Polymers containing silane groups

Abstract

The present invention relates to silane group containing polymers obtained from the reaction of (i) a polymer containing isocyanate groups and having an NCO content of 0.3 to 4 wt% and a monomeric diisocyanate content of not more than 0.3 wt%, which is obtained from the reaction of at least one monomeric diisocyanate with at least one polyether polyol in a molar ratio of NCO / OH of at least 3 / 1 and subsequent removal of the major part of the unconverted monomeric diisocyanate by a suitable separation method, and (ii) at least one aminosilane, mercaptosilane or hydroxysilane in a stoichiometric ratio of at least 1 mole of the amino-, mercapto- or hydroxysilane per one mole equivalent of isocyanate groups. The silane group containing polymers are storage stable, can be well handled at room temperature even without plasticizer or solvent dilution, enable curable compositions with excellent processability, faster curing, higher strength with good ductility and, in a further preferred embodiment, with improved thermal stability. They are particularly suitable as ingredients for sealants, adhesives or coatings which can be cured by means of moisture.

Description

Technical Field

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

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

[0003] Various routes are known for preparing polymers containing silane groups. On the one hand, there are so-called MS polymers, which are obtained by hydrosilylation of allyl ether-terminated polyether polyols. On the other hand, there are so-called SPUR polymers, which are obtained by reacting isocyanatosilanes with polyether polyols. Finally, there are polymers containing silane groups, which result from the reaction of aminosilanes or hydroxysilanes with isocyanate-containing polymers obtained by reacting polyether polyols with monomeric diisocyanates.

[0004] The latter are of particular interest for their mechanical properties, particularly their good strength and high ductility. The isocyanate-containing polymers used as starting materials for their preparation are prepared by reacting monomeric diisocyanates and polyether diols in an NCO / OH ratio of approximately 2 / 1, as described, for example, in US Pat. No. 6,545,087 or US Pat. No. 9,790,315. They contain a considerable amount of monomeric diisocyanates and chain-extended polymers in which two or more polyether diols are linked via the monomeric diisocyanates. Due to these side reaction components, the resulting silane-containing polymers have a high viscosity, so they generally must be diluted with a considerable amount of plasticizer in order to flow freely at room temperature and thus be handled efficiently. However, this limits the degree of freedom in formulating moisture-curing adhesives, sealants, or coatings with regard to their plasticizer content. In particular, for the sealing of porous substrates and the bonding of plastics, sealants and adhesives with very low plasticizer contents are required to prevent plasticizer migration and any damage to the substrate. Furthermore, these known polymers containing silane groups still need improvement with respect to curing rate, strength and thermal stability.

[0005] EP 1237967, US Pat. No. 6884904, or EP 1553118 describe isocyanate-containing polymers in which monomeric diisocyanates are reacted with polyether polyols at an NCO / OH ratio significantly above 2 / 1, and the unconverted monomeric diisocyanate is then distilled off. This results in advantages with regard to the viscosity and EHS classification of the resulting isocyanate-containing polymers. SUMMARY OF THE INVENTION

[0007] The object of the present invention is to provide polymers containing silane groups which can be processed efficiently at room temperature even without dilution with plasticizers or solvents and which enable faster curing and / or higher strength while having good ductility and elasticity and / or improved thermal stability.

[0008] This object is achieved by the silane-group-containing polymer claimed in claim 1. It is obtained by reacting an isocyanate-group-containing polymer with an aminosilane, mercaptosilane, or hydroxysilane in a stoichiometric ratio of at least 1 / 1 relative to the isocyanate groups. The isocyanate-group-containing polymer is obtained by reacting a monomeric diisocyanate with a polyether polyol in an NCO / OH ratio of at least 3 / 1 and subsequently removing the majority of the unconverted monomeric diisocyanate. The silane-group-containing polymer of the present invention contains no isocyanate groups and virtually no silane adducts of the monomeric diisocyanate and contains only very small amounts of chain-extended polymer components. Consequently, it has a particularly low viscosity at room temperature and enables moisture-curing compositions with very good processability. Surprisingly, the polymers of the present invention exhibit particularly rapid curing and, in some cases, particularly high strength (tensile strength and / or elastic modulus and / or Shore hardness). The polymers according to the invention can be used to produce sealants, adhesives, or coatings that are particularly storage-stable and can be processed very efficiently, with very low or no plasticizers or solvents, such as those not obtainable with conventional silane-containing polymers based on isocyanate-containing polymers. The products obtained using the polymers according to the invention surprisingly have advantageous properties even after curing, such as, in particular, improved thermal stability and / or particularly high strength and particularly high ductility.

[0009] Further aspects of the invention are the subject matter of further independent claims. Particularly preferred embodiments of the invention are the subject matter of the dependent claims. Detailed Description of the Invention

[0011] The present invention provides a silane group-containing polymer obtained by reacting the following substances in a stoichiometric ratio of at least 1 mole of aminosilane, mercaptosilane or hydroxysilane per mole equivalent of isocyanate groups:

[0012] (i) a polymer containing isocyanate groups and having an NCO content of 0.3% to 4% by weight and a monomeric diisocyanate content of not more than 0.3% by weight, 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 the major part of the unconverted monomeric diisocyanate by suitable separation methods, and

[0013] (ii) at least one aminosilane, mercaptosilane or hydroxysilane.

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

[0015] “NCO content” refers to the content of isocyanate groups (in % by weight).

[0016] An "organosilane" or simply "silane" is an organic compound having at least one silane group.

[0017] An “alkoxysilane group” or simply a “silane group” is a silyl group to which an organic radical is bonded, which has one to three, in particular two or three, hydrolyzable alkoxy groups on the silicon atom.

[0018] “Aminosilane,” “mercaptosilane,” or “hydroxysilane” refers to an organosilane having an amino group, a mercapto group, or a hydroxyl group, respectively, on the organic radical in addition to the silane group.

[0019] "Molecular weight" refers to the molar mass (g / mole) of a molecule or a molecular residue. "Average molecular weight" refers to the number average molecular weight (M) of a polydisperse mixture of oligomeric or polymeric molecules or molecular residues. n ). It is measured by gel permeation chromatography (GPC) using polystyrene as a standard.

[0020] The term "molar ratio" in relation to reactive groups relates to the ratio of the number of molar equivalents of the corresponding reactive groups.

[0021] The dashed line in the formula represents in each case the bond between the substituent and the molecular group to which it belongs.

[0022] "Plasticizer" refers to a nonvolatile substance that is not chemically incorporated into the polymer during the curing process and that exerts a plasticizing effect on the cured polymer.

[0023] A substance or composition is said to be "storage-stable" or "storable" when it can be stored in a suitable container at room temperature for an extended period of time, generally at least 3 months to 6 months or more, without such storage resulting in any change in its application properties or performance characteristics to an extent relevant for its use.

[0024] "Room temperature" refers to a temperature of 23°C.

[0025] All industry standards and specifications mentioned in this document relate to the versions valid at the time of initial submission.

[0026] Unless otherwise indicated, weight percent (wt%), abbreviated as wt%, refers to the mass proportion of a constituent component of a composition or molecule based on the total composition or total molecules. The terms "mass" and "weight" are used synonymously herein.

[0027] The polymer containing silane groups according to the present invention does not contain isocyanate groups.

[0028] It is liquid at room temperature and has a low viscosity. In particular, it can be effectively processed at room temperature even without dilution with a plasticizer or solvent.

[0029] The silane group-containing polymer is preferably substantially free of plasticizers and solvents. In particular, it contains less than 1% by weight of plasticizer. When used in a curable composition, such a polymer allows complete freedom in whether, how much, and which type of plasticizer the composition contains.

