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WO2013079344A1 - Substances réticulables sur la base de polyuréthanes à terminaison organyloxysilane - Google Patents

Substances réticulables sur la base de polyuréthanes à terminaison organyloxysilane Download PDF

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Publication number
WO2013079344A1
WO2013079344A1 PCT/EP2012/072980 EP2012072980W WO2013079344A1 WO 2013079344 A1 WO2013079344 A1 WO 2013079344A1 EP 2012072980 W EP2012072980 W EP 2012072980W WO 2013079344 A1 WO2013079344 A1 WO 2013079344A1
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Prior art keywords
radicals
formula
mol
compounds
polyether
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PCT/EP2012/072980
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German (de)
English (en)
Inventor
Volker Stanjek
Lars Zander
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Wacker Chemie AG
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Wacker Chemie AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1021—Polyurethanes or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the invention relates to crosslinkable compositions based on silane-terminated polyurethanes, processes for their preparation and their use as adhesives and sealants, in particular adhesives with high Switzerlandscherf strength.
  • isocyanate-crosslinking PU adhesives are used. These usually contain isocyanate-functional polyurethane polymers based on aromatic polyisocyanates. Such systems cure by a reaction of the isocyanate groups with (air) moisture.
  • PU adhesives cure by means of a chemical crosslinking reaction and can bind to numerous substrates (eg wood, metals, ceramic substrates, glass, etc.) via chemical bonds, they usually show very good mechanical properties and are also relatively resistant to external ⁇ Weather) influences such as moisture or direct water contact.
  • isocyanate-curing adhesives also have some, sometimes massive, systemic disadvantages.
  • one-component PU adhesive systems generally show only moderate cure speeds.
  • the isocyanate regeneration can in principle be greatly accelerated by suitable catalysis. But since such catalysis basically also catalyze undesired side reactions of the isocyanate groups (eg formation of allophanates, uretdiones, isocyanurates etc.), the corresponding systems then no longer have sufficient storage stability.
  • Another disadvantage of most isocyanate-crosslinking living substances is the health classification, which ranges from sensitizing to toxic. Particularly critical here is the amount of remaining monomeric isocyanates in the uncured adhesive, which are difficult to remove. This is problematic for the end user, i. the craftsman or do-it-yourself user, because he not only with the cured and thus isocyanate-free and completely harmless product, but also with the not yet cured and thus isocyanate-containing adhesive or with the monomeric isocyanates contained in this adhesive in contact comes. With the inexperienced do-it-yourselfer, there is the particular danger that the products may not be used expertly and / or properly. Additional hazards also include inappropriate storage, e.g. within reach of children, out.
  • Isocyanate-curing adhesives that have only very low levels of volatile isocyanates and thus are at least free of labeling are slightly cheaper. However, these are usually based on aliphatic isocyanates, which in turn are less reactive. These adhesives are therefore suitable for applications in which it depends on a quick setting of the adhesive, once again less favorable than conventional PU adhesives.
  • silane crosslinking in which alkoxysilane-functional prepolymers first hydrolyze on contact with atmospheric moisture and then cure by a condensation reaction.
  • the corresponding silane-functional - mostly silane-terminated - prepolymers are generally toxicologically completely harmless.
  • alkoxysilyl groups have long been known. On contact with water or atmospheric moisture, these alkoxysilane-terminated polymers are already able at room temperature to condense with elimination of the alkoxy groups.
  • adhesives based on alkoxysilane-crosslinking polymers in the cured state not only show good adhesion properties on some substrates, but also very good mechanical properties, since they have a certain tensile strength and can be highly elastic on the one hand. Therefore, the corresponding materials are particularly suitable for sealants and elastic adhesives with moderate tensile shear strength. In many applications, one-component systems ⁇ 1K systems) are preferred which harden when exposed to atmospheric moisture.
  • a disadvantage of most common silane-crosslinking systems is the fact that although moderate tensile shear strengths are achievable, which are typically in the order of 1-4 MPa, tensile shear strengths> 5 MPa are not or at best reachable in very unusual formulations.
  • these precipitated formulations again have other limitations, e.g. a black coloration based on the use of carbon black as filler, as described, for example, in WO 02/090411.
  • no tensile strengths> 6.5 MPa can be achieved with the formulations described in WO 02/090411.
  • silane-crosslinking systems Another possibility for increasing the tensile strength of silane-crosslinking systems is the incorporation of short-chain diols into silane-crosslinking polyurethanes, as described in WO
  • silane-crosslinking systems as described in WO2011 / 026658. Be here achieves very high tensile shear strengths of up to 16 MPa through the use of silane-terminated polyurethanes based on extremely short-chain polyols. This leads, on the one hand, to the fact that the resulting silane-crosslinking polymers have a very high density of hydrogen bonds
  • the invention relates to mixtures (A) containing at least two different compounds of the formula
  • Y is an x-valent organic radical
  • R 3 may be identical or different and is hydrogen, a monovalent, optionally substituted, SiC-bonded hydrocarbon radical, a group - (CR 1 2 ) b'-SiR a (OR 2 ) 3-a or a group -CH (COOR ') -CH 2 ⁇ COOR' means may be the same or different and represents a monovalent, optionally substituted hydrocarbon est,
  • SiC-bonded hydrocarbon radical may be the same or different and represents a monovalent, optionally substituted, SiC-bonded hydrocarbon radical
  • the carbon atom may be identical or different and represents hydrogen atom or a monovalent, optionally substituted hydrocarbon radical which may be attached to the carbon atom via nitrogen, phosphorus, oxygen, sulfur or carbonyl group,
  • radicals Y contain at least one aromatic group and that part of the radicals Y contains at least one polyether unit, the average molecular weight M n (number average) of all polyether units contained in the radicals Y being between 1500 and 6500 g / mol is.
