetoaceto)diisobutoxytitanium(IV), bis(ethylacetoaceto)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 available from Dorf Ketal); Tytan PBT, TET, X85, TAA, ET, S2, S4, or S6 (all available 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 available from Kenrich Petrochemicals) is particularly suitable.

[0102] A particularly suitable organozirconate is the commercially available product Ken-React ® NZ ® 38J, KZ ® TPPJ, KZ ® TPP, NZ ® 01, 09, 12, 38, 44, or 97 (all available from Kenrich Petrochemicals) or Snapcure ® 3020, 3030, and 1020 (all available from Johnson Matthey & Brandenberger).

[0103] A particularly suitable organic aluminate is the commercially available product K-Kat 5218 (available from King Industries).

[0104] Nitrogen compounds suitable as catalysts are particularly amines, e.g., particularly N-ethyldiisopropylamine, N,N,N',N'-tetramethylalkylenediamine, polyoxyalkyleneamine, 1,4-diazabicyclo[2.2.2]octane; aminosilanes, e.g., particularly 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-N'-[3-(trimethoxysilyl)propyl]ethylenediamine or analogs 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 of carbodiimide and amine, 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.

[0105] A combination of different catalysts, in particular a combination of at least one metal catalyst and at least one nitrogen compound, is also suitable.

[0106] Preferred catalysts are organotin compounds, organotitanates, amines, particularly aminosilanes, amidines, guanidines, or imidazoles.

[0107] Suitable adhesion promoters and / or crosslinking agents are, in particular, aminosilanes, mercaptosilanes, epoxysilanes, (meth)acrylosilanes, anhydridosilanes, carbamatosilanes, alkylsilanes or iminosilanes, or oligomeric forms of these silanes, or adducts of primary aminosilanes and epoxysilanes or (meth)acrylosilanes or anhydridosilanes. Particularly suitable are 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 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 a silicon, or oligomeric forms of these silanes.

[0108] Particularly suitable desiccants 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. Here, vinyltrimethoxysilane is preferred when the polymer containing the silane group has a methoxysilane group, and vinyltriethoxysilane is preferred when the polymer containing the silane group has an ethoxysilane group.

[0109] Suitable plasticizers are, in particular, carboxyl esters, 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 bis(2-ethylhexyl) terephthalate or bis(2-ethylhexyl) cyclohexane-1,4-dicarboxylate, or hydrogenated diisononyl terephthalate or diisononyl It is in the form of cyclohexane-1,4-dicarboxylate, isophthalate, trimellitate, adipate, particularly dioctyl adipate, azelate, sebacate, benzoate, polyol, particularly polyether polyol or polyester polyol, glycol ether, glycol ester, polyether mono- or polyol having blocked hydroxyl groups, particularly acetate groups, organic phosphate or sulfonic acid esters, polybutene or natural fats or oils, particularly fatty acid methyl or ethyl esters also known as "biodiesel," or plasticizers derived from epoxidized soybean or linseed oil.

[0110] Suitable fillers are, in particular, ground or precipitated calcium carbonate coated with optional fatty acids, particularly stearates; barites; quartz powder; quartz sand; dolomite; wollastonite; calcined kaolin; sheet silicates, such as mica or talc; zeolites; silica, including aluminum hydroxide, magnesium hydroxide, and finely divided silica from a pyrolysis process; cement; gypsum; fly ash; industrially produced carbon black; graphite; metal powders, for example, aluminum, copper, iron, silver, or steel; PVC powder; or hollow beads. Precipitated fatty acid-coated calcium carbonate and / or carbon black are preferred.

[0111] Additionally suitable components include the following auxiliary agents and additives:

[0112] - Additional oligomers or polymers containing silane groups;

[0113] - Solvent;

[0114] - Fibers, particularly glass fibers, carbon fibers, metal fibers, ceramic fibers, polymer fibers, such as polyamide fibers or polyethylene fibers, or natural fibers, such as wool, cellulose, hemp, or sisal;

[0115] - Nanofillers such as graphene or carbon nanotubes;

[0116] - Dyes;

[0117] - Inorganic or organic pigments, particularly titanium dioxide, chrome oxide, or iron oxide;

[0118] - Rheology modifiers, in particular thickeners, in particular 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;

[0119] - Stabilizer against oxidation, heat, light, or UV radiation;

[0120] - Natural resins, fats, or oils, such as rosin, shellac, linseed oil, castor oil, or soybean oil;

[0121] - Non-reactive polymers, in particular homopolymers or copolymers of unsaturated monomers, in particular those 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);

[0122] - Flame-retardant materials, in particular the previously mentioned fillers aluminum hydroxide or magnesium hydroxide, or organophosphate esters;

[0123] - Additives, in particular wetting agents, leveling agents, defoaming agents, degassing agents, stabilizers against oxidation, heat, light or UV radiation, or biocides.