[0030] The polymer containing silane groups preferably has silane groups of formula (I)

[0031]

[0032] in

[0033] b is 0, 1 or 2, in particular 0 or 1,

[0034] R 1 is an alkyl group which optionally contains an ether group and has 1 to 10 carbon atoms,

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

[0036] X is O, S or NR 3 , where R 3 is H or a monovalent hydrocarbon radical having 1 to 20 carbon atoms, which optionally has heteroatoms in the form of alkoxysilyl, ether or carboxylate groups.

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

[0038] More preferably, R 1 Such polymers containing silane groups are particularly reactive.

[0039] Furthermore, it is particularly preferred that R 1 Such polymers containing silane groups are particularly stable during storage and are toxicologically favorable.

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

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

[0042] Most preferably, X is NR 3 , R 3 yes where R 4 is methyl or ethyl, especially ethyl.

[0043] When X=NR 3 In the case of R 2 Preferred is a 1,3-propylene group, a 1,3-butylene group or a 1,4-butylene group, wherein the butylene group may be substituted with one or two methyl groups, and more preferred is a 1,3-propylene group.

[0044] In the case of X=O, R 2 Preferred are divalent hydrocarbon groups having 6 to 12 carbon atoms and having an acylamino group, a carbamate group or a morpholino group, particularly those of the formula group.

[0045] The preferred silane groups of formula (I) enable high strength and high ductility to be achieved.

[0046] Preferably, the silane group-containing polymer has an average of 1.3 to 4, more preferably 1.5 to 3.5, and especially 1.7 to 3.5 silane groups per molecule.

[0047] Particularly preferred polymers containing silane groups are linear and have an average of 1.7 to 2, preferably 1.8 to 2, and in particular 1.9 to 2, silane groups per molecule. Such polymers enable particularly high ductility to be achieved.

[0048] Particularly preferred polymers containing silane groups are branched and have an average of 2.1 to 3, preferably 2.2 to 3, silane groups per molecule.

[0049] The average molecular weight M of the polymer containing silane groups n It is preferably 3,000-30,000 g / mol, more preferably 5,000-20,000 g / mol.

[0050] The NCO content of the polymer containing isocyanate groups from which the polymer containing silane groups is derived is preferably from 0.3% to 3.5% by weight, in particular from 0.4% to 2.5% by weight.

[0051] The average molecular weight M of the isocyanate group-containing polymer nIt is preferably 2500-30000 g / mol, more preferably 4000-20000 g / mol.

[0052] The isocyanate group-containing polymer preferably has a monomeric diisocyanate content of not more than 0.25% by weight, preferably not more than 0.2% by weight and in particular not more than 0.15% by weight.

[0053] Suitable monomeric diisocyanates are commercially available aromatic or aliphatic diisocyanates, in particular 4,4'-diphenylmethane diisocyanate, optionally containing a proportion of 2,4'- and / or 2,2'-diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate or a mixture thereof with 2,6-toluene diisocyanate (TDI), 1,4-phenylene diisocyanate (PDI), naphthalene 1,5-diisocyanate (NDI), 1,6-hexane diisocyanate (HDI), 2,2(4),4-trimethyl-1,6- Hexamethylene diisocyanate (TMDI), cyclohexane-1,3- or -1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI), perhydro-2,4'- or 4,4'-diphenylmethane diisocyanate (HMDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, m- or p-xylylene diisocyanate (XDI), m-tetramethylxylylene diisocyanate (TMXDI) or a mixture thereof.

[0054] Particularly preferably, the monomeric diisocyanate is selected from MDI, TDI, HDI and IPDI.

[0055] Among them, IPDI is particularly preferred. The silane group-containing polymer obtained therefrom has a particularly low viscosity and imparts to the composition particularly good processability, high ductility, and particularly good light stability.

[0056] Among these, MDI, especially 4,4'-diphenylmethane diisocyanate (4,4'-MDI), is particularly preferred. The silane-containing polymers obtained therefrom have surprisingly low viscosities and result in compositions with good processability, particularly high strength, and exceptionally good thermal stability. In contrast, silane-containing polymers prepared from conventional MDI-based isocyanate-containing polymers have very high viscosities and must be diluted with large amounts of plasticizers or solvents to prevent gelation during preparation.

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

[0058] Preferably, the polyether polyol contains 1,2-ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, 1,2-butylene oxide or 1,4-butylene oxide as repeating units.

[0059] More preferably, it mainly or only has 1,2-propyleneoxy groups. More particularly, it has 80 wt% to 100 wt% of 1,2-propyleneoxy groups and 0 wt% to 20 wt% of 1,2-ethyleneoxy groups based on all repeating units.

[0060] Polyoxyalkylene diols and / or polyoxyalkylene triols are particularly suitable, in particular the polymerization products of ethylene oxide or 1,2-propylene oxide or 1,2- or 2,3-butylene oxide or oxetane or tetrahydrofuran or mixtures thereof, which can be polymerized with the aid of starter molecules having two or more active hydrogen atoms, in particular starter molecules such as water, ammonia or compounds having a plurality of OH or NH groups such as 1,2-ethylene glycol, 1,2- or 2,3-butylene oxide or oxetane or tetrahydrofuran or mixtures thereof. 2- or 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycol or tripropylene glycol, the isomeric butanediols, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, cyclohexane-1,3- or 1,4-dimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol or aniline or mixtures of the aforementioned compounds.

[0061] Particularly preferred are polyoxypropylene diols, polyoxypropylene triols or ethylene oxide-terminated polyoxypropylene diols or triols. These are polyoxyethylene / polyoxypropylene mixed polyols which are obtained, in particular, by further alkoxylating polyoxypropylene diols or triols with ethylene oxide at the end of a polypropoxylation reaction and thus ultimately having primary hydroxyl groups.

[0062] Preference is given to polyether polyols having an unsaturation level of less than 0.02 meq / g, in particular less than 0.01 meq / g.

[0063] The OH number of the polyether polyol is preferably from 5 to 58 mg KOH / g, in particular from 6 to 40 mg KOH / g.

[0064] The average molecular weight M of polyether polyol n Preferably it is 2000-20000 g / mol.

[0065] The polyether polyols preferably have an average OH functionality of 1.7-3.

[0066] The polyether polyol is preferably a polyether diol. Such a polymer containing silane groups can impart particularly high ductility to the composition.

[0067] The polyether diols preferably have an average OH functionality of from 1.7 to 2, preferably from 1.8 to 2, in particular from 1.9 to 2. Due to their production, commercially available polyether diols contain a certain content of monols, so that their average OH functionality is usually slightly below 2.

[0068] The polyetherdiols preferably have an OH number of 5 to 58 mg KOH / g, in particular 6 to 33 mg KOH / g.

[0069] Particularly preferred are polyether diols having an OH value of 5 to 20 mg KOH / g, in particular 6 to 15 mg KOH / g. Such polymers impart particularly high ductility and elasticity to the composition.

[0070] The isocyanate group-containing polymers prepared with the polyether diols preferably have an NCO content of 0.3% to 3.5% by weight, in particular 0.4% to 2.2% by weight.

[0071] In a preferred embodiment of the present invention, the polyether polyol is a polyether triol having an average OH functionality of 2.2 to 3. Due to their production, commercially available polyether triols contain a certain content of monols, so their average OH functionality is usually slightly below 3.

[0072] Such polymers containing silane groups impart particularly good thermal stability to the composition after curing.

[0073] The OH number of the polyether triol is preferably from 15 to 58 mg KOH / g, in particular from 20 to 40 mg KOH / g.

[0074] The isocyanate group-containing polymers prepared using the polyethertriols preferably have an NCO content of 0.8% to 3.5% by weight, in particular 1.2% to 2.5% by weight.

[0075] Very particularly preferred are polymers containing silane groups derived from polyether triols and 4,4'-MDI as the monomeric diisocyanate. These polymers cannot be obtained by conventional methods without the addition of large amounts of plasticizers or solvents, as they gel during the preparation process. When proportioned and used in moisture-curing compositions based on silane-containing polymers, they can significantly increase strength while simultaneously increasing ductility and improving thermal stability.

