EP3380542A1

EP3380542A1 - Binder systems containing alkoxysilane groups-carrying prepolymers and epoxide compounds, and the use thereof

Info

Publication number: EP3380542A1
Application number: EP16788110.1A
Authority: EP
Inventors: Frank Schubert; Wilfried Knott; Frank GRIMMELT; Anke Lewin
Original assignee: Evonik Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2015-11-26
Filing date: 2016-10-28
Publication date: 2018-10-03
Also published as: CN108291020A; WO2017089068A1; TW201731915A; US20180305596A1; JP2019502781A

Abstract

The invention relates to curable mixtures containing at least one binder composition and at least one curing agent mixture and optionally one or more alkoxysilane compounds, and the use thereof.

Description

Binder systems containing alkoxysilyl groups bearing prepolymers and

Epoxy compounds and their use

The invention relates to curable mixtures containing at least one binder composition and at least one hardener mixture and optionally one or more alkoxysilane compounds and their use.

Polymers bearing alkoxysilyl groups, such as polyethers, polysiloxanes or polyurethanes, have been known for a long time and are used as binders in moisture-curing adhesive / sealant formulations. The adhesives / sealants are characterized by their high ductility and elasticity in the cured state, but they often lack mechanical strength and good adhesion properties on critical substrates such as plastics. Especially when used in thicker layers and at low humidity, the curing is slow and the surfaces are often not sufficiently tack-free. This is especially true for the widely used silyl-terminated polymers due to their low functionality density of reactive alkoxysilyl groups.

Cured epoxy resins, however, are e.g. for the very high strength, the good chemical and temperature resistance and the high adhesive strength on numerous substrates known. Epoxy resins also cure with amines in the absence of humidity and even below room temperature. Disadvantages of some applications are the low extensibility and increased brittleness of the cured epoxy resins. The pronounced exothermic heat of reaction during curing, except in heavily filled systems, usually does not allow application in thicker layers.

In practice, it has proven difficult to achieve a balanced property profile of good extensibility and elasticity combined with good adhesion, rapid curing, high mechanical strength and chemical resistance. Therefore, according to the prior art, there has been no lack of attempts to develop binders which combine such positive properties.

EP 0186191 B1 discloses curable mixtures of an alkoxysilyl-functional polymer, an epoxy resin, an aminosiloxane or aminosilane and a curing agent for the epoxy resin. The disadvantage is that the four components can be mixed only immediately before application in order to avoid the premature curing reaction of the epoxy resin. The choice of useful alkoxysilyl-functional polymers is limited to e.g. Polyethers, polyesters, polyacrylates, polyolefins and polysulfides. The group of silyl-modified polyurethanes is not included. EP 0186191 B1 further states that alkoxysilyl-functional polymers with pendant silyl groups are unsuitable, since they lead to embrittlement in the described curable mixtures.

EP 0370463 describes two-component systems, wherein component A is a mixture of alkoxysilyl-functional polymer and epoxy hardener, component B is a mixture of Epoxy resin and an Sn-containing catalyst and the two components A and B are brought together in the application. The usable alkoxysilyl-functional polymers are also limited to, for example, polyethers, polyesters, polyacrylates, polyolefins and polysulfides and do not comprise silyl-modified polyurethanes.

EP 0671437 claims one-component systems of an alkoxysilyl-functional polymer, a curing catalyst for the alkoxysilyl-functional polymer, an epoxy resin and a ketimine. Such mixtures are storage stable in the absence of moisture. When used in the presence of moisture, the amine hardener is released from the ketimine and at the same time the crosslinking reaction of the alkoxysilyl groups is initiated. EP 0671437 states that good performance properties are obtained only with silane-terminated polymers. EP 0794230 discloses one-component systems as in EP 0674137, which have improved storage stability by the addition of a carbonyl compound.

EP 1679329 describes specific one-part silyl polymer epoxy resin systems containing selected ketimine compounds derived from cyclohexanediamine. The curable mixtures embodied in EP 1679329 lead to the desired good mechanical strengths only with a very high use of epoxy resin, based on the alkoxysilyl-terminated polymer. Thus, it is necessary to use the epoxy resin in terms of mass to 70% to 500% based on the mass of alkoxysilyl-functional polymer. Accordingly, a high amount of epoxy hardener is required so that the total mixture has only small mass fractions of the silyl polymer in the overall system.