[0124] It may be desirable to apply specific components to chemical or physical drying before mixing them into the composition.

[0125] 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 polymer containing silane groups.

[0126] In a preferred embodiment of the present invention, the curable composition comprises at least one polymer containing a silane group of the present invention derived from a polyether triol and at least one additional polymer containing a silane group, particularly a linear silane group.

[0127] The weight ratio between the polymer of the present invention containing silane groups derived from a polyether triol and an additional polymer containing silane groups is preferably in the range of 10 / 90 to 70 / 30, particularly 15 / 85 to 60 / 40.

[0128] The additional polymer containing silane groups is preferably,

[0129] - Polymer of the present invention containing silane groups derived from polyether diols;

[0130] - A polymer containing silane groups derived from a polymer containing isocyanate groups from the reaction of a monomeric isocyanate and a polyether polyol, particularly a diol, in an NCO / OH molar ratio in the range of 1.3 to 2.5 / 1, particularly 1.8 to 2.5 / 1, without the subsequent removal of the monomeric diisocyanate;

[0131] - A polyether containing an allyl group and a polyether containing a silane group obtained from the reaction with a hydrosilane, in particular a diisocyanate, optionally having a chain extension;

[0132] - A polyether containing a silane group obtained from copolymerization with an alkylene oxide and an epoxysilane having optional chain extension, in particular with a diisocyanate;

[0133] - Polyether polyols involving chain extension using optional diisocyanates, in particular polyethers containing silane groups obtained from the reaction of a diol with an isocyanatosilane,

[0134] It is selected from a group consisting of.

[0135] The polymer of the present invention containing silane groups derived from polyether triols particularly improves the thermal stability of the composition and possibly its strength and / or elongation.

[0136] The curable composition is manufactured specifically to exclude moisture and stored in a moisture-tight container at room temperature. Suitable moisture-tight containers are made of optionally coated metal and / or plastic, specifically drums, transport boxes, hobbocks, buckets, canisters, cans, bags, tubular bags, cartridges, or tubes.

[0137] A curable composition may be in the form of a one-component composition or a two-component composition. A "one-component" composition refers to a composition in which all components of the composition are mixed and stored together in the same container and cured by moisture. A "two-component" composition refers to a composition in which the components of the composition exist as two different components stored in separate containers. The two components are not mixed with each other immediately before or during the application of the composition, so that when the mixed composition is cured, the curing proceeds or is completed solely by the action of moisture.

[0138] The curable composition is preferably a one-component composition. If proper packaging and storage are provided, it generally has storage stability for several months to up to one year or longer.

[0139] When a curable composition is applied, the present silane groups come into contact with moisture, initiating the curing process. Curing proceeds at different rates depending on temperature, the type of contact, the amount of moisture, and the presence of any catalyst. In the case of curing by air humidity, a film is first formed on the surface of the composition. Skin time is a measure of the curing speed. This results in the cured composition.

[0140] 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 or releasing water and / or a catalyst and / or a curing agent may be mixed into the composition at the time of application, or the composition may be brought into contact with such an accelerator component after application. The curable composition is preferably applied at ambient temperatures, 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. Curing is preferably performed at ambient temperatures as well.

[0141] In the cured state, the composition possesses remarkable elastic properties, particularly high strength and high elongation, excellent thermal stability, and excellent adhesion to various substrates. As a result, it is suitable for many 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, or glazing adhesive; as a bodywork sealant, seam sealant, or cavity sealant; and as a floor covering, floor coating, balcony coating, roof coating, or parking lot coating.

[0142] It is preferable to use a curable composition as an elastic adhesive, elastic sealant, or elastic coating.

[0143] The curable composition can be formulated to have a paste-like consistency with structurally viscous properties. This type of composition is applied, for example, by a commercial cartridge in the form of a bead, which may essentially have a circular or triangular cross-section, or by a suitable device such as a keg or hobbock. The curable composition can also be formulated to be fluid and "self-leveling" or slightly thixotropic and pourable for application. As a coating, it can be distributed continuously and flatly, for example, to a desired layer thickness, using a roller, slide bar, toothed applicator, or trowel. In one operation, a layer thickness typically ranging from 0.5 to 3 mm, particularly from 1 to 2.5 mm, is applied.