[0076] The NCO / OH molar ratio in the preparation of the isocyanate group-containing polymer is preferably 3 / 1 to 20 / 1, more preferably 4 / 1 to 15 / 1, in particular 5 / 1 to 13 / 1.

[0077] The reaction is preferably carried out at a temperature of 20 to 160° C., in particular 40 to 140° C., with exclusion of moisture, optionally in the presence of a suitable catalyst.

[0078] After the reaction, the monomeric diisocyanate remaining in the reaction mixture is removed by suitable separation methods up to the stated residual content.

[0079] A preferred separation method is distillation, in particular thin-film distillation or short-path distillation, preferably under reduced pressure.

[0080] Particular preference is given to a multistage process in which the monomeric diisocyanate is removed in a short-path evaporator at a jacket temperature of 120 to 200° C. and a pressure of 0.001 to 0.5 mbar.

[0081] In the case of 4,4'-MDI, which is preferred as the monomeric diisocyanate, distillative removal is particularly demanding. For example, it must be ensured that the condensate does not solidify and clog the system. It is preferred to operate at a jacket temperature of 160-200°C at 0.001-0.5 mbar and condense the removed monomeric diisocyanate at a temperature of 40-60°C.

[0082] The monomeric diisocyanate is preferably reacted with the polyether polyol and subsequently the majority of the monomeric diisocyanate remaining in the reaction mixture is removed without the use of solvents or entrainers.

[0083] The monomeric diisocyanate removed after the reaction is preferably subsequently reused, ie used again for preparing the isocyanate-group-containing polymer.

[0084] During the reaction, the OH groups of the polyether polyol react with the isocyanate groups of the monomeric diisocyanate. This also results in a so-called chain extension reaction, in which the OH groups and / or isocyanate groups of the reaction product between the polyol and the monomeric diisocyanate react. The higher the NCO / OH ratio selected, the less chain extension occurs, the lower the polydispersity, and therefore the lower the viscosity of the resulting polymer. A measure of the chain extension reaction is the average molecular weight of the polymer, or the width and distribution of the peaks in GPC analysis. Another measure is the effective NCO content of the monomer-free polymer, which is calculated relative to the theoretical NCO content calculated from the reaction of each OH group with the monomeric diisocyanate.

[0085] The isocyanate-containing polymer preferably contains only a low content of chain-extending components. The NCO content of the polymer is preferably at least 90%, in particular at least 95%, of the theoretical NCO content, calculated from the addition of one mole of monomeric diisocyanate per mole of OH groups of the polyether polyol.

[0086] Polymers containing isocyanate groups are liquid at room temperature and have a low viscosity, contain a low content of monomeric diisocyanates, and are very storage-stable with the exclusion of moisture.

[0087] It is reacted with at least one aminosilane, mercaptosilane or hydroxysilane in a stoichiometric ratio of at least 1 mol of aminosilane, mercaptosilane or hydroxysilane per molar equivalent of isocyanate groups, thereby giving the polymers according to the invention containing silane groups.

[0088] The aminosilane, mercaptosilane or hydroxysilane used for reacting with the isocyanate group-containing polymer is preferably a silane of formula (II)

[0089]

[0090] where R 1 、R 2 , X and b are as defined above.

[0091] Preferred silanes of formula (II) are selected from 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-hydroxypropionamide, N-(3-trimethoxysilylpropyl)-4-hydroxypentanamide, N-(3-trimethoxysilylpropyl)-4-hydroxyoctanamide, N-(3-trimethoxysilylpropyl)-5-hydroxydecanamide, N-(3-trimethoxysilylpropyl)-2-hydroxypropylcarbamate, 2-morpholino-4(5)-(2-trimethoxysilylethyl)cyclohexan-1-ol, 2-morpholino-4(5)-(2-trimethoxysilylethyl)cyclohexan-1-ol, 1-morpholino-3-(3-(triethoxysilyl)propoxy)propan-2-ol, and corresponding analogs with ethoxy groups instead of methoxy groups on silicon.

[0092] Particularly preferred silanes of the 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-hydroxypropionamide, N-(3-triethoxysilylpropyl)-2-hydroxypropionamide, N-(3-dimethoxymethylsilylpropyl)-2-hydroxypropionamide or N-(3-diethoxymethylsilylpropyl)-2-hydroxypropionamide.

[0093] The aminosilane, mercaptosilane or hydroxysilane is reacted with the isocyanate group-containing polymer in a stoichiometric ratio of at least 1 mol of aminosilane, mercaptosilane or hydroxysilane per molar equivalent of isocyanate groups. The stoichiometric ratio is preferably 1 to 1.3, preferably 1 to 1.2, and in particular 1 to 1.1 mol of aminosilane, mercaptosilane or hydroxysilane per molar equivalent of isocyanate groups.

[0094] The reaction is carried out at a temperature of 20-160° C., in particular 60-120° C. Catalysts are optionally used, in particular tertiary amines or metal compounds, in particular bismuth(III), zinc(II), zirconium(IV) or tin(II) compounds or organotin(IV) compounds.

[0095] As mentioned above, particularly preferred silane-containing polymers are those derived from polyethertriols. These silane-containing polymers have an average of more than 2, preferably 2.1 to 4, and especially 2.2 to 3.5, silane groups per molecule. This results in particularly good thermal stability of the composition after curing.

[0096] It is preferably used in combination with further, preferably linear, polymers containing silane groups, wherein the polymers containing silane groups according to the invention are particularly capable of achieving improved thermal stability.

[0097] Particularly preferred polymers containing silane groups are derived from IPDI as monomeric diisocyanate. They therefore have, in particular, silane groups of the formula (Ia) or (Ib)

[0098]

[0099] where R 1 、R 2 , X and b have the definitions given. Such polymers achieve high ductility and particularly high light stability as well as particularly good thermal stability.

[0100] Very particular preference is given to polymers containing silane groups which are derived from polyethertriols and 4,4′-MDI as monomeric diisocyanate.

[0101] It therefore has in particular a silane group of formula (Ic)

[0102]

[0103] where R 1 、R 2 , X and b have the definitions given.

[0104] Conventionally, such polymers cannot be obtained without the addition of large amounts of plasticizers or solvents, as they would gel during the preparation process. They impart particularly high strength and particularly good thermal stability to the composition. Particularly preferred is their use in combination with further, preferably linear, silane-group-containing polymers, thereby achieving improved strength, very high ductility, and improved thermal stability.

[0105] Polymers containing silane groups are storage-stable when moisture is excluded. When in contact with moisture, the silane groups hydrolyze. This forms silanol groups (Si-OH groups), which in turn form siloxane groups (Si-O-Si groups) through subsequent condensation reactions. As a result of these reactions, the polymer solidifies to form a cross-linked plastic. The moisture for solidification can come from the air (air moisture), or the polymer can be contacted with a water-containing component, for example by applying, spraying, or mixing in. During the curing process, the silanol groups can condense with, for example, the hydroxyl groups of the substrate to which the polymer has been applied, thereby further improving adhesion to the substrate during crosslinking.

[0106] The present invention further provides a method for preparing a polymer containing silane groups, characterized in that

[0107] (a) reacting at least one monomeric diisocyanate with at least one polyether polyol having an OH value of 5 to 58 mg KOH / g, in particular 6 to 40 mg KOH / g, in an NCO / OH molar ratio of at least 3 / 1,

[0108] (b) then removing the majority of the unconverted monomeric diisocyanate by suitable separation methods,

[0109] (c) and the obtained isocyanate group-containing polymer is finally reacted with at least one aminosilane, mercaptosilane or hydroxysilane in a stoichiometric ratio of at least 1 mol of aminosilane, mercaptosilane or hydroxysilane per molar equivalent of isocyanate groups.