  • the number-average molar mass M n is determined by means of size
  • mixtures (A) according to the invention are preferably those containing compounds (AI) of the formula and compounds (A2) of the formula
  • Y 1 is an x'-valent organic radical which contains at least two urethane groups, at least two groups Y 2 and at least one polyether unit, wherein the average molecular weight M n of all polyether units contained in the radicals Y 1 is between 1500 and 6000 g / mol lies.
  • Y 2 is an unsubstituted or substituted oxygen radical of 6 to 40 carbon atoms which has at least one aromatic group and is free of urethane, urea, polyether and polyester groups
  • x 'and x r ' each independently in formula (I) have the meaning given for x and R
  • R 1 , R 2 , R 3 , a and b have one of the meanings given in formula (1).
  • the mixture (A) according to the invention preferably comprises less than 10% by weight, more preferably less than 5% by weight, in particular less than 1% by weight, of compounds of the formula (I) which do not have any of the formulas (I ') or (I''), in each case based on the total mass of all compounds of the formula (I) in the mixture (A).
  • the mixture (A) contains no compounds of the formula (I) which do not correspond to one of the formulas ( ⁇ ') or (I'').
  • the mixture (A) according to the invention contains at least 5 mol%, more preferably at least 10 ol-%, in particular at least 20 mol% of compounds of formula (I '') in each case based on the total of compounds of the formulas ⁇ ! ' ) and ⁇ ! '' ⁇ in the mixture (A).
  • the mixture (A) according to the invention preferably contains not more than 80 mol%, more preferably not more than 50 mol% of compounds of the formula (I ''), based in each case on the total of compounds of the formulas (I ') and (II'') the mixture (A).
  • the mixture ⁇ A) according to the invention can contain only one type of compound of the formulas (I and (X) as well as mixtures of different types of compounds of the formulas ⁇ IM and (X 'M)
  • Formulas ⁇ IM and ( ⁇ 'M contain in which more than 90%, preferably more than 95%, more preferably more than 98%, of all of the radicals Y 1 or Y 2 bound silyl groups are identical is a mixture (A) which contains, at least in part, compounds of the formulas (IM and ( ⁇ 'M in which different silyl groups are bonded to a radical Y 1 or Y 2.
  • radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-penyl radical; Hexyl radicals, such as the n-hexyl radical; Heptyl radicals, such as the n-heptyl radical; Octyl radicals, such as the n-octyl radical, iso-octyl radicals and the 2, 2, -trimethylpentyl radical are nonyl radicals, such as the n-nonyl radical; Decyl radicals, such as the n-decyl radical; Dodecyl radicals, such as the n-dodecyl radical; Octadecyl radicals, such as the n-
  • substituted radicals R are haloalkyl radicals, such as the 3, 3, 3-trifluoro-n-propyl radical, the 2, 2, 2, 2 ", 2 ' , 2'-hexafluoroisopropyl radical and the heptafluoroisopropyl radical, and haloaryl radicals, such as the o-, m- and p-chlorophenyl.
  • Radicals R are preferably all monovalent hydrocarbon radicals having 1 to 6 carbon atoms which are substituted by halogen atoms, particularly preferably alkyl radicals having 1 or 2 carbon atoms, in particular the methyl radical.
  • radicals R 1 are hydrogen, the radicals indicated for R and optionally substituted by nitrogen, phosphorus, oxygen, sulfur, carbon or carbonyl group bonded to the carbon atom, optionally substituted hydrocarbon radicals.
  • Radical R 1 is preferably hydrogen atom and hydrocarbon radicals having 1 to 20 carbon atoms, in particular hydrogen atom.
  • radical R 2 are hydrogen atom or the examples given for radical R.
  • the radicals R 2 are preferably hydrogen atoms or alkyl radicals having 1 to 10 carbon atoms optionally substituted by halogen atoms, more preferably alkyl radicals having 1 to 4 carbon atoms, in particular the methyl and ethyl radical.
  • the radical R 3 is preferably a group
  • R, R ⁇ R 1, R 2, a and b equal to a in formula (I) given meanings or an optionally substituted hydrocarbon radical having 1 to 20 carbon atoms, particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an optionally halogen-substituted aryl group having 6 to 20 carbon atoms, in particular a linear; branched or cyclic alkyl group having 1 to 8 carbon atoms.
  • radicals R ' are preferably alkyl groups having 1 to 10 carbon atoms, particularly preferably methyl, ethyl or propyl radicals.
  • radicals R 3 are optionally substituted hydrocarbon radicals are the radicals specified for R, in particular cyclohexyl, cyclopentyl, n- and iso-propyl, n-, iso- and t-butyl-, the various sterioisomers of the pentyl radical, he- xyl radicals or heptyl radicals and the phenyl radical.
  • a is preferably bound to the groups Y 2 .
  • the radicals Y 1 are on average at least 70% by weight, preferably at least 80% by weight, in particular at least 90% by weight, of urethane groups, groups Y 2 and polyether units, in each case based on the average total weight of all radicals
  • radicals Y 1 consisting solely of urethane groups and Y 2 units polyether.
  • the polyether units contained in the groups Y 1 are preferably branched and / or unbranched polyether units having an average molecular weight M n of 2500 to 5000 g / mol. They preferably have no or one branch point.
  • the polyethers contained in the groups Y 1 correspond to the formula
  • R may be the same or different and is an optionally substituted alkyl radical having 2 to 10 carbon atoms
  • n is an integer, with the proviso that n has on average a size such that the polyether units have an average molar mass M n of 1500 to 6000 g / mol, preferably 2500 to 5000 g / mol.
  • R 4 is preferably alkyl radicals having 2 to 4 carbon atoms, more preferably groups of the formulas -CH 2 -CH 2 -, -CH (CH 3 ) -CH 2 - and -CH 2 -CH (CH 3 ) -, in particular to
  • the radicals Y 2 are preferably a divalent toluyl radical or a divalent diphenylmethane radical.
  • the mixture (A) according to the invention can be prepared in any manner, e.g. by mixing different compounds of the formula (I),
  • the mixture (A) according to the invention can preferably be prepared by reacting polyols, aromatic di- and / or polyisocyanates and inosilanes.