The prior art lacks curable systems that combine the positive properties of alkoxysilyl-functional polymers and epoxies: good ductility, elasticity and through-cure with simultaneously good adhesion to various substrates, high mechanical strength and durability. Such silyl polymer-epoxy resin combinations must also be sufficiently stable on storage and easy to process and be used optionally as one- or two-component systems.

It is therefore an object of the present invention to provide curable mixtures which fulfill this balanced property profile.

Surprisingly, it has been found that compositions containing a binder composition and a hardener mixture as described in the claims overcome at least one disadvantage of the prior art. The present invention relates to curable mixtures containing at least one binder composition (A)

Compound (a1) at least one silyl polyether having at least two alkoxysilyl groups on the side, and

Compound (a2) at least one epoxide compound

and at least one hardener mixture (B) containing

Compound (b1) at least one curing catalyst for crosslinking the polyether side chain alkoxysilyl groups and

Compound (b2) at least one hardener for the epoxy compound and

optionally one or more alkoxysilane compounds.

Preferred compounds (a1) are silyl polyethers preferably have on average preferably at least more than two, more preferably at least three, more preferably more than three, three and up to 20 pendent alkoxysilyl groups.

The curable mixtures according to the invention are preferably 2-component mixtures comprising component (A) and component (B) which are mixed together shortly before application, component (A) corresponding to the binder composition (A) and component (B) to the hardener mixture ( B), wherein the optional alkoxysilane compound has been previously added to component (A) or component (B).

The optional alkoxysilane compound may optionally be included in either Component (A) or Component (B), depending on functionality and reactivity. This also applies to the possible further constituents of the curable mixture.

The alkoxysilane compounds which have epoxide groups are preferably added to component (A), in particular alkoxysilane compounds which have no free amino groups, that is to say also those not defined below, preferably component (A).

Preferably, the amino-containing and imine-containing alkoxysilane compounds of component (B) are added. Preferably, from 0.01 to 20% by weight of alkoxysilane compounds, based on the total amount of alkoxysilane compounds plus component (A), preferably from 0.5 to 15% by weight, of component (A) are added. Preferably, the alkoxysilane compounds are added to either component (A) or component (B). More preferably, the alkoxysilane compounds are added exclusively to the component (B). The 2-component mixtures are advantageous because their handling is easy.

More preferably, the curable mixtures according to the invention are 1- component mixtures, ie they already contain mixed components (A) and (B), and optionally one or more alkoxysilane compounds.

Preferred compounds (a1) are silyl polyethers which carry on average at least three and up to 10 pendent alkoxysilyl groups and which can be prepared by way of the alkoxylation of epoxide-functional alkoxysilanes with the aid of double metal cyanide (DMC) catalysts. These silyl polyethers are preferably prepared according to the process disclosed in EP 2093244 B1.

More preferably, these silyl polyethers are compounds of the formula (1)

Formula 1 )

in which

a is an integer from 1 to 3, preferably 3,

b is an integer from 0 to 2, preferably 0 to 1, more preferably 0, and the sum of a and b is 3,

c is an integer from 0 to 22, preferably from 1 to 12, more preferably from 2 to

8, most preferably from 3 to 4 and especially equal to 1 or 3, d is an integer greater than 2 up to 500, preferably greater than 2 to 100, especially

preferably from 3 to 20 and especially preferably from 3 to 10,

e is an integer from 0 to 10,000, preferably 1 to 4000, particularly preferably 10 to 2000 and in particular 20 to 500,

f is an integer from 0 to 1000, preferably 0 to 100, particularly preferably 0 to 50 and in particular 0 to 30,

g is an integer from 0 to 1, 000, preferably 1 to 200, particularly preferably 2 to 100 and in particular 3 to 70, h, i and j independently of one another are integers from 0 to 500, preferably 0 to 300, particularly preferably 0 to 200 and in particular 0 to 100,

n is an integer between 2 and 8, preferably 5,

k is an integer from 1 to 6, preferably 2 to 4,

R is one or more identical or different radicals selected from linear or branched, saturated, mono- or polyunsaturated alkyl radicals having 1 to 20, in particular 1 to 6 carbon atoms or haloalkyl groups having 1 to 20 carbon atoms. R preferably corresponds to methyl, ethyl, propyl, isopropyl, n-butyl and sec-butyl groups, especially methyl and ethyl, in particular ethyl