[0144] In particular, as a substrate suitable for bonding, sealing, or coating,

[0145] - Glass, glass ceramics, screen-printed ceramics, concrete, mortar, cement screed, fiber cement, especially fiber cement boards, bricks, tiles, gypsum, especially gypsum boards or anhydride screeds, or natural stone such as granite or marble;

[0146] - Non-ferrous metals including metals or alloys, such as aluminum, copper, iron, steel, and surface-finished metals or alloys, such as zinc-plated or chrome-plated metals;

[0147] - 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;

[0148] - Paint or varnish, especially automotive topcoat;

[0149] - Repair or leveling compound based on PCC (polymer-modified cement mortar) or ECC (epoxy resin-modified cement mortar);

[0150] - Asphalt or bitumen;

[0151] - Leather, fabric, paper, wood, resin, wood materials combined with, for example, phenol, melamine, or epoxy resin, additional materials referred to as resin / fabric composites or polymer composites;

[0152] - In particular, there are insulation foams made of EPS, XPS, PUR, PIR, rock wool, glass wool, or foamed glass.

[0153] 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.

[0154] It is possible to combine or seal two identical or two different materials.

[0155] After combining or sealing two materials, a combined or sealed article is obtained. This article may be a building structure or part thereof, particularly a civil engineering building structure above or below ground, a bridge, a roof, a staircase, or a facade, or an industrial 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 component thereof.

[0156] In one embodiment, the curable composition further comprises at least one epoxy resin. This composition preferably has two components. It comprises, in particular, at least one additional component selected from aminosilanes, epoxysilanes, vinylsilanes, polyamines having two or three primary or secondary aliphatic amino groups, and an accelerator for the reaction of epoxy groups. It optionally further comprises water. It is preferable that the compound having amino groups and the epoxy resin are not the same component.

[0157] The weight ratio of the polymer containing silane groups to the epoxy resin is preferably in the range of 20 / 80 to 70 / 30.

[0158] These compositions exhibit particularly high strength, with a high content of epoxy resin enabling particularly very high strength, and a polymer containing a high content of silane groups enabling high elongation and elasticity along with high strength.

[0159] Suitable epoxy resins are liquid epoxy resins that are free-flowing at room temperature and have a glass transition temperature of less than 25°C. Liquid epoxy resins based on bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, or bisphenol A / F diglycidyl ether, which optionally contain a certain proportion of solid bisphenol A resin or phenol novolak, are preferably of technical grade quality and are commercially available, for example, from Dow, Huntsman, or Momentive.

[0160] Silanes particularly suitable for such compositions include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, vinyltrimethoxysilane, or vinyltriethoxysilane.

[0161] Suitable polyamines include, in particular, 2,2-dimethylpropane-1,3-diamine, pentane-1,3-diamine (DAMP), pentane-1,5-diamine, 1,5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethylpentane-1,5-diamine (C11 neodiamine), hexane-1,6-diamine, 2,5-dimethylhexane-1,6-diamine, 2,2(4),4-trimethylhexamethylenediamine (TMD), heptane-1,7-diamine, octane-1,8-diamine, nonane-1,9-diamine, decane-1,10-diamine, undecane-1,11-diamine, dodecane-1,12-diamine, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine or IPDA), 2(4)-methyl-1,3-diaminocyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, bis(4-amino-3-ethylcyclohexyl)methane, bis(4-amino-3,5-dimethylcyclohexyl)methane, bis(4-amino-3-ethyl-5-methylcyclohexyl)methane, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane (NBDA), 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0 2,6] Decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), menthan-1,8-diamine, 1,3-bis(aminomethyl)benzene (MXDA) or 1,4-bis(aminomethyl)benzene, 3-(2-aminoethyl)aminopropylamine, bis(hexamethylene)triamine (BHMT), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA) or higher homologues of linear polyethyleneamine, dipropylenetriamine (DPTA), N-(2-aminoethyl)propane-1,3-diamine (N3 amine), N,N'-bis(3-aminopropyl)ethylenediamine (N4 amine), N,N'-bis(3-aminopropyl)-1,4-diaminobutane, N5-(3-aminopropyl)-2-methylpentane-1,5-diamine, N3-(3-aminopentyl)pentane-1,3-diamine, N5-(3-amino-1-ethylpropyl)-2-methylpentane-1,5-diamine or N,N'-bis(3-amino-1-ethylpropyl)-2-methylpentane-1,5-diamine, 2-aminoethylpiperazine, 3-dimethylaminopropylamine (DMAPA), N,N-dimethyldi(1,3-propylene)triamine (DMAPAPA), N,N'-bis(aminoethyl)piperazine, N,N'-bis(aminopropyl)piperazine, N,N-bis(3-aminopropyl)methylamine, N,N-bis(3-aminopropyl)ethylamine, 4-aminomethyloctane-1,8-diamine, 1,3,5-tris(aminomethyl)benzene, 1,3,5-Tris(aminomethyl)cyclohexane, Tris(2-aminoethyl)amine, Tris(2-aminopropyl)amine, Tris(3-aminopropyl)amine, N-Benzylethane-1,2-Diamine, N-Benzylpropane-1,2-Diamine, N-Benzyl-1,3-Bis(aminomethyl)benzene, N-2-ethylhexyl-1,3-Bis(aminomethyl)benzene, N-(2-phenylethyl)-1,3-Bis(aminomethyl)benzene, 3,6-Dioxaoctane-1,8-Diamine, 4,7-Dioxadecane-1,10-Diamine, 4,7-Dioxadecane-2,9-Diamine, 4,9-Dioxadodecane-1,12-Diamine, 5,8-Dioxadodecane-3,10-Diamine, 4,7,10-trioxatridecane-1,13-diamines or higher oligomers of these diamines, bis(3-aminopropyl)polytetrahydrofuran or other polytetrahydrofurandiamines, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, polyoxyalkylenedi- or -triamines, particularly Jeffamine, ® D-230, Jeffamine ® D-400, Jeffamine ® D-2000, Jeffamine ® EDR-104, Jeffamine ® EDR-148, Jeffamine ® EDR-176, Jeffamine ® T-403, Jeffamine ® T-3000, Jeffamine ® There are T-5000 (all available from Huntsman), or these or additional polyamines and epoxy resins or monoepoxides, such as, in particular, adducts of cresyl glycidyl ether, and also called polyamidoamines or Mannich bases, in particular phenalkamines.