  • Another object of the invention are mixtures (A) preparable by reaction of
  • Another object of the invention is a process for preparing the mixtures ⁇ A) by reacting
  • the polyols (a) used according to the invention are preferably branched or unbranched polyetherpolyols, preferably polypropyleneglycols, in particular unbranched polypropyleneglycols or polypropylene glycols having a branching point.
  • the polyols (a) used according to the invention have an average molar mass M n of preferably 2500 to 5000 g / mol. Most preferably, they have no branching point.
  • component (a) it is also possible to use mixtures of unbranched and singly branched polyols.
  • Polyols (a) used according to the invention are commercially available products or can be prepared by processes customary in chemistry.
  • component (b) used according to the invention are all conventional di- or polyisocyanates, such as e.g. Diisocyanato-diphenylmethane (MDI), both in the form of crude or industrial MDI and in the form of pure 4,4 'or 2,4' isomers or mixtures thereof, tolyl diisocyanate (TDI) in the form of its various regioisomers, in particular 2,4 - As well as the 2, 6 -TDI and mixtures of these regioisomers.
  • MDI Diisocyanato-diphenylmethane
  • TDI tolyl diisocyanate
  • Isocyanates (b) used according to the invention are commercially available products or can be prepared by processes customary in chemistry.
  • polyol (a) is preferably used in amounts such that at least 0.2 mol, more preferably at least 0.3 mol, in particular, of the NCO groups of component (b) and of any further NCQ.sub.min-containing components present in the reaction mixture at least 0.4 mol, hydroxyl groups of component (a) are used.
  • polyol (a) is preferably used in amounts such that at most 0.8 mol, more preferably at most 0.7 mol, per mole of NCO groups of component (b) and further NCO-containing components optionally present in the reaction mixture, in particular at most 0.6 mol, hydroxyl groups of component (a) are used.
  • component (c) is um
  • component (c) is preferably used in amounts such that at least 0.2 mol, particularly preferably at least 0.3 mol, in particular at least 0.4, are present for 1 mol of isocyanate groups of component (b) and other isocyanate-functional components present in the reaction mixture Mol, amine groups of component (c) are used and reacted with the isocyanate groups.
  • component (c) is preferably used in amounts such that per mole of NCO groups of the component
  • the optional further components may be isocyanate-reactive compounds (d) which are different from component (a) and (c), monoisocyanates (e) and catalysts (f).
  • optionally used component (d) are compounds having one or more NH, OH or SH functions.
  • monomeric alcohols such as methanol, ethanol or butanol, preferably alcohols having at least 6 carbon atoms, particularly preferably alcohols having at least 8 carbon atoms, in particular having at least 10 carbon atoms, can be used as optionally used component ⁇ d), where the alcohols (d) preferably have linear or branched alkyl radicals.
  • These alcohols also react with the di- or polyisocyanates (b). This results in compounds analogous to formula (I) whose chain ends are not sufficient. are ultimately silanterminiert, but also have a certain proportion urethanstreeter alkyl end groups.
  • component (d) it is also possible to use monomeric alcohols having 2 to 4 hydroxyl groups, preferably 2 hydroxyl groups, e.g. Glycol, propanediol, glycerol and pentaerythritol, wherein 1, ⁇ butanediol or dimer diol, such as. Pripol 2033 from Croda, are particularly preferred. If component (d) is used, these are preferably amounts which, for 1 mol of NCO groups of component (b) and of further NCO-containing components optionally present in the reaction mixture, are at most 0.20 mol, especially before 0 , 1 mole, NCO-reactive groups of component (d) are used. For the preparation of the mixture (A) according to the invention, preferably no component (d) is used.
  • 2 hydroxyl groups e.g. Glycol, propanediol, glycerol and pentaerythritol, wherein 1, ⁇ butanediol or dimer diol
  • compounds having an isocyanate group (e) can be used as further components, e.g. Butyl isocyanate, cyclohexyl isocyanate or phenyl isocyanate.
  • component (e) are preferably amounts which, for 1 mol of NCO groups of component (b), are at most 0.20 mol, more preferably at most 0.1 mol, in particular 0.05 mol, NCO- Groups of component € are used.
  • NCO- Groups of component € are used for the preparation of the mixture (A) according to the invention preferably no component (e) is used.
  • the preparation according to the invention of the mixtures (A) can be carried out in the presence of a catalyst (f), which is preferred.
  • catalysts (f) are bismuth-containing catalysts such as the Borchi ® Kat 22, Borchi ® Kat VP 0243, Borchi ® Kat VP 0244 from Fa. Borchers GmbH, as well as those compounds (F) are described below as catalysts Kärtungskata-. If catalysts (f) are used to prepare the mixtures (A), amounts of from 0.001 to 5 parts by weight, in particular from 0.05 to 1 part by weight, based in each case on 100 parts by weight of mixture (A), are preferred.
  • the mixture (A) has been prepared from educts which are at least 80% by weight, particularly preferably at least 90% by weight, in particular at least 95% by weight, very particularly preferably 100% components (a), (b) and (c), in each case based on the total weight of all components (a) to ⁇ e).
  • the components (a), (b), (c) and the optionally further components are used in an amount ratio according to which at least 0.6 and preferably at most 1.4, more preferably at least 0, per 1 isocyanate group, 8 and at most 1.2, isocyanate-reactive groups come.
  • the components used in the process according to the invention may each be a type of such a component as well as a mixture of at least two types of a respective component.
  • reaction steps may optionally be carried out in the presence of a catalyst. If additionally one or more components (d) and / or (e) are used, these can in principle be added to the reaction mixture at any time. However, if desired, monoisocyanate compounds (e) to be used are used together with component (b) and further isocyanate-reactive compounds (d) to be used are preferably added to the reaction mixture together or else directly before or after component (a). In addition to this preferred method of preparation but also many variations of the method according to the invention are conceivable.