R is a hydroxyl group or a k-functional radical, preferably a saturated or unsaturated linear, branched or cyclic or further substituted oxyorganic radical having 1 to 1500 carbon atoms, the chain also being interrupted by heteroatoms such as O, S, Si and / or N. may, or an oxyaromatic system-containing radical or an optionally branched silicone-containing organic radical, which for binding to the fragment with the index k a

Has oxygen,

R ² or R ³ , and R ⁵ or R ^{6 is the} same or independently of one another H or a saturated or optionally mono- or polyunsaturated, also further substituted, optionally mono- or polyvalent hydrocarbon radical, preferably a methyl, ethyl, propyl or Butyl, vinyl, allyl or phenyl, especially methyl, ethyl or

Phenyl, particularly preferably methyl,

R ⁴ corresponds to a linear or branched alkyl radical of 1 to 24 carbon atoms or an aromatic or cycloaliphatic radical which may optionally in turn carry alkyl groups;

R ⁷ and R ⁸ are independently either hydrogen, alkyl, alkoxy, aryl or

aralkyl,

R ⁹ , R ⁰ , R and R ² are independently either hydrogen, alkyl, alkenyl, alkoxy, aryl or aralkyl groups. The hydrocarbon radical may be bridged cycloaliphatically or aromatically via the fragment Z, where Z may be both a divalent alkylene and alkenylene radical,

with the proviso that the fragments with the indices d, e, f, and / or h are mutually freely permutable, that is interchangeable within the polyether chain and optionally randomly distributed and thus in the sequence within the polymer chain are interchangeable used becomes.

Preference is given to those silyl polyethers of the formula (1) in which the sum of the indices d, e, f, g, h, i to j is 10 to 10 000, preferably 20 to 5000, more preferably 30 to 1000.

The polyethers of the formula (1) have a statistical structure. Statistical distributions are built in blocks with any number of blocks and any sequence or subject to a randomized distribution, they can also be of alternating construction or also form a gradient over the chain, in particular they can also form all mixed forms, in which optionally groups of different distributions can follow one another. Special designs may cause statistical distributions to be constrained by execution. For all areas that are not affected by the restriction, the statistical distribution does not change. Cyclic anhydrides and carbon dioxide are inserted randomly only, ie not in homologous blocks. The index numbers given in the formulas given here and the value ranges of the specified indices are to be understood as the mean values of the possible statistical distribution of the actual structures present and / or their mixtures. This also applies to structural formulas which are exactly reproduced as such. In the context of this invention, the term polyether encompasses both polyethers, polyetherols, polyether alcohols, polyether esters, but also polyether carbonates, which are optionally used synonymously with one another. It is not necessary for the term "poly" to be associated with a multitude of ether functionalities or alcohol functionalities in the molecule or polymer. Rather, this merely indicates that at least repeating units of individual monomer units or compositions are present which have a higher molecular weight Molar mass and also also have a certain polydispersity.

The word fragment "poly" in the context of this invention includes not only exclusively compounds having at least 3 repeating units of one or more

Monomers in the molecule, but especially those compositions of compounds which have a molecular weight distribution and thereby have an average molecular weight of at least 200 g / mol. This definition takes into account the fact that it is common practice in the field of technology considered to refer to such compounds as polymers even if they do not seem to satisfy a polymer definition analogous to OECD or REACH directives.

R is a fragment derived from the initiator or starting compounds for the alkoxylation reaction.

The starting compounds have hydroxyl groups in a number corresponding to at least the index k. The OH-functional starting compounds used are preferably compounds having molar masses of from 18 to 10,000 g / mol, in particular from 50 to 2000 g / mol, and having from 1 to 6, preferably from 2 to 4, hydroxyl groups. More preferably, R is a hydroxyl group or a k-functional saturated or unsaturated linear, branched or cyclic or further substituted oxyorganic radical having 1 to 1500 carbon atoms, which may optionally also be interrupted by heteroatoms such as O, S, Si or N; more preferably, R (-H) k is a hydroxyalkyl-functional siloxane or a hydroxy-functional polyethersiloxane.

More preferably, the starting compounds are selected from the group of alcohols, polyetherols, hydroxyl-functional polyether esters, hydroxyl-functional polyether carbonates, hydroxyl-functional polybutadienes and hydrogenated hydroxyl-functional polybutadienes or phenols having 1 to 6 hydroxyl groups and with molar masses of 50 to 5000 g / mol.