[0110] The present invention further provides a curable composition comprising the polymer containing silane groups according to the present invention and at least one further component selected from the group consisting of a catalyst, a crosslinking agent, a tackifier, a desiccant, a plasticizer and a filler.

[0111] Suitable catalysts are metal catalysts and / or nitrogen-containing compounds which promote the crosslinking of polymers containing silane groups.

[0112] Suitable metal catalysts are especially compounds of titanium, zirconium, aluminum or tin, especially organotin compounds, organotitanates, organozirconates or organoaluminates, which compounds especially have alkoxy groups, aminoalkoxy groups, sulfonate groups, carboxyl groups, 1,3-diketonate groups, 1,3-ketoester groups, dialkylphosphate groups or dialkylpyrophosphate groups.

[0113] Particularly suitable organotin compounds are dialkyltin oxides, dialkyltin dichlorides, dialkyltin dicarboxylates and dialkyltin diketonates, 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.

[0114] Particularly suitable organic titanates are bis(ethylacetoacetoxy)diisobutoxytitanium(IV), bis(ethylacetoacetoxy)diisopropoxytitanium(IV), bis(acetylacetonato)diisopropoxytitanium(IV), bis(acetylacetonato)diisobutoxytitanium(IV), tris(oxyethyl)aminediisopropoxytitanium(IV), bis[tris(oxyethyl)amine]diisopropoxytitanium(IV), bis(2-ethylhexane-1,3-dioxide)titanium(IV), tris[2-((2-aminoethyl)amino)ethoxy]ethoxytitanium(IV), bis(neopentyl(diallyl)oxy)diethoxytitanium(IV), tetrabutoxytitanium(IV), tetra(2-ethylhexyloxy)titanate, tetra(isopropoxy)titanate or polybutyl titanate. Commercially available products are particularly suitable. AA, GBA, GBO, AA-75, AA-65, AA-105, DC, BEAT, BTP, TE, TnBT, KTM, TOT, TPT, or IBAY (all from DorfKetal); Tytan PBT, TET, X85, TAA, ET, S2, S4, or S6 (all from Borica Company Ltd.); and TTS, 7, 9QS, 12, 26S, 33DS, 38S, 39DS, 44, 134S, 138S, 133DS, 158FS or 44 (all from Kenrich Petrochemicals).

[0115] Particularly suitable organozirconates are commercially available products 38J, TPPJ, TPP, 01, 09, 12, 38, 44 or 97 (all from Kenrich Petrochemicals) or 3020, 3030, 1020 (all from Johnson Matthey & Brandeberger).

[0116] A particularly suitable organoaluminate is the commercially available product K-Kat 5218 (from King Industries).

[0117] Suitable nitrogen-containing compounds as catalysts are, in particular, amines, such as, in particular, N-ethyldiisopropylamine, N,N,N′,N′-tetramethylalkylenediamine, polyoxyalkyleneamines, 1,4-diazabicyclo[2.2.2]octane; aminosilanes, such as, in particular, 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-N′-[3-(trimethoxysilyl)propyl]ethylenediamine or analogs thereof having ethoxy groups replacing the methoxy groups on the silicon; cyclic amidines, such as, in particular, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 6-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene; guanidines, such as, in particular, tetramethylguanidine, 2-guanidinobenzimidazole, guanidine acetylacetonate, 1,3-di-o-tolylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, or reaction products of carbodiimides and amines, such as, in particular, polyetheramines or aminosilanes; or imidazoles, such as, in particular, N-(3-trimethoxysilylpropyl)-4,5-dihydroimidazole or N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0118] Combinations of different catalysts, in particular combinations of at least one metal catalyst and at least one nitrogen-containing compound, are also suitable.

[0119] Preferred catalysts are organotin compounds, organotitanates, amines, especially aminosilanes, amidines, guanidines or imidazoles.

[0120] Suitable adhesion promoters and / or crosslinkers are, in particular, aminosilanes, mercaptosilanes, epoxysilanes, (meth)acryloylsilanes, anhydridesilanes, carbamatesilanes, alkylsilanes or iminosilanes, or oligomeric forms of these silanes, or adducts of primary aminosilanes with epoxysilanes, (meth)acryloylsilanes or anhydridesilanes. 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 in which methoxysilyl groups are replaced on the silicon by ethoxysilane groups, or oligomeric forms of these silanes.

[0121] Particularly suitable desiccants are tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, organosilanes having a functional group in the α-position of the silyl group, in particular N-(methyldimethoxysilylmethyl)-O-methylcarbamate or (methacryloyloxymethyl)silane, methoxymethylsilane, orthoformates, as well as calcium oxide or molecular sieves. Preference is given to vinyltrimethoxysilane or vinyltriethoxysilane. When the branched polymer containing silyl groups has methoxysilane groups, vinyltrimethoxysilane is preferred, while when the branched polymer containing silyl groups has ethoxysilane groups, vinyltriethoxysilane is preferred.

[0122] Suitable plasticizers are, in particular, carboxylic acid esters, such as phthalates, in particular diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di(2-propylheptyl) phthalate (DPHP), hydrogenated phthalates or 1,2-cyclohexanedicarboxylates, in particular hydrogenated diisononyl phthalate or diisononyl 1,2-cyclohexanedicarboxylate (DINCH), terephthalates, in particular di(2-ethylhexyl) terephthalate (DOTP) or diisononyl terephthalate (DINT), hydrogenated terephthalates or 1,4-cyclohexanedicarboxylates, in particular hydrogenated di(2-ethylhexyl) terephthalate or di(2-ethylhexyl) 1,4-cyclohexanedicarboxylate, or hydrogenated diisononyl terephthalate or diisononyl 1,4-cyclohexanedicarboxylate, isophthalates, trimellitates, adipates, in particular dioctyl adipate, azelates, sebacates, benzoates, polyols, in particular polyether polyols or polyester polyols, glycol ethers, glycol esters, polyether mono- or polyols having blocked hydroxyl groups, in particular in the form of acetate groups, organic phosphates or sulfonates, polybutenes or plasticizers derived from natural fats or oils, in particular fatty acid methyl or ethyl esters, also known as "biodiesel", or epoxidized soybean oil or linseed oil.

[0123] Suitable fillers are, in particular, ground or precipitated calcium carbonate, barite, quartz powder, quartz sand, dolomite, wollastonite, calcined kaolin, sheet silicates such as mica or talc, zeolites, aluminum hydroxide, magnesium hydroxide, silicon dioxide including highly dispersed silicon dioxide from pyrogenic processes, cement, gypsum, fly ash, industrially produced carbon black, graphite, metal powders, for example of aluminum, copper, iron, silver or steel, PVC powder or hollow beads, optionally coated with fatty acids, in particular stearates. Precipitated calcium carbonate and / or carbon black coated with fatty acids is preferred.

[0124] Further suitable components are, in particular, the following auxiliaries and additives:

[0125] – other oligomers or polymers containing silane groups;

[0126] – solvents;

[0127] - fibers, in particular 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;

[0128] – nanofillers, such as graphene or carbon nanotubes;

[0129] -dye;

[0130] – inorganic or organic pigments, in particular titanium dioxide, chromium oxide or iron oxide;

[0131] - rheology modifiers, in particular thickeners, in particular layered silicates such as bentonites, castor oil derivatives, hydrogenated castor oil, polyamides, polyamide waxes, polyurethanes, urea compounds, fumed silica, cellulose ethers or hydrophobically modified polyoxyethylenes;

[0132] – Stabilizers against oxidation, heat, light or UV radiation;

[0133] – natural resins, fats or oils, such as rosin, shellac, linseed oil, castor oil or soybean oil;

[0134] - non-reactive polymers, in particular homopolymers or copolymers of unsaturated monomers, in particular chosen from ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth)acrylates, in particular polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene / vinyl acetate copolymers (EVA) or atactic poly-α-olefins (APAO);

[0135] - flame-retardant substances, in particular the fillers already mentioned, such as aluminium hydroxide or magnesium hydroxide, or organic phosphates;

[0136] - Additives, in particular wetting agents, leveling agents, defoamers, deaerators, stabilizers against oxidation, heat, light or UV radiation, or biocides.