  • reaction sequence can in principle also be reversed, and first a reaction between the isocyanate component (b) and the silane component (c) are carried out before the polyol component (a) is added. It is also conceivable to add the silane component (c) and the polyol component (a) either simultaneously but via separate feed lines to the reaction mixture or to use them together as a mixture and to react with the isocyanate component (b). In these process variants as well, any further components (d) and / or (e) can in principle be added to the reaction mixture at any time, but it is the same above-mentioned preferred combinations of (b) and (e) or (a) and (d).
  • the polyol component (a) could first be reacted only with a part of the isocyanate component (b) and the NCO- or OH-functional intermediate product obtained depending on the stoichiometry could only be reacted in the following reaction steps with the remaining parts of the isocyanate component (b ) as well as the
  • Silane component (c) are reacted.
  • the process according to the invention is preferably carried out at temperatures of at least 0 ° C., particularly preferably at least 20 ° C. and preferably at most 150 ° C., in particular at most 100 ° C.
  • the process according to the invention is preferably carried out with the exclusion of (atmospheric) moisture and the pressure of the surrounding atmosphere, ie about 900 to 1100 hPa.
  • the process of the invention may be continuous, e.g. in a tubular reactor with several juxtaposed or consecutive dosing points, or discontinuously, e.g. in a conventional reaction vessel with stirrer, done.
  • the mixture according to the invention or prepared according to the invention (A) may contain, in addition to compounds of the formula (I), further substances, for example unreacted silane radicals and also catalyst (f).
  • the mixture (A) according to the invention is preferably isocyanate-free.
  • the isocyanate purity can also be achieved if the abovementioned excesses of NCO groups, based on the NCO-reactive groups, are used because the excess NCO groups are also present, for example, with urethane and / or urea units formed Allophanat- or Biurethbil- education can react.
  • the mixture (A) according to the invention preferably has an average molecular weight M n of at least 400 g / mol, particularly preferably at least 800 g / mol, and preferably at most 10,000 g / mol, particularly preferably at most 8,000 g / mol, in particular at most 5 000 g / mol, on.
  • the viscosity of the mixture (A) is preferably at least 1 Pas, preferably at least 10 Pas, more preferably at least 20 Pas, and preferably at most 1000 Pas, preferably at most 500 Pas, in particular at most 200 Pas, each measured at 25 ° C.
  • mixtures according to the invention or prepared according to the invention (A) can be used for all purposes to which hitherto silane-terminated polyurethanes have also been used.
  • the mixtures according to the invention or prepared according to the invention (A) are storable with the exclusion of water and can be crosslinked on entry of water at room temperature, which results in a multiplicity of possible applications.
  • the crosslinkable compositions may contain all further substances which have hitherto been used in crosslinkable compositions, Another object of the invention are crosslinkable compositions containing (M)
  • radicals Y contain at least one aromatic group and that part of the radicals Y contains at least one polyether unit, wherein the average molecular weight M n of all polyether units contained in the radicals Y is between 1500 and 6500 g / mol, optionally
  • Component (A) is preferably those comprising compounds ⁇ AI) and (A2).
  • compositions (M) according to the invention preferably contain component (A) in concentrations of 50 to 99% by weight, more preferably 60 to 98% by weight, if they are transparent compositions.
  • the compositions ⁇ M) according to the invention preferably contain the component (A) in concentrations of 10 to 70% by weight, particularly preferably 20 to 60% by weight.
  • compositions (M) are moisture-curing, i. they are preferably liquid or pasty masses which harden on contact with moisture and / or atmospheric moisture.
  • component (B) it is possible to use all polymers which hitherto have known condensable groups and do not correspond to formula (I).
  • Polymers (B) used according to the invention preferably contain no urea units.
  • polymers (B) are alkoxysilane-terminated polyethers (B1). These preferably have average molecular weights M n of from 1 000 to 50 000 g / mol, in particular from 8 000 to 30 000 g / mol. Corresponding products are commercially available, for example, under the name MS polymer from Kaneka or GENIOSIL STP-E from Wacker Chemie AG.
  • the compositions (M) according to the invention preferably contain no silane-crosslinking polymers (B) which are not silane-terminated polyethers (B1).
  • compositions (M) according to the invention comprise silane-crosslinking polyethers (B1), these are amounts of preferably at most 50% by weight, in particular at most 25% by weight, and at least 1% by weight, in particular at least 5% by weight. %, in each case based on the weight of the total mass (M). In a particularly preferred embodiment of the invention, however, the compositions (M) according to the invention contain no polymers (B) which do not correspond to the formula (I) at all.
  • the basic nitrogen-containing organosilicon compounds (C) present in the compositions (M) according to the invention are preferably organosilicon compounds containing units of the formula D c Si ⁇ OR s ⁇ d R s e O (4- c -ae) / 2 ( VII), in which
  • R 5 may be identical or different and is hydrogen atom or optionally substituted hydrocarbon este
  • D may be identical or different and represents a monovalent, SiC-bonded radical with basic nitrogen
  • R 5 may be the same or different and a monovalent, optionally substituted SiC-bonded, of basic
  • c 0, 1, 2, 3 or 4, preferably 1,
  • d is 0, 1, 2 or 3, preferably 1, 2 or 3, more preferably 2 or 3, and
  • e is 0, 1, 2 or 3, preferably 1 or 0, with the proviso that the sum of c + d + e is less than or equal to 4 and at least one residue D is present per molecule.
  • optionally substituted hydrocarbon radicals R 5 are the examples given for the radical R.
  • the radicals R s are preferably hydrogen atom and optionally halogen atoms substituted hydrocarbon radicals having 1 to 18 carbon atoms, more preferably hydrogen and hydrocarbon radicals having 1 to 10 carbon atoms, in particular methyl and ethyl radical.
  • radical R s are the examples given for R.
  • the radicals R G are preferably hydrocarbon radicals having 1 to 18 carbon atoms which are optionally substituted by halogen atoms, more preferably hydrocarbon radicals having 1 to 5 carbon atoms, in particular the methyl radical.