More preferably, the starting compounds are selected from water, allyl alcohol, butanol, octanol, dodecanol, stearyl alcohol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, ethylene glycol, 1, 3-propylene glycol, di-, tri- and polyethylene glycol, 1, 2-propylene glycol , Di- and polypropylene glycol, 1, 4-butanediol, 1, 6-hexanediol, trimethylolpropane, glycerol, pentaerythritol, sorbitol, cellulose sugar, lignin or other compounds based on natural compounds, hydroxyl groups, called. More preferably, the starting compounds are selected from water, allyl alcohol, butanol, octanol, decanol, dodecanol, stearyl alcohol, 2-ethylhexanol, ethylene glycol, di-, tri- and polyethylene glycol, 1, 2-propylene glycol, di- and polypropylene glycol, trimethylolpropane, glycerol , Pentaerythritol. Particularly preferred

Allyl alcohol, butanol, octanol, polyethylene glycol, and polypropylene glycol. The radical R further more preferably corresponds to the alcohol radicals mentioned here, ie the alcohols in which at least the hydrogen of a hydroxyl group has been replaced by the fragment with the index k of the formula (1), more preferably R is butoxy, allyloxy, octyloxy, dodecyloxy, oxyethoxy , Oxypropoxy, alpha, omega bisoxy polyethylene glycol, alpha, omega bisoxypropylene glycol.

In addition to compounds having aliphatic and cycloaliphatic OH groups, any compounds having 1 to 6 phenolic OH functions are suitable. These include, for example, phenol, alkyl and aryl phenols, bisphenol A and novolacs.

Preferably, the alkoxysilyl moiety in the silyl polyethers of formula (1) is a trialkoxysilyl moiety, more preferably a triethoxysilyl moiety. More preferred are the silyl polyethers bearing side alkoxysilyl groups, where a is 3, b is zero, c is an integer from 2 to 8, d is an integer from 2 to 10, e is an integer from 20 to 4,000, the indices f, g , h, i and j are zero, k is an integer from 1 to 4, the radicals R are methyl or ethyl, R is butoxy, allyloxy, alpha, omega bisoxypolyethylene glycol, alpha, omega bisoxypropylene glycol, the radicals R ² or R ³ , and R ⁵ or R ^{6 are the} same or independently of one another hydrogen or methyl.

Particularly preferred are the polymers carrying side-chain alkoxysilyl groups, where a is 3, b is zero, c is an integer from 2 to 8, d is an integer from 3 to 10, e is an integer from 20 to 4000, the indices f, g , h, i and j are zero, k is an integer from 2 to 4, the radicals R are methyl or ethyl, R is alpha, omega bisoxy polyethylene glycol, alpha, omega bisoxy-polypropylene glycol, the radicals R ² or R ³ and R ⁵ or R ^{6 are the} same or independently of one another hydrogen or methyl. As shown by ²⁹ Si NMR and GPC investigations, the process-related presence of chain-ending OH groups causes the possibility of transesterification reactions on the silicon atom both during the DMC-catalyzed production and, for example, in a subsequent process step. Formally, the alkyl radical R bound to the silicon via an oxygen atom is exchanged for a long-chain modified alkoxysilyl polymer radical. Bimodal as well as multimodal GPC curves show that the formula (1) only reproduces the complex chemical reality in a simplified way.

The diversity of chemical structures and molar masses is also reflected in the broad molecular weight distributions of M _w / M _n of usually> 1.5, which are typical for silyl polyethers of the formula (1) and completely unusual for conventional DMC-based polyethers.

Likewise preferred compounds (a1) are urethanized, sidewise alkoxysilyl-modified silyl polyethers. More preferably, polyethers containing alkoxysilyl groups and containing at the same time urethane groups are present, which on average, based on the individual molecule, have more than two pendent alkoxysilyl groups per urethane group.

The urethane groups may also be converted at least partially into allophanates, biuret and / or urea groups in subsequent reactions. These urethanized silyl polyethers can be prepared by the reaction described in EP2289961 (US201 1046305) by reacting isocyanates with the hydroxyl-functional silyl polyethers of the formula (1). More preferably, the urethanized silyl polyethers are prepared according to the method disclosed in EP2289961 (US2011046305).

These urethanized silyl polyethers are advantageously characterized by the fact that their higher alkoxysilyl functionality and thus the crosslink density and through hardening can be adjusted specifically and within wide limits. In this way, the disadvantages described silane-terminated polymers and prior art side-by-side alkoxysilyl-modified polymers of the prior art avoided.