[0162] MPMD, TMD, 1,2-Diaminocyclohexane, 1,3-Diaminocyclohexane, 1,4-Diaminocyclohexane, 1,3-Bis(aminomethyl)cyclohexane, 1,4-Bis(aminomethyl)cyclohexane, IPDA, 2(4)-Methyl-1,3-Diaminocyclohexane, Bis(4-aminocyclohexyl)methane, NBDA, MXDA, BHMT, TETA, TEPA, N4 amine, DMAPAPA, N-Benzylethane-1,2-Diamine, average molecular weight M in the range of 200 to 500 g / mol n Polyoxypropylenediamine or -triamine having, or MPMD or adducts of propane-1,2-diamine and cresyl glycidyl ether are preferred.

[0163] Promoters suitable for the reaction of epoxy groups include, in particular, acids or compounds that can be hydrolyzed by acids, particularly organic carboxylic acids such as salicylic acid, organic sulfonic acids such as p-toluenesulfonic acid, sulfonic acid esters, phosphoric acids, or nitrates such as calcium nitrate, or tertiary amines such as 1,4-diazabicyclo[2.2.2]octane, triethanolamine, imidazoles such as N-methylimidazole, N-vinylimidazole, or 1,2-dimethylimidazole, amidin or guanidine, phenols, Mannich bases such as 2,4,6-tris(dimethylaminomethyl)phenol, or compounds having mercapto groups.

[0164] More preferably, the epoxy resin-containing curable composition comprises at least one aminosilane and optionally a vinylsilane, optionally 2,4,6-tris(dimethylaminomethyl)phenol, optionally a polyamine and optionally a tin catalyst.

[0165] These epoxy resin-containing curable compositions are cured by mixing the two components of the composition together and bringing the composition into contact with moisture. The present silane groups react with moisture as described above, and the present epoxy groups react with primary or secondary amino groups and / or each other, and the aminosilanes can link the polyether polymer phase and the epoxy resin phase to each other through the silane groups and through the amino groups. As a result, high-quality materials with high strength, impact resistance, and stability are produced, and depending on the ratio between the silane-containing polymer and the epoxy resin, the elongation and elasticity may increase or decrease.

[0166] The present invention further provides a cured composition obtained from a curable composition after contacting the curable composition with moisture.

[0167] Examples

[0168] Working embodiments for further explaining the described invention are presented below. The invention is, of course, not limited to these described working embodiments.

[0169] "Standard climate conditions" ("SCC") represent a temperature of 23±1℃ and a relative humidity of 50±5%.

[0170] Unless otherwise specified, chemicals from Sigma-Aldrich were used.

[0171] Diisodecyl phthalate in the form of Palatinol® 10-P (from BASF) was used.

[0172] viscosity The temperature-controlled Rheotec RC30 cone-plate viscometer (cone diameter 25 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 10 s -1 Measured as ).

[0173] Monomeric diisocyanates Content After pre-derivation with N-propyl-4-nitrobenzylamine, it was determined by HPLC (detection via photodiode array; 0.04 M sodium acetate / acetonitrile as mobile phase).