[0137] It may be advisable to chemically or physically dry certain ingredients before mixing into the composition.

[0138] The curable composition preferably contains 5 to 80% by weight, more preferably 10 to 70% by weight and in particular 20 to 60% by weight of the polymer containing silane groups.

[0139] In a preferred embodiment of the present invention, the curable composition comprises at least one polymer containing silane groups derived from a polyether triol according to the invention and at least one further polymer containing silane groups, in particular a linear polymer.

[0140] The weight ratio between the polymer containing silane groups derived from polyethertriol according to the invention and the further polymer containing silane groups is preferably from 10 / 90 to 70 / 30, in particular from 15 / 85 to 60 / 40.

[0141] The further polymers containing silane groups are preferably selected from:

[0142] - polymers containing silane groups derived from polyether diols according to the invention;

[0143] - polymers containing silane groups, which are derived from polymers containing isocyanate groups from the reaction of monomeric isocyanates with polyether polyols, in particular diols, in an NCO / OH molar ratio of 1.3 to 2.5 / 1, in particular 1.8 to 2.5 / 1, without subsequent removal of the monomeric diisocyanate;

[0144] - polyethers containing silane groups, obtained by reaction of allyl-containing polyethers with hydrosilanes, optionally with chain extension, in particular with diisocyanates;

[0145] - polyethers containing silane groups, obtained by copolymerization of alkylene oxides and epoxysilanes, optionally with chain extension, in particular with diisocyanates;

[0146] - Polyethers containing silane groups, obtained by chain-extending polyether polyols, especially diols, with isocyanatosilanes, optionally using diisocyanates.

[0147] The polymers of the invention containing silane groups and derived from polyethertriols improve in particular the thermal stability and possibly the strength and / or ductility of the compositions.

[0148] The curable composition is prepared, in particular, under exclusion of moisture and stored at ambient temperature in a moisture-proof container. Suitable moisture-proof containers consist, in particular, of optionally coated metal and / or plastic, and are in particular drums, containers, pails, barrels, boxes, cans, bags, hose bags, cartridges or tubes.

[0149] The curable composition may be in the form of a one-component composition or a two-component composition.

[0150] A "one-part" composition refers to a composition in which all ingredients of the composition are mixed together, stored in the same container, and can be cured with moisture.

[0151] A "two-component" composition is one in which the components of the composition are present in two different components stored in separate containers. The two components are not mixed with one another until shortly before or during application of the composition, whereupon the mixed composition cures, wherein curing is effected or completed solely by the action of moisture.

[0152] The curable composition is preferably a one-component composition. In suitable packaging and storage, it is storage stable, typically for several months to a year or more.

[0153] When the curable composition is applied, the silane groups present come into contact with moisture, thereby initiating the curing process. Curing proceeds at different rates depending on the temperature, the nature of the contact, the amount of moisture, and the presence of any catalysts. In the case of curing by air moisture, a skin first forms on the surface of the composition. The so-called skin formation time is a measure of the curing rate.

[0154] This results in a cured composition.

[0155] 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 which contains or releases water and / or a catalyst and / or a curing agent can be mixed into the composition during application, or the composition can be brought into contact with such an accelerator component after application.

[0156] The curable composition is preferably applied at ambient temperature, in particular in the range of about -10 to 50°C, preferably in the range of -5 to 45°C, in particular in the range of 0 to 40°C.

[0157] Curing is preferably likewise carried out at ambient temperature.

[0158] In the cured state, the composition exhibits remarkable elasticity, particularly high strength and ductility, good thermal stability, and good adhesion properties on various substrates. It is therefore suitable for a wide variety of applications, particularly as a sealant, adhesive, covering, coating, or paint for construction or industrial applications, for example as a joint sealant, flooring adhesive, assembly adhesive, window adhesive, or for sealing car bodies, seams, or cavities, as a floor covering, floor coating, balcony coating, roof coating, or garage coating.

[0159] The curable composition is preferably used as an elastic adhesive or an elastic sealant or an elastic coating.

[0160] The curable composition can be formulated so that it has a pasty consistency with structural adhesive properties. Such a composition is applied with the aid of a suitable device, such as from a commercially available cartridge or bucket or pail, for example in the form of a bead, which can have a substantially circular or triangular cross-section.

[0161] The curable composition can also be formulated to be fluid and so-called "self-leveling" or only slightly thixotropic and can be poured for application. As a coating, it can then be distributed flatly until the desired layer thickness is achieved, for example, using a roller, a slide bar, a toothed scraper, or a trowel. In practice, a layer thickness in the range of 0.5 to 3 mm, in particular 1 to 2.5 mm, is typically applied.

[0162] Suitable substrates for bonding, sealing or coating are, in particular:

[0163] – glass, glass ceramics, screen-printed ceramics, concrete, mortar, cement screeds (Estrich), fiber cement, in particular fiber cement board, bricks, tiles, gypsum, in particular gypsum board or anhydrite screeds, or natural stone such as granite or marble;

[0164] – metals or alloys such as aluminium, copper, iron, steel, non-ferrous metals, including metals or alloys with surface finishes such as zinc- or chromium-plated metals;

[0165] - plastics, in particular hard or soft PVC, polycarbonate (PC), polyamide (PA), polyester, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, wherein the surface of the plastics has optionally been treated by means of plasma, corona or flame;

[0166] – paints or varnishes, especially automotive topcoats;

[0167] – Repair or levelling materials based on PCC (polymer-modified cement mortar) or ECC (epoxy-modified cement mortar);

[0168] – tar or bitumen;

[0169] - leather, fabric, paper, wood, wooden materials bonded with resins such as phenolic resins, melamine resins or epoxy resins, resin-fabric composites or other so-called polymer composites;

[0170] – Insulating foams, in particular those made from EPS, XPS, PUR, PIR, rock wool, glass wool or foamed glass (expanded glass).

[0171] If desired, the substrate can be pretreated before application, in particular by physical and / or chemical cleaning methods or by applying an activator or primer.

[0172] Two identical or two different substrates can be bonded or sealed.

[0173] After bonding or sealing the two substrates, a bonded or sealed article is obtained. The article can be a building structure or a part thereof, in particular a building, bridge, roof, stairwell, or facade of an above-ground or underground structure, or it can be an industrial or consumer product, in particular a window, pipe, household appliance, or a means of transport, such as, in particular, an automobile, bus, truck, rail vehicle, ship, airplane, or helicopter, or an installed component thereof.

[0174] In one embodiment, the curable composition further comprises at least one epoxy resin. This composition is preferably a two-component composition. It particularly comprises at least one further component selected from aminosilanes, epoxysilanes, vinylsilanes, polyamines having two or three primary or secondary aliphatic amino groups, and accelerators for epoxy reactions. It may also optionally comprise water.

[0175] The compound having an amino group and the epoxy resin are preferably not in the same component.

[0176] The weight ratio between the polymer containing silane groups and the epoxy resin is preferably 20 / 80 to 70 / 30.

[0177] Such compositions have particularly high strength, with the high content of epoxy resin enabling particularly high strength and the high content of polymer containing silane groups enabling high ductility and elasticity as well as high strength.

[0178] Suitable epoxy resins are especially liquid epoxy resins which are flowable at room temperature and have a glass transition temperature below 25°C.

[0179] Preference is given to liquid epoxy resins based on bisphenol A diglycidyl ether, bisphenol F diglycidyl ether or bisphenol A / F diglycidyl ether, in particular epoxy resins of technical quality, such as are commercially available from Dow, Huntsman or Momentive, which optionally include a proportion of solid bisphenol A resin or phenol novolac.