  • radicals D are radicals of the formulas H 2 N (CH 2 ) 3 -,
  • radical D is the H 2 N (CH 2 ) 3 -,
  • silanes of the formula (VII) used according to the invention are all silanes which have already been mentioned as examples of component (c), as well as their partial hydrolysates, and also H 2 N (CH 2 ) 2 NH (CH 2 ) 3 -Si (OCH 3) 3, H 2 N (CH 2) 2 NH (CH 2) 3 - Si ⁇ OC 2 H s) 3, H 2 N (CH 2) 2 NH (CH 2) 3 -Si ( OCH 3 ) 2 CH 3 , H 2 N (CH 2 ) 2 NH (CH 2 ) 3 -Si (OC 2 H 5 ) 2 CH 3 , H 2 N ⁇ CH 2 ) 2 NH (CH 2 ) 3 ⁇ Si ( OH) 3, H 2 N (CH 2) 2 NH (CH 2) 3 - Si (OH) 2 CH 3, H 2 N (CH 2) 2 NH ⁇ CH 2) 2 NH (CH 2) 3 -Si ( OCH 3 ) 3 ,
  • H 2 W (CH 2 ) 2 NH ⁇ CH 2 ) 2 NH (CH 2 ) 3 -Si (OC 2 H 5 ) 3 , as well as their partial hydrolysates, wherein H 2 N (CH 2 ) 2 NH (CH 2 ) 3 -Si (OCH 3 ) 3 , H 2 N (CH 2 ) 2 NH (CH 2 ) 3 -Si (OC 2 H 5 ) 3 , H 2 N (CH 2 ) 2 NH (CH 2 ) 3 -Si (OCH 3 ) 2 CH 3 , cyclo-CeHnNH (CH 2 ) 3 -
  • the organosilicon compounds ⁇ C) used according to the invention can also assume the function of a curing catalyst or cocatalyst in the compositions (M) according to the invention. Furthermore, the organosilicon compounds (C) used according to the invention can act as mediators and / or as water scavengers.
  • organosilicon compounds (C) used according to the invention are commercially available products or can be prepared by processes customary in chemistry.
  • compositions (M) according to the invention comprise component (C) in amounts of preferably 0.01 to 25 parts by weight, more preferably 0.1 to 10 parts by weight, in particular 0.5 to 5 parts by weight, based in each case on 100 parts by weight of component (A).
  • the fillers (D) optionally used in the compositions (M) according to the invention may be any known fillers known to date.
  • fillers (D) are non-reinforcing fillers, ie fillers having a BET surface area of preferably up to 50 m 2 / g, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, talc, kaolin, zeolites, metal oxide powder, such as aluminum, titanium -, iron or zinc oxides or their mixed oxides, Bariumsulf t, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass and plastic powder, such as polyacrylonitrile powder; Reinforcing fillers, ie fillers with a BET surface area of more than 50 m 2 / g, such as pyrogenic silica, precipitated silica, precipitated chalk, carbon black, such as furnace and acetylene black and silicon-aluminum mixed oxides of large BET surface area; Aluminiumtrihydroxid, hollow spherical fillers, such as ceramic microspheres, such as
  • the optionally used fillers (D) are preferably calcium carbonate, talc, aluminum trihydroxide and silicic acid, with calcium carbonate and aluminum trihydroxide being particularly preferred.
  • Preferred calcium carbonate types are ground or precipitated and optionally surface-treated with fatty acids such as stearic acid or its salts.
  • the preferred silica is preferably fumed silica.
  • Optionally used fillers (D) have a moisture content of preferably less than 1 wt .-%, particularly preferably less than 0.5 wt .-%.
  • compositions (M) according to the invention contain fillers (D), they are amounts of preferably 10 to 1000 parts by weight, more preferably 50 to 500 parts by weight, in particular 70 to 200 parts by weight, in each case based on 100 parts by weight of component (A).
  • the compositions of the invention (M) preferably contain fillers (D).
  • the compositions ⁇ M) according to the invention as fillers ⁇ D) comprise a combination of
  • silica in particular fumed silica
  • the silicone resins (E) optionally used in the compositions (M) according to the invention are preferably compounds containing units of the formula
  • R 7 may be the same or different and is hydrogen atom, a monovalent, Sic-bonded, optionally substituted aliphatic or aromatic hydrocarbon radical,
  • R 8 may be the same or different and is hydrogen or a monovalent, optionally substituted hydrocarbon radical
  • f 0, 1, 2 or 3
  • g is 0, 1, 2 or 3, preferably 0, 1 or 2, particularly preferably 0 or 1, with the proviso that the sum of f + g is less than or equal to 3 and in at least 50%, preferably at least 60% of the formula (VIII) f is 0 or 1.
  • Component (E) preferably consists of at least 90% by weight of units of the formula (VIII).
  • Component (E) is particularly preferably composed exclusively of units of the formula (VIII).
  • radicals R 7 are the examples given above for R.
  • R 7 is optionally taken together with Halogen atoms substituted, monovalent SiC-bonded aliphatic or aromatic hydrocarbon radicals having 1 to 18 carbon atoms, particularly preferably the methyl or phenyl reat.
  • at least 40%, preferably at least 50% of the units of the formula ⁇ VIII) have a radical R 7 which is a phenyl radical.
  • radical R 8 are hydrogen atom or the examples given for radical R.
  • the radicals R e are preferably hydrogen atoms or alkyl radicals optionally substituted by halogen atoms having 1 to 10 carbon atoms, more preferably the methyl and ethyl radicals.
  • silicone resins which can be used as component (E) are organopolysiloxane resins which consist essentially, preferably exclusively, of (Q) units of the formulas Si0 4/2 , Si (OR 8 ) 0 3/2 , Si (OR 8 ) 2 0 2 / 2 and Si (OR 8 ) 3O1 / 2, (T) units of the formulas PhSiO 3/2 , PhSi (OR 8 ) O 2/2 and PhSi (OR 8 )? i / 2, (D) units of the formulas
  • Me 3 SiOi / 2 consist, wherein Me is a methyl radical, Ph is a phenyl radical and R 8 is hydrogen or optionally substituted by halogen atoms substituted alkyl radicals having 1 to 10 carbon atoms, particularly preferably hydrogen atom or alkyl radicals having 1 to 4 carbon atoms, wherein the resin per mole of (T) units preferably contains 0-2 mole (Q) units, 0-2 mole (D) units and 0-2 mole (M) units.