[0174] Preparation of a polymer containing isocyanate groups by removing monomers:

[0175] Polymer D-1:

[0176] Polyoxypropylene diol (OH value 10 mg KOH / g, Acclaim ® 12200N, obtained from Covestro) 812.0 g (0.15 equivalents (eq) OH) and IPDI (1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, Vestanat ®166.6 g (1.5 equivalents of NCO) (IPDI, obtained from Evonik) was reacted at 80°C by a known method to obtain a polymer having an NCO content of 5.7 wt%, a viscosity of 11.0 Pa·s at 20°C, and a monomer IPDI content of about 9.5 wt%. Subsequently, most of the volatile components, particularly the monomer IPDI, were removed by distillation in a short-distance evaporator (jacket temperature 160°C, pressure 0.1 to 0.005 mbar). The linear polymer obtained accordingly exhibited an NCO content of 0.85 wt%, a viscosity of 19.1 Pa·s at 20°C, and a monomer IPDI content of 0.06 wt%.

[0177] Polymer D-2:

[0178] Ethylene oxide-terminated polyoxypropylene triol (OH value 28 mg KOH / g, Desmophen ® 725.0 g of 5031 BT (obtained from Covestro) and 275 g of diphenylmethane 4,4'-diisocyanate (Desmodur 44 MC L, obtained from Covestro) were converted at 80°C according to a known method into a polymer having a 7.6 wt% NCO content, a viscosity of 6.5 Pa·s at 20°C, and a monomer diphenylmethane 4,4'-diisocyanate content of about 20 wt%. Subsequently, most of the volatile components, particularly the monomer diphenylmethane 4,4'-diisocyanate, were removed by distillation in a short-range evaporator (jacket temperature 180°C, pressure 0.1 to 0.005 mbar, condensation temperature 47°C). The polymer obtained accordingly exhibited 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%.

[0179] Polymer D-3:

[0180] Ethylene oxide-terminated polyoxypropylene triol (OH value 28 mg KOH / g, Desmophen ®5031 BT, obtained from Covestro) 780.0g and IPDI (1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, Vestanat ® 220 g of IPDI (obtained from Evonik) was converted into a polymer having a monomer IPDI content of 6.4 wt%, a viscosity of 4.1 Pa·s at 20°C, and about 12 wt% by a known method at 80°C in the presence of 0.01 g of dibutyltin dilaurate. Subsequently, volatile components, particularly most of the monomer IPDI, were removed by distillation in a short-range evaporator (jacket temperature 160°C, pressure 0.1 to 0.005 mbar). The polymer obtained accordingly exhibited a monomer IPDI content of 1.9 wt%, a viscosity of 8.2 Pa·s at 20°C, and 0.02 wt%.

[0181] Polymer D-4:

[0182] Polyoxypropylene diol (OH value 28 mg KOH / g, Acclaim ® 727.0 g of diphenylmethane 4,4'-diisocyanate (4200, obtained from Covestro) and 273.0 g of diphenylmethane 4,4'-diisocyanate (Desmodur 44 MC L, obtained from Covestro) were converted at 80°C by a known method into a polymer having an NCO content of 7.4 wt%, a viscosity of 5.2 Pa·s at 20°C, and a monomeric diphenylmethane 4,4'-diisocyanate content of about 17 wt%. Subsequently, most of the volatile components, particularly the monomeric diphenylmethane 4,4'-diisocyanate, were removed by distillation in a short-range evaporator (jacket temperature 180°C, pressure 0.1 to 0.005 mbar, condensation temperature 47°C). The linear polymer obtained accordingly exhibited an NCO content of 1.8 wt%, a viscosity of 13.3 Pa·s at 20°C, and a monomeric diphenylmethane 4,4'-diisocyanate content of 0.08 wt%.

[0183] iso Preparation of conventional polymers containing cyanate groups:

[0184] Polymer C-1: (NCO / OH = 2.1 / 1)

[0185] Polyoxypropylene diol (OH value 10 mg KOH / g, Acclaim ® 12200N (obtained from Covestro) 1000.0g, diisodecyl phthalate 122.8g, IPDI (1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, Vestanat ® 41.6 g of IPDI (obtained from Evonik) and 0.12 g of dibutyltin dilaurate were converted into 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% by a known method at 90°C.

[0186] Polymer C-2: (NCO / OH = 2.1 / 1)

[0187] Ethylene oxide-terminated polyoxypropylene triol (OH value 28 mg KOH / g, Desmophen ® 190.0 g of 5031 BT (obtained from Covestro) and diphenylmethane 4,4'-diisocyanate (Desmodur ® 25.0 g of 44 MC L (obtained from Covestro) was converted at 80°C by a known method. The reaction mixture gelled during the reaction and was not suitable for further use.