[0180] Particularly suitable silanes for this composition are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, vinyltrimethoxysilane or vinyltriethoxysilane.

[0181] Suitable polyamines are especially 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), menthane-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-benzylpropyl-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-diamine or higher oligomers of these diamines, bis(3-aminopropyl)polytetrahydrofuran or other polytetrahydrofuran diamines, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, polyoxyalkylene di- or triamines, in particular D-230, D-400, D-2000, EDR-104, EDR-148, EDR-176, T-403, T-3000, T-5000 (both from Huntsman), or adducts of these or other polyamines with epoxy resins or monoepoxides, such as especially o-cresyl glycidyl ether, and so-called polyamidoamines or so-called Mannich bases, especially phenalkamines.

[0182] Preferred are 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, polyoxypropylene diamine or triamine, and the average molecular weight M n 200-500 g / mol, or an adduct of MPMD or propane-1,2-diamine and o-cresyl glycidyl ether.

[0183] Suitable accelerators for the epoxy reaction are, in particular, acids or compounds which can be hydrolyzed to acids, in particular organic carboxylic acids such as salicylic acid, organic sulfonic acids such as p-toluenesulfonic acid, sulfonic esters, phosphoric acid, or nitrates such as, in particular, calcium nitrate, or tertiary amines such as, in particular, 1,4-diazabicyclo[2.2.2]octane, triethanolamine, imidazoles such as, in particular, N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole, amidines or guanidines, phenols, Mannich bases such as, in particular, 2,4,6-tris(dimethylaminomethyl)phenol, or compounds having mercapto groups.

[0184] Particularly 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.

[0185] This curable composition containing epoxy resin is solidified by mixing the two components of the composition with each other and contacting the composition with moisture. As mentioned above, the silane groups present in this process react with moisture, and the epoxy groups present react with primary or secondary amino groups and / or with each other, and aminosilane can connect the polyether polymer and the epoxy resin to each other via the silane groups and via the amino groups. This forms a high-quality material with high strength, high impact toughness, high stability and, depending on the ratio between the silane-containing polymer and the epoxy resin, greater or less ductility and elasticity.

[0186] The present invention also provides a cured composition obtained from the curable composition after contacting it with moisture. Example

[0187] In the following, examples are introduced which are intended to further illustrate the invention described. The invention is of course not limited to these described examples.

[0188] “Standard climatic conditions” (“NK”) mean a temperature of 23±1° C. and a relative humidity of 50±5%.

[0189] Unless otherwise stated, chemicals used were from Sigma-Aldrich.

[0190] Diisodecyl phthalate as 10-P (from BASF) was used.

[0191] Viscosity was measured using a thermostated Rheotec RC30 cone-plate viscometer (cone diameter 25 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 10 s -1 ) determination.

[0192] The content of monomeric diisocyanate was determined by HPLC (detection by photodiode array; 0.04 M sodium acetate / acetonitrile as mobile phase) before prior derivatization with the aid of N-propyl-4-nitrobenzylamine.

[0193] Preparation of isocyanate-containing polymers with exclusion of monomers:

[0194] Polymer D-1:

[0195] 812.0 g (0.15 eq OH) of polyoxypropylene glycol (OH value 10 mg KOH / g, 12200N from Covestro) and 166.6 g (1.5 eq NCO) IPDI (1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, IPDI (from Evonik) was reacted at 80° C. by known methods to give a polymer having an NCO content of 5.7 wt.%, a viscosity of 11.0 Pa·s at 20° C. and a monomeric IPDI content of about 9.5 wt.%.

[0196] Subsequently, volatile components, in particular most of the monomeric IPDI, were removed by distillation in a short-path evaporator (jacket temperature 160° C., pressure 0.1-0.005 mbar). The linear polymer thus obtained had an NCO content of 0.85 wt.%, a viscosity of 19.1 Pa·s at 20° C., and a monomeric IPDI content of 0.06 wt.%.

[0197] Polymer D-2:

[0198] 725.0 g of ethylene oxide-terminated polyoxypropylene triol (OH value 28 mg KOH / g, 5031BT from Covestro) and 275 g of 4,4'-diphenylmethane diisocyanate ( 44MC L from Covestro) was converted by known methods at 80° C. into a polymer having an NCO content of 7.6 wt. %, a viscosity of 6.5 Pa·s at 20° C. and a monomeric 4,4′-diphenylmethane diisocyanate content of about 20 wt. %.

[0199] Subsequently, the volatile components, in particular the majority of the monomeric 4,4'-diphenylmethane diisocyanate, were distilled off in a short-path evaporator (jacket temperature 180°C, pressure 0.1-0.005 mbar, condensation temperature 47°C). The polymer thus obtained had an NCO content of 1.7 wt.%, a viscosity of 19 Pa·s at 20°C, and a monomeric 4,4'-diphenylmethane diisocyanate content of 0.04 wt.%.

[0200] Polymer D-3:

[0201] 780.0 g of ethylene oxide-terminated polyoxypropylene triol (OH value 28 mg KOH / g, 5031BT from Covestro) and 220 g IPDI (1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, IPDI (from Evonik) was converted by known methods at 80° C. in the presence of 0.01 g of dibutyltin dilaurate into a polymer having an NCO content of 6.4 wt. %, a viscosity of 4.1 Pa·s at 20° C. and a monomeric IPDI content of about 12 wt. %.

[0202] Subsequently, volatile components, particularly most of the monomeric IPDI, were distilled off in a short-path evaporator (jacket temperature 160° C., pressure 0.1-0.005 mbar). The polymer thus obtained had an NCO content of 1.9 wt.%, a viscosity of 8.2 Pa·s at 20° C., and a monomeric IPDI content of 0.02 wt.%.

[0203] Polymer D-4:

[0204] 727.0 g of polyoxypropylene glycol (OH value 28 mg KOH / g, 4200, from Covestro) and 273.0 g of 4,4'-diphenylmethane diisocyanate ( 44MC L from Covestro) was converted by known methods at 80° C. into a polymer having an NCO content of 7.4 wt. %, a viscosity of 5.2 Pa·s at 20° C. and a content of monomeric 4,4′-diphenylmethane diisocyanate of about 17 wt. %.

[0205] Subsequently, volatile components, particularly the majority of monomeric 4,4'-diphenylmethane diisocyanate, were distilled off in a short-path evaporator (jacket temperature 180°C, pressure 0.1-0.005 mbar, condensation temperature 47°C). The linear polymer thus obtained had an NCO content of 1.8 wt.%, a viscosity of 13.3 Pa·s at 20°C, and a monomeric 4,4'-diphenylmethane diisocyanate content of 0.08 wt.%.

[0206] Preparation of conventional isocyanate group-containing polymers:

[0207] Polymer C-1: (NCO / OH=2.1 / 1)

[0208] 1000.0 g of polyoxypropylene glycol (OH value 10 mg KOH / g, 12200N, from Covestro), 122.8 g diisodecyl phthalate, 41.6 g IPDI (1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, IPDI (from Evonik) and 0.12 g of dibutyltin dilaurate were converted by known methods at 90° C. into a polymer having an NCO content of 0.63 wt. %, a viscosity of 31 Pa·s at 20° C. and a monomeric IPDI content of about 0.5 wt. %.

[0209] Polymer C-2: (NCO / OH=2.1 / 1)

[0210] 190.0 g of ethylene oxide-terminated polyoxypropylene triol (OH value 28 mg KOH / g, 5031BT from Covestro) and 25.0 g of 4,4'-diphenylmethane diisocyanate ( 44MC L from Covestro) was converted by known methods at 80° C. The reaction mixture gelled during the reaction and could not be used further.