The urethanized silyl polyethers preferably comprise the catalyst and / or its residues of the urethanization reaction, this catalyst and its residues more preferably being present in the amount of the crosslinking reaction of the polyoxyalkysilyl-bearing polyethers and the curing agents of the epoxide groups, which is unsuitable for the function of the compound ( b2), more preferably, the urethanized silyl polyethers comprise the catalyst in not more than one tenth of the amount of compound (b2) required.

More preferably, the urethanized silyl polyethers are preparable as reaction products of the reaction of

x1) at least one silyl polyether of the formula (1),

x2) with at least one compound having one or more isocyanate groups, x3) optionally in the presence of one or more catalysts,

x4) optionally in the presence of further reactive toward the reaction products components, in particular those having functional groups with protic hydrogen, such as alcohols, amines, thiols, polyetherols, alkoxysilanes and / or water.

As isocyanate group-containing compounds x2), all known isocyanates are preferred. More preferred are aromatic, aliphatic and cycloaliphatic polyisocyanates having a number average molecular weight of less than 800 g / mol. Further more preferred are diisocyanates selected from 2,4- / 2,6-toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI),

Triisocyanatononane (TIN), naphthyl diisocyanate (NDI), 4,4 ^{'-Diisocyanatodicyclohexylmethan,} 3- isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate = IPDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2-methylpentamethylene diisocyanate, 2,2,4 trimethyl-hexamethylene diisocyanate (THDI), dodecamethylene diisocyanate, 1, 4-diisocyanatocyclohexane, 4,4'-diisocyanato-3,3 ^{'-dimethyl-dicyclohexylmethane,} 4,4'-

Diisocyanatodicyclohexylpropane (2,2), 3-isocyanatomethyl-1-methyl-1-isocyanatocyclohexane (MCI), 1, 3-diisooctylcyanato-4-methylcyclohexane, 1, 3-diisocyanato-2-methylcyclohexane and α, α , α ', α'-tetramethyl-m- or -p-xylylene diisocyanate (TMXDI), as well as consisting of these compounds mixtures. Particularly preferred are hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and / or 4,4'-diisocyanatodicyclohexylmethane.

If the isocyanate group-containing compound x2) is used in molar excess with respect to the OH groups of the silylpolyether component, terminal NCO-bearing reactive prepolymers are formed. Compounds with isocyanate-reactive groups can be added to these NCO groups. For example, mono- or polyhydric alcohols, a and polyhydric amines, thiols, OH-functional alkoxysilanes, aminoalkoxysilanes, amino-functional polymers, polyetherols, polyols, polyesterols, acrylated alcohols such as hydroxyethyl acrylate as well as silicone polyether copolymers having OH-functional polyether radicals are introduced.

When an excess of the OH-functional silyl polyether of the formula (1) is used with respect to the NCO groups of the isocyanate component, urethanized polyols having terminal OH groups and bearing alkoxysilyl groups are formed. These urethanized alkoxysilyl polymers can be modified at their OH groups with isocyanates. In the simplest case, alkyl, aryl, arylalkyl monoisocyanates are reacted with the OH groups of the silyl polyether to form the respective adduct and simultaneous end-capping of the reactive chain end of the silyl polyether used. For this purpose, e.g. Methyl, ethyl, butyl, hexyl, octyl, dodecyl, stearyl isocyanate. Particularly preferred monofunctional isocyanates are those which in turn carry crosslinkable alkoxysilyl groups in the molecule. These preferably include isocyanatoalkyl-trialkoxysilanes and isocyanatoalkyl-alkyldialkoxysilanes.

Preferred alkoxysilane-functional monoisocyanates are (isocyanatomethyl) trimethoxysilane, (isocyanatomethyl) triethoxysilane, (isocyanatomethyl) methyldimethoxysilane,

(Isocyanatomethyl) -methyldiethoxysilane, (3-isocyanatopropyl) trimethoxysilane, (3-isocyanatopropyl) -methyldimethoxysilane, (3-isocyanatopropyl) triethoxysilane and (3-isocyanatopropyl) -methyldiethoxysilane used. More preferred are (3-isocyanatopropyl) trimethoxysilane and triethoxysilane.