[0188] Silane of the chemical formula (II) used :

[0189] Silan A-1 Ethyl N-(3-trimethoxysilylpropyl)aminosuccinate (351.5 g / mol) obtained by reacting 3-aminopropyltrimethoxysilane and diethyl maleate in a molar ratio of about 1 / 1

[0190] Silane A-2Diethyl N-(3-triethoxysilylpropyl)aminosuccinate (393.6 g / mol) obtained by reacting 3-aminopropyltriethoxysilane and diethyl maleate in a molar ratio of about 1 / 1

[0191] Silane A-3 N-(3-diethoxymethylsilylpropyl)-2-hydroxypropanamide (263.4 g / mol) obtained by reacting 3-aminopropyldiethoxymethylsilane and L-lactide in a molar ratio of about 2 / 1

[0192] Silane Preparation of a polymer containing:

[0193] Polymer S-1: (The present invention)

[0194] 300g of, prepared as described above Polymer D-1 In the initial packing of, 25.1g of under a moisture-excluded nitrogen atmosphere Silane A-2 ...was added, and the mixture was stirred at 60°C until isocyanate groups were no longer detected via FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored in a moisture-free environment. It was transparent and exhibited a viscosity of 40 Pa·s at 20°C the day after preparation.

[0195] Polymer S-2: (The present invention)

[0196] 300g of, prepared as described above Polymer D-1 In the initial packing of 16.8g under a moisture-excluded nitrogen atmosphere Silane A-3 and 0.06g of Bi catalyst (Coscat ® 83 (obtained from Vertellus) was added, and the mixture was stirred at 80°C until no further isocyanate groups were detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored in a moisture-free environment. It was transparent and exhibited a viscosity of 90 Pa·s at 20°C the day after preparation.

[0197] Polymer S-3: (The present invention)

[0198] 247.0g of, prepared as described above Polymer D-2 In the initial packing of 36.2g under a moisture-excluded nitrogen atmosphere Silan A-1 ...was added, and the mixture was stirred at 60°C until no further isocyanate groups were detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored in a moisture-free environment. It was transparent and exhibited a viscosity of 357 Pa·s at 20°C on the day after preparation.

[0199] Polymer S-4: (The present invention)

[0200] 221.0g of, prepared as described above Polymer D-3 In the initial packing of 36.2g under a moisture-excluded nitrogen atmosphere Silan A-1 ...was added, and the mixture was stirred at 60°C until no further isocyanate groups were detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored in a moisture-free environment. It was transparent and exhibited a viscosity of 70 Pa·s at 20°C the day after preparation.

[0201] Polymer S-5: (The present invention)

[0202] 233.3g of, prepared as described above Polymer D-4 In the initial packing of 36.2g under a moisture-excluded nitrogen atmosphere Silan A-1 ...was added, and the mixture was stirred at 60°C until no further isocyanate groups were detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored in a moisture-free environment. It was transparent and exhibited a viscosity of 108 Pa·s at 20°C on the day after preparation.

[0203] Polymer R-0: (comparison)

[0204] 333.3g of, prepared as described above Polymer C-1 In the initial packing of 18.1g under a moisture-excluded nitrogen atmosphere Silan A-1 ...was added, and the mixture was stirred at 60°C until no further isocyanate groups were detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored in a moisture-free environment. It contained 10 wt% of a plasticizer (diisodecyl phthalate), was transparent, and exhibited a viscosity of 99 Pa·s at 20°C on the day after preparation.

[0205] Polymer R-1: (comparison)

[0206] 333.3g of, prepared as described above Polymer C-1 In the initial packing of 20.2g under a moisture-excluded nitrogen atmosphere Silane A-2 ...was added, and the mixture was stirred at 60°C until no further isocyanate groups were detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored in a moisture-free environment. It contained approximately 10 wt% of a plasticizer (diisodecyl phthalate), was transparent, and exhibited a viscosity of 79 Pa·s at 20°C on the day after preparation.

[0207] Polymer R-2: (comparison)

[0208] 333.3g of, prepared as described above Polymer C-1 In the initial packing of, 13.6g of under a moisture-excluded nitrogen atmosphere Silane A-3 and 0.06g of Bi catalyst (Coscat ® 83 (obtained from Vertellus) was added, and the mixture was stirred at 80°C until no further isocyanate groups were detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored in a moisture-free environment. It contained 10 wt% of plasticizer (diisodecyl phthalate), was transparent, and exhibited a viscosity of 113 Pa·s at 20°C on the day after preparation.