[0211] Silane of formula (II) used:

[0212] Silane A-1 N-(3-trimethoxysilylpropyl)aminosuccinic acid diethyl ester (351.5 g / mol), obtained by reacting 3-aminopropyltrimethoxysilane and diethyl maleate in a molar ratio of about 1 / 1

[0213] Silane A-2 N-(3-triethoxysilylpropyl)aminosuccinic acid diethyl ester (393.6 g / mol), obtained by reacting 3-aminopropyltriethoxysilane and diethyl maleate in a molar ratio of about 1 / 1

[0214] Silane A-3 N-(3-diethoxymethylsilylpropyl)-2-hydroxypropionamide (263.4 g / mol), obtained by reacting 3-aminopropyldiethoxymethylsilane with L-lactide in a molar ratio of about 2 / 1

[0215] Preparation of polymers containing silane groups:

[0216] Polymer S-1: (Present invention)

[0217] Under a nitrogen atmosphere with no moisture, 300 g of polymer D-1 prepared as described above was initially charged, 25.1 g of silane A-2 was added, and the mixture was stirred at 60°C until no isocyanate groups were detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored with no moisture. It was transparent and had a viscosity of 40 Pa·s at 20°C one day after production.

[0218] Polymer S-2: (Present invention)

[0219] In a nitrogen atmosphere with no moisture, 300 g of the polymer D-1 prepared as described above was pre-placed, mixed with 16.8 g of silane A-3 and 0.06 g of Bi catalyst ( 83, from Vertellus) and stirred the mixture at 80°C until no isocyanate groups could be detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored with the exclusion of moisture. It was transparent and had a viscosity of 90 Pa·s at 20°C one day after preparation.

[0220] Polymer S-3: (present invention)

[0221] Under a nitrogen atmosphere with no moisture, 247.0 g of the polymer D-2 prepared above was initially charged, 36.2 g of silane A-1 was added, and the mixture was stirred at 60°C until no isocyanate groups were detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored with no moisture. It was transparent and had a viscosity of 357 Pa·s at 20°C one day after preparation.

[0222] Polymer S-4: (Present invention)

[0223] Under a nitrogen atmosphere with no moisture, 221.0 g of the polymer D-3 prepared above was initially charged, 36.2 g of silane A-1 was added, and the mixture was stirred at 60°C until no isocyanate groups were detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored with no moisture. It was transparent and had a viscosity of 70 Pa·s at 20°C one day after preparation.

[0224] Polymer S-5: (present invention)

[0225] Under a nitrogen atmosphere with no moisture, 233.3 g of polymer D-4 prepared as described above was initially charged, 36.2 g of silane A-1 was added, and the mixture was stirred at 60°C until no isocyanate groups were detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored with no moisture. It was transparent and had a viscosity of 108 Pa·s at 20°C one day after preparation.

[0226] Polymer R-0: (Comparison)

[0227] Under a nitrogen atmosphere with no moisture, 333.3 g of the polymer C-1 prepared above was initially charged, 18.1 g of silane A-1 was added, and the mixture was stirred at 60°C until no isocyanate groups were detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored with no moisture. It contained 10 wt.% of a plasticizer (diisodecyl phthalate), was transparent, and had a viscosity of 99 Pa·s at 20°C one day after preparation.

[0228] Polymer R-1: (Comparative)

[0229] Under a nitrogen atmosphere with no moisture, 333.3 g of the polymer C-1 prepared as described above was initially charged, 20.2 g of silane A-2 was added, and the mixture was stirred at 60°C until no isocyanate groups were detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored with no moisture. It contained approximately 10 wt.% of a plasticizer (diisodecyl phthalate), was transparent, and had a viscosity of 79 Pa·s at 20°C one day after preparation.

[0230] Polymer R-2: (Comparative)

[0231] In a nitrogen atmosphere with no moisture, 333.3 g of the polymer C-1 prepared as described above was pre-placed, mixed with 13.6 g of silane A-3 and 0.06 g of Bi catalyst ( 83, from Vertellus) and stirred at 80°C until no isocyanate groups were detected by FT-IR spectroscopy. The resulting polymer was cooled to room temperature and stored under the exclusion of moisture. It contained 10 wt.% of a plasticizer (diisodecyl phthalate), was transparent, and had a viscosity of 113 Pa·s at 20°C one day after preparation.

[0232] Polymer SPUR-1: (Comparison)

[0233] 190.0 g of 5031BT and 19.5 g of 3-isocyanatopropyltrimethoxysilane were converted into a polymer containing silane groups. The resulting polymer was cooled to room temperature and stored under the exclusion of moisture. It was transparent and had a viscosity of 5 Pa·s at 20°C one day after preparation.

[0234]

[0235] Table 1: Overview of the prepared polymers containing silane groups

[0236] 1 The present invention 2 contrast

[0237] Moisture-curing composition:

[0238] Compositions Z1-Z12:

[0239] For each composition, the ingredients listed in Table 2-3 were mixed in the amounts listed (parts by weight) using a centrifugal mixer (SpeedMixer TM The mixture was mixed at 3000 rpm for one minute with the exclusion of water using a DAC 150, FlackTek Inc., and stored with the exclusion of water.

[0240] The following test compositions were used:

[0241] As a measure of the storage stability, the viscosity was measured after storage at room temperature in sealed aluminum tubes with exclusion of moisture for one day (1 d RT) and after 7 days at 60° C. in a forced-air oven (7 d 60° C.).

[0242] As a measure of the open time, the skinning time (HBZ) was determined. For this purpose, a few grams of the composition were applied to cardboard in a layer thickness of approximately 2 mm, and the time period was measured under standard climatic conditions until no residue remained for the first time when the surface of the composition was gently tapped with an LDPE pipette.

[0243] As a measure of hardness and thermal stability, the Shore A hardness is determined on specimens cured under standard climatic conditions for 7 days (7d NK) in accordance with DIN 53505 or stored under standard climatic conditions for 7 days and subsequently stored in an air-circulating oven at 80°C, 90°C or 100°C for the specified time and temperature.

[0244] To determine the mechanical properties, the composition was applied to a silicone-coated release paper to give a film with a thickness of 2 mm, which was stored under standard climatic conditions for 14 days, after which several dumbbell-shaped specimens with a length of 75 mm, a stem length of 30 mm and a stem width of 4 mm were punched out of the film and tested at a tensile rate of 200 mm / min in accordance with DIN EN 53504 to determine the tensile strength (force at break), the elongation at break and the 5% modulus of elasticity (at an elongation of 0.5-5%) and the 50% modulus of elasticity (at an elongation of 0.5-50%).

[0245] As a measure of the strength of the adhesive bond, the tensile shear strength (ZSF) was determined on glass. For this purpose, two pieces were degreased with isopropanol and The bonded test specimens were prepared by bonding glass panes pretreated using an Aktivator 205 (from Sika Schweiz AG) in an overlapping adhesive joint with dimensions of 12 x 25 mm and a thickness of 4 mm, with the glass panes projecting at the top. After 14 days of storage under standard climatic conditions, the tensile shear strength was determined at a rate of 20 mm / min in accordance with DIN EN 1465.

[0246] The results are reported in Tables 2-3.

[0247] Comparative Examples are indicated by (Ref.).

[0248]

[0249]

[0250] Table 2: Composition (parts by weight) and properties of Z1-Z6. "nb" stands for "not determined"

[0251] 1 Socal U1S2 (from Solvay)

[0252] 2 Jeffamine T-403 (from Huntsman)

[0253] 3 3-Aminopropyltriethoxysilane

[0254] 4Vinyltriethoxysilane

[0255] 5 1,8-Diazabicyclo[5.4.0]undec-7-ene

[0256]

[0257]

[0258] Table 3: Composition (parts by weight) and properties of Z7-Z12. "nm" means "not measurable" because it is too soft (destroyed)

[0259] 1 3-Aminopropyltrimethoxysilane

[0260] 2 Vinyltrimethoxysilane

[0261] 3 1,8-Diazabicyclo[5.4.0]undec-7-ene

[0262] 4 Dibutyltin dilaurate

[0263] As can be seen from Table 3, the inventive compositions Z8-Z10 and Z12 have good thermal stability, while the comparative compositions Z7 and Z11 have insufficient thermal stability. After storage at 90°C for 14 days and at 100°C for 7 days, their Shore A test samples were damaged to the point where they could not be measured.