Preferred compounds (a2) are the epichlorohydrin-derived glycidyl ethers, glycidyl esters and glycidyl amines, more preferably bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycidyl ethers of novolaks (epoxy novolac resins), hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether , tert-butylglycidyl ether, diglycidylaniline, tetraglycidylmethylenedianiline, triglycidylaminophenol,

1,6-hexanediglycidyl ether, 1,4-butanediglycidyl ether, cyclohexanedimethyl diglycidyl ether, alkyl glycidyl ether, benzyl glycidyl ether, trimethylolpropane triglycidyl ether,

Pentaerythritol tetraglycidyl ethers, brominated glycidyl ethers such as tetrabromobisphenol A diglycidyl ethers, alkyl glycidyl esters, triglycidyl isocyanurate, allyl glycidyl ethers, poly (alkylene glycol) diglycidyl ethers and epoxide compounds of unsaturated hydrocarbons and unsaturated fats or fatty acids. Likewise preferred are oligomeric and polymeric epoxide compounds selected from polyolefins bearing epoxide groups and siloxanes or epoxide compounds which have been formed by chain extension, preferably from diglycidyl ethers having OH-functional compounds. Particularly preferred are epoxy compounds having two or more than two epoxide groups per molecule. The compound (a1) and the compound (a2) are preferably used in the mass ratio of 100/1 to 1/100. Preferably, the mass ratio is 100/5 to 20/100. It may be advantageous to combine mixtures of a plurality of epoxide compounds (a2) and mixtures of several silylpolyethers (a1) carrying lateral alkoxysilyl groups in order to set specific property profiles.

The compound (b1) is preferably a catalyst selected from hydrolysis / condensation catalysts for alkoxysilanes, organic tin compounds, tetraalkylammonium compounds, guanidine compounds, guanidine-siloxane compounds and bismuth catalysts,

Preferred compounds (b1) are the hydrolysis / condensation catalysts known to the skilled person for alkoxysilanes. Preferably, as the curing catalysts, organic tin compounds, e.g. Dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin diacetate, dibutyltin dioctoate, or dioctyltin dilaurate, dioctyltin diacetylacetonate, dioctyltin diketanoate, dioctylstannoxane, dioctyltin dicarboxylate, dioctyltin oxide, preferably dioctyltin diacetylacetonate, dioctyltin dilaurate,

Dioctyltin diketanoate, dioctylstannoxane, dioctyltin dicarboxylate, dioctyltin oxide, particularly preferably dioctyltin diacetylacetonate and dioctyltin dilaurate. Furthermore, zinc salts such as zinc octoate, zinc acetylacetonate and zinc 2-ethylcaproate, or tetraalkylammonium compounds such as N, N, N-trimethyl-N-2-hydroxypropylammonium hydroxide, N, N, N-trimethyl-N-2-hydroxypropylammonium-2 ethylhexanoate or choline-2-ethylhexanoate. Preference is given to the use of zinc octoate (zinc 2-ethylhexanoate) and the tetraalkylammonium compounds, more preferably that of zinc octoate. More preferred are bismuth catalysts, e.g. Borchi® catalysts, titanates, e.g. Titanium (IV) isopropylate, iron (III) compounds, e.g. Iron (III) acetylacetonate,

Aluminum compounds, such as aluminum triisopropylate, aluminum tri-sec-butylate and other alcoholates and aluminum acetylacetonate, calcium compounds, such as calcium disodium ethylenediamine tetraacetate or calcium diacetylacetonate, or amines, for example triethylamine, tributylamine, 1,4-diazabicyclo [2,2,2] octane, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, N, N-bis (N, N-dimethyl-2-aminoethyl) -methylamine, N, N-dimethylcyclohexylamine, Ν, Ν-dimethylphenylamine, N-ethylmorpholine, etc. Also organic or inorganic Brönsted acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid or benzoyl chloride, hydrochloric acid, phosphoric acid their mono- and / or diesters, such as butyl phosphate , (Iso) propyl phosphate, dibutyl phosphate, etc. are preferred as catalysts. More preferred are guanidine group-bearing organic and silicon-organic compounds. Of course, combinations of several catalysts can be used. In addition, photolatent bases can also be used as catalysts, as described in WO 2005/100482.

The curing catalyst (b1) is used in amounts of 0, 1 to 5.0 wt .-%, preferably 0.2 to 4.0 wt .-% and particularly preferably 0.5 to 3 wt .-% based on the sum of the Component (A), the compound (b1) and the optional alkoxysilane compounds used.

Preferred compounds (b2) are amines or imines, wherein the amines carry as active nitrogen at least one hydrogen on the nitrogen and the imines have as active nitrogen no hydrogen but one C = N double bond.