  • Preferred examples of silicone resins which can be used as components (E) are organopolysiloxane resins which consist essentially, preferably exclusively, of T units of the formulas
  • PhSi0 3/2 , PhSi (OR 8 ) 0 2/2 and PhSi (OR 8 ) 2 0i / 2 optionally T in units of the formulas MeSi0 3 / a , MeSi (OR s ) 0 2/2 and MeSi (OR 8 ) 2 0 1/2 and optionally D units of the formulas Me 2 Si0 2/2 and
  • the silicone resins which can be used as components (E) preferably have a number average molecular weight M n of at least 400 g / mol and more preferably of at least 600 g / mol.
  • the silicone resins which can be used as components (E) are commercial products, e.g. to different
  • compositions (M) according to the invention contain component (E), these are amounts of at least 5 parts by weight, more preferably at least 10 parts by weight, in particular at least 50 parts by weight and preferably at most 1000 parts by weight, more preferably at most 500 parts by weight, in particular at most 300 parts by weight based on 100 parts by weight of the mixture (A).
  • the catalysts (P) optionally used in the compositions (M) according to the invention may be any, hitherto known catalysts for compositions which cure by silane condensation.
  • metal-containing curing catalysts (F) are organic titanium and organic compounds, for example titanic acid esters, such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate and titanium tetraacetyl acetonate; Tin compounds, such as dibutyl indole dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutylzincindioctanoate, dibutyltin acetylacetonate, dibutyltin oxides, and corresponding dioctyltin compounds.
  • titanic acid esters such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate and titanium tetraacetyl acetonate
  • Tin compounds such as dibutyl indole dilaurate, dibutyltin maleate, dibutyltin di
  • metal-free curing catalysts (F) are basic compounds, such as triethylamine, tributylamine, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4.3.0] o ⁇ -5-ene, 1, 8-diazabicyclo [5.4.0] undec-7-ene, ⁇ , ⁇ -bis (N, N-dimethyl-2-aminoethyl) methylamine, N, N-diraethylcyclohexylamine, N, -dimethylphenylamine and W -Ethylmorpholinin.
  • basic compounds such as triethylamine, tributylamine, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4.3.0] o ⁇ -5-ene, 1, 8-diazabicyclo [5.4.0] undec-7-ene, ⁇ , ⁇ -bis (N,
  • acidic compounds such as phosphoric acid and its esters, toluenesulfonic acid, sulfuric acid, nitric acid or organic carboxylic acids, e.g. Acetic acid and benzoic acid.
  • the optionally used catalysts (F) are metal-containing curing catalysts, preferably tin-containing catalysts.
  • This embodiment of the invention is particularly preferred when component (A) consists entirely or at least partially, ie at least 90% by weight, preferably at least 95% by weight, of compounds of the formula (I) in which b is not equal to 1.
  • the compositions () of the invention comprise catalysts (F), they are amounts of preferably 0.01 to 20 parts by weight, more preferably 0.05 to 5 parts by weight, in each case based on 100 parts by weight of component (A).
  • the adhesion promoters (G) optionally used in the compositions (M) according to the invention may be any adhesion promoters hitherto known to cure by silane condensation.
  • adhesion promoters are epoxysilanes, such as glycidoxypropyltrimethoxysilanes, glycidoxypropylmethyldimethoxysilane, glycidoxypropyltriethoxysilane or glycidoxypropylmetyldiethoxysilane, 2- (3-triethoxysilylpropyl) maleic anhydride, N, (3-trimethoxysilylpropyl) urea, N- (3 Triethoxysilylpropyl) urea, N ⁇ (trimethoxysilylmethyl) urea, N- (methyldimethoxysilymethyl) urea, N- (3-triethoxysilylmethyl) urea, N- (3-methyldiethoxysilylmethyl) urea, O-methylcarbamatomethyl-1-methyldimethoxy ilane, O-ethylcarbamatomethyltrimethoxysilane, O-ethylcarbamat
  • compositions (M) according to the invention comprise adhesion promoters (G), these are amounts of preferably 0.5 to 30 parts by weight, more preferably 1 to 10 parts by weight, based in each case on 100 parts by weight of component ⁇ A).
  • the water scavengers (H) optionally used in the compositions (M) according to the invention may be any water scavengers described for systems which cure by silane condensation atoxyl.
  • water scavengers are silanes, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, O-methylcarbamatomethylmethyldimethoxysilane, O-methylcarbamatomethyltrimethoxysilane, O-ethylcarbamatomethylmethyldiethoxysilane, O-ethylcarbamatomethyltriethoxysilane, and / or their partial condensates and orthoesters such as 1, 1, 1-trimethoxyethane, 1, 1, l-triethoxyethane, trimethoxymethane and triethoxymethane.
  • silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, O-methylcarbamatomethylmethyldimethoxysilane, O-methylcarbamatomethyltrimethoxysilane, O-ethylcarbamatomethylmethyldiethoxysi
  • compositions (M) according to the invention comprise water scavengers (H), these are amounts of preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, based in each case on 100 parts by weight of component (A).
  • the non-reactive plasticizers (I) optionally used in the compositions (M) according to the invention may be any plasticizers known to date for silane-crosslinking systems. Examples of non-reactive plasticizers (I) are phthalic esters (e.g., dioctyl phthalate, diisooctyl phthalate and di-n-octyl phthalate), perhydrogenated phthalic acid esters ⁇ e.g.
  • 1,2-cyclohexanedicarboxylic acid diisononyl ester and 1,2-cyclohexanedicarboxylic acid dioctyl ester) adipic acid esters e.g., dioctyl adipate
  • benzoic acid esters glycol esters, esters of saturated alkanediols (e.g.