[0209] Polymer SPUR-1: (comparison)

[0210] Desmophen ® 190.0 g of 5031 BT and 19.5 g of 3-isocyanatopropyltrimethoxysilane were converted into a silane-containing polymer at 80°C by a known method. The resulting polymer was cooled to room temperature and stored in a moisture-free environment. It was transparent and exhibited a viscosity of 5 Pa·s at 20°C on the day following preparation.

[0211]

[0212] Moisture-curing composition:

[0213] Compositions Z1 to Z12:

[0214] For each composition, the ingredients specified in Tables 2 and 3 were mixed in specified amounts (parts by weight) using a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) with moisture exclusion for 1 minute at 3000 rpm, and stored in a state with moisture excluded.

[0215] The composition was tested as follows:

[0216] As a measure of storage stability, viscosity After storing in a sealed aluminum tube with moisture excluded at room temperature for 1 day ( 1d RT ), after storing in an air-circulating oven at 60℃ for 7 days ( 7d 60℃ ) measured.

[0217] Skin time as a measure of open time ( ST ) was measured. To do this, under standard climate conditions, a few grams of the composition were applied to a cardboard layer about 2 mm thick, and the time at which no residue remained on the LDPE pipette used to gently tap the surface of the composition was determined.

[0218] As a measure of hardness and thermal stability, Shore AHardness was determined according to DIN 53505 for a test specimen (7d SCC) cured for 7 days under standard climate conditions, or for a test specimen cured for 7 days under standard climate conditions and then stored for a specified time at a specified temperature in an air-circulating oven at 80°C, 90°C, or 100°C.

[0219] To determine mechanical properties, the composition was applied to a silicone-coated release liner to produce a 2 mm thick film, the film was stored for 14 days under standard climatic conditions, and several dumbbells measuring 75 mm in length with a bar length of 30 mm and a bar width of 4 mm were punched out of the film and these tensile strength (Breaking force), Breaking elongation and MoE 5% (at an elongation rate of 0.5%-5%) and MoE 50% Tested according to DIN EN 53504 at a strain rate of 200 mm / min for (at 0.5%–50% elongation). As a measure of adhesive bond strength, lap shear strength ( LSS ) was determined in the glass. To this end, the overlapping adhesive bond was degreased with isopropanol so that the glass plate protruded from the upper end having dimensions of 12 x 25 mm and a thickness of 4 mm, and Sika ® A combined test specimen was prepared by combining two glass plates pretreated with Aktivator 205 (Sika Schweiz AG). After a storage time of 14 days under standard climate conditions, the lap shear strength was determined according to DIN EN 1465 at a strain rate of 20 mm / min.

[0220] The results are reported in Tables 2 and 3.

[0221] Comparative example is ( Ref. It is confirmed as ).

[0222]

[0223]

[0224] From Table 3, the composition of the present invention Z8inside Z10 and Z12 While exhibiting excellent thermal stability, the comparative composition Z7 and Z11 It is evident that it exhibits inadequate thermal stability. After storage at 90°C for 14 days and at 100°C for 7 days, the Shore A test specimen was destroyed to the point where measurement was impossible.

[0225] 2-component composition containing epoxy resin:

[0226] Compositions Z13 and Z14:

[0227] For each composition, 62.2 parts by weight (PW) of a polymer containing silane groups as specified in Table 4, 1.4 PW of diisodecyl phthalate, 2.4 PW of vinyltrimethoxysilane, and 27.4 PW of 1,2-diaminocyclohexane (Dytek ® DCH-99 (available from Invista), 2.3 PW of 3-aminopropyltrimethoxysilane, 2.3 PW of 2,4,6-tris(dimethylaminomethyl)trisphenol (Ancamine® K54, available from Evonik), 0.4 PW of stabilizer (Irganox 1010, available from BASF), 1.5 PW of carbon black, and 0.1 PW of dibutyltin dilaurate were mixed using a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) to the first Ingredient 1 Manufactured and stored the mixture without moisture.

[0228] For each composition, 70.2 PW bisphenol A diglycidyl ether (Araldite ® GY 250, obtained from Huntsman), 23.4 PW Hexanediol Diglycidyl Ether (Araldite ® DY-H, obtained from Huntsman), 0.5 PW emulsifier, 1.9 PW water, 2.4 PW fuming silica, 1.5 PW carbon black, and 0.1 PW dibutyltin dilaurate were treated with a centrifugal mixer to produce the second Ingredient 2We further manufactured and stored this mixture.