Preferred compounds (b2) are all compounds having at least one primary or secondary amine group. Preferably, amines having at least two hydrogens reactive toward epoxide groups are N-H per molecule. More preferred are ethylenediamine, 1,6-diaminohexane, diaminocyclohexane, isophoronediamine, trimethyl-1,6-hexanediamine, m-xylylenediamine, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, polyoxyalkylenepolyamines, aminosiloxanes, aminosilanes, polyethylenimine. Further preferred are the adduct hardeners known to the person skilled in the art, which have resulted from the addition of a polyamine to an epoxide compound, as well as the group of polyaminoamides and polyaminoimidazolines which are prepared from polyamines and carboxylic acids, in particular fatty acids. More preferred are mixtures of amines.

The amount of compound (b2) depends on the amount of epoxide compound (a2) in the curable mixtures. The molar ratio of epoxide groups of the compounds (a2) to reactive NH groups, the amines or active nitrogens in imines, the compounds (b2) is preferably between 2: 1 to 1: 3, preferably between 1, 5: 1 to 1: 2 , particularly preferred are approximately stoichiometric ratios of 1, 2: 1 to 1: 1.5. The curing reaction begins immediately after contacting the epoxy compound

Compound (b2), if it has free amino groups, regardless of the presence of moisture.

The curable mixtures of the 2-component systems according to the invention are therefore applied immediately after mixing the components and are then not storage-stable.

For the preparation of 1-component systems, preference is given to using imines with active nitrogen as compound (b2). The curable mixtures according to the invention as 1-component systems have the advantage that they are storage-stable, since the crosslinking reaction of the compounds (a1) is controlled by the presence of water, anhydrous systems So even if all components are mixed with the exclusion of moisture do not cross-link.

Preferably, imines contain as a verb a structural element of the formula (2)

Formula (2)

in which

Ai and A2 are independently hydrogen, or an organic radical, wherein the radicals Ai and A2 preferably from the condensation reaction (ie a reaction with elimination of one equivalent of water) of an amine-functional compound B-NH2 with a carbonyl compound and thus preferably correspond to the radicals of the carbonyl compound used, wherein in the event that the radicals derived from a compound having a keto function, both radicals Ai and A2 are each an organic radical and in the event that the radicals from a compound which has an aldehyde function, at least one of the two radicals Ai and A2 is an organic radical and the other radical is hydrogen, and B is any organic radical or an organomodified siloxane or silane radical , Ai and A2 may be part of a ring and linked to each other via an organic radical.

Depending on the nature of the radicals Ai and A2, such compounds are often also referred to as ketimines or Schiff bases. More preferably, the imines have two or more imine groups in the molecule. The imines used according to the invention may contain residues of the starting materials, if e.g. one of the starting materials was used in a molar excess or the condensation reaction was incomplete. As aldehydes or ketones are preferably acetaldehyde, propionaldehyde, butyraldehyde,

Benzaldehyde, cinnamaldehyde, salicylaldehyde, toluene aldehyde, anisaldehyde, acrolein, crotonaldehyde, acetone, methyl ethyl ketone, ethyl butyl ketone, ethyl n-propyl ketone, methyl isobutyl ketone, methyl amyl ketone, diethyl ketone, methyl isopropyl ketone, methyl n-propyl ketone, diisopropyl ketone, diisobutyl ketone, methyl pentyl ketone, cyclohexanone, cyclopentanone, Acetophenone, benzophenone and / or isophorone used. Particular preference is given to using those aldehydes or ketones of the above list which have a boiling point above 80 ° C., preferably above 100 ° C., since these have very excellent storage stabilities in curable mixtures of the invention. Particularly preferred are 2-heptanone, benzaldehyde, methyl isobutyl ketone, cyclohexanone, anisaldehyde and / or cinnamaldehyde.

In principle, all compounds having at least one primary amine group for Preparation of the imine compounds are used. Preferred are amines having at least two primary amine groups -NH 2 per molecule. More preferred are amines having two amine groups selected from ethylenediamine, 1,6-diaminohexane, diaminocyclohexane, isophoronediamine, trimethyl-1,6-hexanediamine, m-xylylenediamine, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, N-aminoethylpiperazine, polyoxyalkylenepolyamines, aminosiloxanes, aminosilanes , Polyethyleneimine.

The imines of the formula (2) are latent amine hardeners in the absence of water. Only in the presence of water do they split back into the carbonyl compound and the respective amine and trigger the curing reaction with the epoxide groups. They are therefore preferably suitable for the production of inventive curable 1-component systems.