  • polyethers eg polyethylene glycols and Polypropylene glycols having molecular weights M n of preferably from 400 to 10,000 g / mol
  • polystyrenes polybutadienes
  • polyisobutylenes paraffinic hydrocarbons and high molecular weight, branched hydrocarbons.
  • compositions (M) according to the invention contain nonreactive plasticizers (I), these are amounts of preferably 0.01 to 100 parts by weight, based on 100 parts by weight of component (A).
  • the compositions (M) according to the invention preferably contain less than 10 parts by weight, more preferably less than 5 parts by weight, in particular less than 2 parts by weight, non-reactive plasticizers (I), in each case based on 100 parts by weight of component (A).
  • compositions (M) of the invention contain no non-reactive plasticizers (I).
  • the additives (J) optionally used in the compositions (M) according to the invention may be any desired additives known to date for silane-crosslinking systems.
  • the additives (J) which may optionally be used according to the invention are preferably anionic antioxidants, UV stabilizers, such as e.g. so-called HALS compounds, fungicides and pigments.
  • compositions (M) according to the invention contain additives (J), these are amounts of preferably from 0.01 to 30% by weight. parts by weight, particularly preferably 0.1 to 10 parts by weight, in each case based on 100 parts by weight of component (A).
  • the additives optionally used according to the invention (K) are preferably tetraalkoxysilanes, e.g. Tetraethoxysilane and / or their partial condensates, plasticizers, reactive plasticizers, rheology additives, flame retardants and organic solvents.
  • Preferred reactive plasticizers CK) are compounds which contain alkyl chains having 6 to 40 carbon atoms and have a group which is reactive with the compounds (A).
  • Examples are isooctyltrimethoxysilane, isooctyltriethoxysilane, N-octyltrimethoxysilane, N-octyltriethoxysilane, decyltrimethoxysilanes, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tetradecyltriraethoxysilane, tetradecyltriethoxysilane, hexadecyltrimethoxysilane, and hexadecyltriethoxysilane.
  • the rheology additives (K) are preferably polyamide waxes, hydrogenated castor oils or stearates.
  • organic solvents (K) are low molecular weight ethers, esters, ketones, aromatic and aliphatic and optionally halogen-containing hydrocarbons and alcohols, the latter being preferred.
  • compositions (M) according to the invention Preferably no organic solvents (K) are added to the compositions (M) according to the invention.
  • the compositions () according to the invention contain one or more components (K), they are in each case amounts of preferably from 0.5 to 200 parts by weight, more preferably from 1 to 100 parts by weight, in particular 2 to 70 parts by weight, in each case based on 100 parts by weight of component (A).
  • compositions (M) according to the invention preferably contain no further components apart from the components (A) to (K).
  • the components used according to the invention may each be one type of such a component as well as a mixture of at least two types of a respective component.
  • compositions (M) according to the invention are preferably formulations having viscosities of preferably from 500 to
  • 1 000 000 mPas more preferably from 1 000 to 500 000 mPas, in particular from 5 000 to 100 000 mPas, in each case at 25 ° C.
  • compositions (M) according to the invention are preferably adhesives or sealants, more preferably adhesives.
  • Another object of the present invention is a process for the preparation of the inventive masses (M) by mixing the individual components in any order.
  • compositions (M) according to the invention can be carried out in any manner known per se, such as by methods and mixing methods, as are customary for the preparation of moisture-curing compositions.
  • component (A) can be used as the mixture according to the invention described above, or the individual compounds of formula (I) contained in mixture (A) can be used separately from one another.
  • This mixing can be carried out at room temperature, ie at temperatures between 0 and 30 ° C and the pressure of the surrounding atmosphere, ie about 900 to 1100 hPa. If desired, however, this mixing can also take place at relatively high temperatures, for example at temperatures in the range from 30 to 130.degree.
  • the mixing according to the invention is preferably carried out with exclusion of moisture.
  • the process according to the invention can be carried out continuously or batchwise.
  • compositions (M) according to the invention are preferably one-component materials which can be stored under exclusion of water and which are crosslinkable at room temperature on the admission of water.
  • the compositions (M) according to the invention can also be part of two-component crosslinking systems in which OH-containing compounds, such as water, are added in a second component.
  • the usual water content of the air is sufficient.
  • the crosslinking of the compositions (M) according to the invention is preferably carried out at room temperature. If desired, it may also be carried out at temperatures higher or lower than room temperature, for example at -5 ° to 15 ° C or at 30 ° to 50 ° C and / or above the normal water content of the air.
  • the crosslinking is carried out at a pressure of 100 to 1100 hPa, in particular at the pressure of the surrounding atmosphere, that is about 900 to 1100 hPa.
  • Another object of the invention are moldings prepared by crosslinking of the mixtures (A) or the compositions of the invention (M), in particular of the masses (M).
  • the shaped bodies according to the invention can be any desired shaped bodies, such as, for example, gaskets, pressings, extruded profiles, coatings, impregnations, potting, lenses, prisms, polygonal structures, laminate or adhesive layers.
  • compositions (M) according to the invention have tensile shear strengths of at least 5 MPa, preferably at least 7 MPa and particularly preferably at least 8 MPa.
  • Another object of the invention is a method for bonding substrates in which the composition of the invention applied to the surface of at least one substrate, this surface is then brought into contact with the second substrate to be bonded and then allowed to crosslink,
  • substrates which can be bonded according to the invention are in particular wood but also plastics including PVC, concrete, mineral substrates, metals, glass, ceramics and painted surfaces. Both identical and different materials can be glued together.
  • Another object of the invention is a method for
  • compositions according to the invention are applied to at least one substrate and is allowed to network.
  • examples include coatings, encapsulation, eg casting compounds for LEDs or other electronic components, the production of molded articles, composite materials and composite ormwel.