[0264] Two-component composition containing epoxy resin:

[0265] Compositions Z13 and Z14:

[0266] For each composition, the mixture was stirred at room temperature using a centrifugal mixer (SpeedMixer TM DAC 150, FlackTek Inc.) was mixed with 62.2 parts by weight (GT) of the silane group-containing polymer shown in Table 4, 1.4 GT of diisodecyl phthalate, 2.4 GT of vinyltrimethoxysilane, 27.4 GT of 1,2-diaminocyclohexane ( DCH-99 from Invista), 2.3 GT of 3-aminopropyltrimethoxysilane, 2.3 GT of 2,4,6-tris(dimethylaminomethyl)phenol ( K54 from Evonik), 0.4 GT of stabilizer (Irganox 1010 from BASF), 1.5 GT of carbon black and 0.1 GT of dibutyltin dilaurate were used to prepare the first component-1, and the mixture was stored under the condition of excluding moisture.

[0267] For each composition, 70.2 GT of bisphenol A diglycidyl ether ( GY 250 from Huntsman), 23.4GT hexanediol diglycidyl ether ( DY-H from Huntsman), 0.5 GT emulsifier, 1.9 GT water, 2.4 GT fumed silica, 1.5 GT carbon black and 0.1 GT dibutyltin dilaurate to prepare the second component-2 and store the mixture.

[0268] The two components were then processed using a centrifugal mixer in a weight ratio of first / second component 0.6 / 1 to obtain a homogeneous liquid and immediately tested as follows:

[0269] To determine the mechanical properties, the mixed composition was cast onto a PTFE-coated film to a thickness of 2 mm and stored under standard climatic conditions. After one day, several dumbbell-shaped specimens, each 75 mm long and 30 mm long by 4 mm wide, were punched out of the film and stored under standard climatic conditions for a further six days. Subsequently, the tensile strength (force at break), elongation at break, and modulus of elasticity at 0.5% to 1% elongation (0.5-1% elastic modulus) and 0.5% to 5% elongation (0.5-5% elastic modulus) were determined at a rate of extension of 2 mm / min, as described in DIN EN 53504. Similarly, several specimens were punched out and stored to determine the tear propagation resistance and tested according to DIN ISO 34 at a rate of extension of 500 mm / min.

[0270] After 7 days under NK, the appearance of all films was visually evaluated. All films were black after curing, had a silky matte surface with absolutely zero tack, and were uniform and free of bubbles. Such films were rated "good."

[0271] These results are reported in Table 4.

[0272] Composition Z-13 Z-14 Polymer in component-1 S-4 S-5 Tensile strength [MPa] 20.3 22.7 Elongation at break 46％ 60％ Elastic modulus 0.5-1% [MPa] 890 1015 Elastic modulus 0.5-5% [MPa] 329 334 Tear propagation resistance [N / mm] 30.8 26.6 Appearance good good

[0273] Table 4: Polymers containing silane groups and properties of compositions Z-13 and Z-14.

[0274] Compositions Z-13 and Z-14 exhibit minimal elastic but predominantly plastic deformation in tensile tests according to DIN EN 53504. They are particularly suitable as structural adhesives for non-positive connections of substrates or as high-hardness and toughness potting compounds.

Claims

1. A polymer containing silane groups, obtained by reacting the following substances in a stoichiometric ratio of at least 1 mole of aminosilane, mercaptosilane or hydroxysilane per molar equivalent of isocyanate groups: (i) a polymer containing isocyanate groups and having an NCO content of 0.3% to 4% by weight and a monomeric diisocyanate content of not more than 0.15% by weight, obtained by reacting at least one monomeric diisocyanate with at least one polyether polyol in an NCO / OH molar ratio of 4 / 1 to 15 / 1 and subsequently removing the major part of the unconverted monomeric diisocyanate by suitable separation methods, and (ii) at least one aminosilane, mercaptosilane or hydroxysilane.

2. The polymer containing silane groups according to claim 1, characterized in that it has silane groups of formula (I) in b is 0, 1, or 2, R 1 is an alkyl group which optionally contains an ether group and has 1 to 10 carbon atoms, R 2 is a divalent hydrocarbon radical having 1 to 12 carbon atoms, which optionally has cyclic and / or aromatic moieties and optionally one or more heteroatoms, and X is O, S or NR 3 , where R 3 is H or a monovalent hydrocarbon radical having 1 to 20 carbon atoms, which optionally has heteroatoms in the form of alkoxysilyl, ether or carboxylate groups.

3. The silane group-containing polymer according to claim 2, characterized in that R 2 It is a divalent hydrocarbon group having an acylamino group, a carbamate group, or a morpholine group.

4. The polymer containing silane groups according to any one of claims 1 to 3, characterized in that it has an average of 1.3 to 4 silane groups per molecule.

5. The polymer containing silane groups according to claim 4, characterized in that it has an average of 1.5 to 3.5 silane groups per molecule.

6. The polymer containing silane groups according to claim 4, characterized in that it has an average of 1.7 to 3.5 silane groups per molecule.

7. The polymer containing silane groups according to claim 1, wherein the monomeric diisocyanate is selected from 4,4'-diphenylmethane diisocyanate, which optionally contains 2,4'- and / or 2,2'-diphenylmethane diisocyanate moieties, 2,4-toluene diisocyanate, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, hexane-1,6-diisocyanate and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane.

8. The silane group-containing polymer according to any one of claims 1 to 3, characterized in that The monomeric diisocyanate is 4,4'-diphenylmethane diisocyanate.

9. The silane group-containing polymer according to any one of claims 1 to 3, characterized in that The polyether polyol has 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.

10. The silane group-containing polymer according to any one of claims 1 to 3, characterized in that The OH value of the polyether polyol is 5-58 mg KOH / g.

11. The silane group-containing polymer according to any one of claims 1 to 3, characterized in that Polyether polyols are polyether diols with an average OH functionality of 1.7-2.

12. The silane group-containing polymer according to any one of claims 1 to 3, characterized in that Polyether polyols are polyether triols with an average OH functionality of 2.2-3.

13. A method for preparing a polymer containing silane groups according to any one of claims 1 to 12, characterized in that (a) reacting at least one monomeric diisocyanate with at least one polyether polyol having an OH value of 5 to 58 mg KOH / g in an NCO / OH molar ratio of 4 / 1 to 15 / 1, (b) then removing the majority of the unconverted monomeric diisocyanate by suitable separation methods, (c) finally reacting the obtained polymer containing isocyanate groups with at least one aminosilane, mercaptosilane or hydroxysilane in a stoichiometric ratio of at least 1 mol of aminosilane, mercaptosilane or hydroxysilane per molar equivalent of isocyanate groups.

14. A curable composition comprising at least one polymer containing silane groups according to any one of claims 1 to 12 and at least one further component selected from the group consisting of catalysts, crosslinkers, tackifiers, desiccants, plasticizers and fillers.

15. The curable composition according to claim 14, characterized in that It comprises at least one polymer containing silane groups as claimed in claim 12 and at least one further polymer containing silane groups.

16. The curable composition according to claim 15, characterized in that The silane group-containing polymer is a linear polymer.

17. The curable composition according to any one of claims 14 to 16, characterized in that It is used as an elastic adhesive or elastic sealant or elastic coating.

18. The curable composition of claim 14, wherein It additionally comprises at least one epoxy resin.

19. A cured composition obtained from the curable composition of any one of claims 14 to 18 after contact with moisture.

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