[0229] Then, the two components were mixed using a centrifugal mixer at a weight ratio of 0.6 / 1 for the first and second components to obtain a homogeneous liquid, which was immediately tested as follows:

[0230] To measure mechanical properties, the mixed composition was poured onto a PTFE-coated film to create a film 2 mm thick and stored under standard climate conditions. After 1 day, several dumbbell-shaped test specimens 75 mm in length with a bar length of 30 mm and a bar width of 4 mm were punched out of the film and stored for an additional 6 days under standard climate conditions. Subsequently, as described in DIN EN 53504, the tensile strength (breaking force), elongation at break, and elastic modulus at an elongation of 0.5% to 1% ( MoE 0.5-1% ) and elastic modulus at elongation of 0.5% to 5% ( MoE 0.5-5% ...decided ). Similarly, by punching multiple test samples tear resistance It was stored for measurement and tested at a strain rate of 500 mm / min according to DIN ISO 34.

[0231] After 7 days under SC, all films appearance They were visually evaluated. All films were black in color after curing, had a silky matte surface, were completely non-sticky, homogeneous, and free of blisters. Such films were referred to as "nice" films.

[0232] These results are recorded in Table 4.

[0233]

[0234] composition Z-13 and Z-14In tensile tests according to DIN EN 53504, they exhibit deformation that is primarily plastic but shows a low level of elasticity. These are particularly suitable as structural adhesives for cohesive bonding of substrates or as encapsulation compounds of high hardness and toughness.

Claims

Claim 1 A polymer containing a silane group, characterized by having (i) a polymer containing an isocyanate group, having an NCO content in the range of 0.3 wt% to 4 wt% and a monomeric diisocyanate content of 0.3 wt% or less, obtained from the reaction of at least one monomeric diisocyanate with at least one polyether polyol at an NCO / OH molar ratio of at least 3 / 1, and the subsequent removal of the unconverted monomeric diisocyanate by a separation method, and (ii) a polymer containing a silane group having a silane group of the following chemical formula (I), obtained by reacting at least one amino-, mercapto-, or hydroxysilane at a stoichiometric ratio such that at least 1 mole of amino-, mercapto-, or hydroxysilane is present per 1 molar equivalent of the isocyanate group. In the above formula, b is 0, 1, or 2, 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. R 3 silver , or a monovalent hydrocarbyl radical derived from L-lactide, where R 4 is methyl or ethyl. Claim 2 A polymer containing silane groups according to claim 1, characterized by having an average of 1.3 to 4 silane groups per molecule. Claim 3 A polymer containing a silane group according to claim 1, characterized in that the monomeric diisocyanate is selected from the group consisting of diphenylmethane 4,4'-diisocyanate, tolylene 2,4-diisocyanate, a mixture of tolylene 2,4-diisocyanate and tolylene 2,6-diisocyanate, hexane 1,6-diisocyanate, and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane. Claim 4 A polymer containing a silane group, characterized in that, in claim 1, the monomeric diisocyanate is diphenylmethane 4,4'-diisocyanate. Claim 5 A polymer containing silane groups according to claim 1, characterized in that the polyether polyol has 80% to 100% by weight of 1,2-propylene oxy groups and 0% to 20% by weight of 1,2-ethylene oxy groups based on all repeating units. Claim 6 A polymer containing silane groups according to claim 1, characterized in that the polyether polyol has an OH number in the range of 5 to 58 mg KOH / g. Claim 7 A polymer containing silane groups according to claim 1, characterized in that the polyether polyol is a polyether diol having an average OH functionality in the range of 1.7 to 2. Claim 8 A polymer containing silane groups according to claim 1, characterized in that the polyether polyol is a polyether triol having an average OH functionality in the range of 2.2 to 3. Claim 9 A method for preparing a polymer containing silane groups according to any one of claims 1 to 8, comprising: (a) reacting at least one monomeric diisocyanate with at least one polyether polyol having an OH value in the range of 5 to 58 mg KOH / g at a molar ratio of at least 3 / 1 NCO / OH; (b) then removing the unconverted monomeric diisocyanate by a separation method; and (c) finally reacting the obtained polymer containing isocyanate groups with at least one amino-, mercapto-, or hydroxysilane at a stoichiometric ratio such that at least 1 mole of amino-, mercapto-, or hydroxysilane is present per 1 molar equivalent of the isocyanate group. Claim 10 A curable composition comprising a polymer containing a silane group according to any one of claims 1 to 8, 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 11 A curable composition according to claim 10, characterized by comprising at least one polymer containing a silane group derived from a polyether triol, and at least one additional polymer containing a silane group. Claim 12 A curable composition characterized by being used as an elastic adhesive, elastic sealant, or elastic coating in claim 10. Claim 13 A curable composition according to claim 10, characterized by additionally comprising at least one epoxy resin. Claim 14 A cured composition obtained after contacting the curable composition according to paragraph 10 with moisture. Claim 15 delete

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