  • Composite molding parts is to be understood here as a uniform molded article made of a composite material which is composed of a crosslinking product of the compositions (M) according to the invention and at least one substrate in such a way that a firm, permanent bond exists between the two parts.
  • the mixtures (A) according to the invention have the advantage that they are easy to prepare.
  • mixtures (A) according to the invention have the advantage that adhesives having excellent properties can be produced therewith.
  • compositions (M) according to the invention have the advantage that they are easy to prepare.
  • the crosslinkable hate (M) according to the invention have the advantage that they are distinguished by a very high storage stability and a high crosslinking rate. Furthermore, the crosslinkable compositions (M) according to the invention have the advantage that they have an excellent adhesion profile.
  • crosslinkable compositions (M) according to the invention have the advantage that they are easy to process.
  • the crosslinkable compositions (M) according to the invention have the advantage that adhesives with high tensile shear strength can be obtained therefrom.
  • all viscosity data refer to a temperature of 25 ° C. Unless otherwise specified, the examples below are at a pressure of the surrounding atmosphere, ie at about 1000 hPa, and at room temperature, ie at about 23 ° C, or at a temperature resulting from combining the reactants at room temperature without additional heating or cooling, and at a relative air humidity of about 50%. Furthermore, all parts and percentages are by weight unless otherwise specified.
  • cooling and heating possibilities are 840 g (0.2 mol) of a polypropylene glycol having an average molecular weight M n of 4200 g / mol (Acclaim * 4200 Fa. Bayer Material Science, D-Leverkusen) submitted and dried for 2 h at 80 ° C and 1 mbar with stirring. It is then cooled to room temperature and then 100 g (0.4
  • the formulation is filled into a 310 ml PE cartridge, stored for 24 hours at 25 ° C and then examined.
  • silane-terminated polyurethane mixture the preparation of which is described in Example 2 are obtainable with 95 g of aluminum trihydroxide having a BET surface area of 3-5 m 2 / g and a d 50 value of 1.7-2.1 ⁇ m available under the name "Martinal OL 104" from Albemarle Corp.) with stirring for one minute at 600 rpm, then 3 g N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (GENIOSIL * GF 9 from Wacker Chemie AG, D-Munich) for 1 minute at 200 rev / min mixed.
  • dibutylzin-bis-acetyl-acetonate are metered in for 2 minutes at 600 rpm and homogenized for 1 minute at 200 rpm at a pressure of 100 mbar and stirred without bubbles.
  • the formulation is filled into a 310 ml PE cartridge, stored for 24 hours at 25 ° C and then examined.
  • cooling and heating options 840 g (0.2 mol) of a polypropylene glycol having an average molecular weight M n of 4200 g / ol (Acclaim 4200 Fa. Bayer Material Science, D-Leverkusen) submitted and dried for 2 h at 80 ° C and 1 mbar with stirring. It is then cooled to room temperature and then 69.7 g (0.4 mol) of an 80:20 mixture of 2,4- and 2,6-TDI are added.
  • N- (2-aminoethyl) -3-aminopropyltrimethoxysilane are (GENIOSIL ® GF 9 from Wacker Chemie AG, D-Munich) for 1 minute at 200 rpm, followed by addition of 0.2 g of dibutyltin bis-acetylacetonate for 2 minutes at 600 rpm and for 1 minute Homogenized at 200 U / min at a pressure of 100 mbar and stirred bubble-free.
  • the formulation is filled into a 310 ml PE-Artuschen, stored for 24 hours at 25 ° C and then examined. The results are shown in Table 3.
  • N- (2-aminoethyl) -3-aminopropyl-trimethoxysilane GIOSIL * GF 9 from Wacker Chemie AG, D-Munich
  • 0.2 g of dibutyltin-bis-acetyl-acetonate are metered in for 2 minutes at 600 rpm and for 1 minute Homogenized at 200 U / min at a pressure of 100 mbar and stirred bubble-free.
  • the formulation is filled into a 310 ml PE cartridge, stored for 24 hours at 25 ° C and then examined.
  • Evaluation of the Adhesive Formulations of Examples 9 and 10 The determination of the tensile shear strengths of the adhesive formulations from Examples 9 and 10 is carried out as described in DIN EN 204. In this case, the adhesive is applied to both beechwoods to be glued, which are then stripped off with a 100 ⁇ m doctor blade. Subsequently, the two woods are joined over an area of 1 x 2 cm with a contact pressure of 5kg. After pressing 24 hours, the woods are stored in the standard climate for the specified period. When determining the Dl value, the tensile shear strength of the two glued woods is measured directly after storage.

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  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne des substances réticulables sur la base de polyuréthanes à terminaison silane contenant au moins deux différentes liaisons de la formule ; Y-[NH-C(=O)-NR3-(CR1 2)b-SiRa(OR2)3 -a] x, dans laquelle les restes et les indices ont la désignation spécifiée dans la revendication 1, à condition que tous les restes (Y) contiennent au moins un groupe aromatique et qu'une partie des restes (Y) contienne au moins une unité de polyéther, la masse molaire moyenne (Mn) de toutes les unités de polyéther contenues dans les restes (Y) étant située entre 1500 et 6500 g/mol. L'invention concerne également un procédé pour leur fabrication et leur utilisation en tant que matériaux de collage et d'étanchéité, notamment en tant que matériaux de collage à haute résistance à la rupture par traction.
PCT/EP2012/072980 2011-12-01 2012-11-19 Substances réticulables sur la base de polyuréthanes à terminaison organyloxysilane Ceased WO2013079344A1 (fr)

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DE102011087604A DE102011087604A1 (de) 2011-12-01 2011-12-01 Vernetzbare Massen auf Basis von organyloxysilanterminierten Polyurethanen
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN106232683A (zh) * 2014-04-17 2016-12-14 瓦克化学股份公司 基于有机基‑氧基硅烷封端的聚合物的可交联物质
CN106279614A (zh) * 2016-08-30 2017-01-04 江苏凯伦建材股份有限公司 一种硅烷改性聚氨酯密封胶预聚体及其制备方法和密封胶

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