As a hardener, in addition to amines, other compounds reactive to epoxides can be used. These include e.g. Mercapto compounds, anhydrides and carboxyl groups and phenolic OH-bearing compounds.

Optionally, the curable mixtures according to the invention comprise one or more alkoxysilane compounds. These alkoxysilane compounds are preferably monomeric silanes and / or polymer-bound silanes which carry as hydrolyzable groups methoxy, ethoxy, i-propoxy, n-propoxy or butoxy, aryloxy or acetoxy groups. The nonhydrolyzable radical is arbitrary. Preferably, the nonhydrolyzable group is an organic group which is functionalized with a group reactive with amines or epoxides. In this way, the silanes participate in the crosslinking reaction and link the resulting polymer networks with each other. In addition, these silanes exert a positive effect as a primer. The alkoxysilane compounds are none

Silyl polyether of the formula (1).

Particularly advantageous is the use of, for example, 3-glycidyloxypropyltrimethoxysilane (Dynasylan® GLYMO, Evonik), 3-glycidyloxypropyltriethoxysilane (Dynasylan® GLYEO, Evonik), 3-glycidyloxypropyl (methyl) dimethoxysilane, 3-glycidyloxypropyl (methyl) diethoxysilane, 2- (3, 4

Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, N-cyclohexylaminomethyltrimethoxysilane, N-cyclohexyl-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane (Dynasylan® AMMO, Evonik), 3-aminopropyltriethoxysilane (Geniosil® GF 93, Wacker, Dynasylan ® AMEO, Evonik), 3-aminopropyl (methyl) dimethoxysilane, 3-aminopropyl (methyl) diethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (Dynasylan® DAMO, Evonik), N- (n-butyl) aminopropyltrimethoxysilane ( Dynasylan® 1 189, Evonik), (3-aminopropyl) methyldiethoxysilane (Dynasylan® 1505, Evonik), trimethoxypropylsilane (Dynasylan 1 146, Evonik). The curable mixtures according to the invention as storage-stable 1-component systems More preferably, imine-modified aminosilanes do not react with epoxides in the absence of moisture. Preferred are imine-functionalized silanes derived from 3-aminopropyltrimethoxysilane (Dynasylan® AMMO), 3-aminopropyltriethoxysilane (Geniosil® GF 93, Dynasylan® AMEO), 3-aminopropyl (methyl) dimethoxysilane, 3-aminopropyl (methyl) diethoxysilane, ( 3-aminopropyl) methyldiethoxysilane (Dynasylan® 1505). Imine-modified silanes which enable storage-stable mixtures in the presence of epoxides and polyethers carrying lateral alkoxysilyl groups for the purposes of this invention are disclosed in WO2015 / 003875. Also useful are mercapto functional silanes such as mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.

The monomeric alkoxysilanes optionally contained in the curable mixtures according to the invention can optionally be added to the curable mixtures individually or in combination of two or more silanes.

The alkoxysilane compounds optionally contained in the curable mixtures according to the invention are preferably from 0.01 to 20 wt .-%, more preferably from 0.5 to 15 wt .-% and particularly preferably from 1 to 10 wt .-% based on the lateral alkoxysilyl groups carrying silyl polyethers a1).

In addition to the components (A) and (B) and optionally alkoxysilane compounds, the curable mixtures according to the invention preferably comprise further additives selected from the group of plasticizers, fillers, solvents, adhesion promoters, rheology additives, stabilizers, catalysts, solvents and drying agents, in particular chemical moisture drying agents.

The curable mixture according to the invention preferably comprises one or more adhesion promoters and / or one or more drying agents, in particular chemical moisture drying agents.

It may be advantageous if the inventive curable mixture comprises a drying agent, for. B. for binding introduced by formulation components, or subsequently introduced by the filling process or storage of water or moisture. In principle, all drying agents known from the prior art can be used as drying agents in the curable mixtures according to the invention. Preference is given as a chemical drying agent vinyltrimethoxysilane (Dynasylan ^® VTMO, Evonik or Geniosil ^® XL 10, Wacker), vinyltriethoxysilane (DYNASYLAN ^® VTEO, Evonik or Geniosil ^® GF 56, Wacker), N-trimethoxysilylmethyl-O-methylcarbamate (Geniosil ^® XL 63, Wacker), N-dimethoxy (methyl) silylmethyl-0-methyl-carbamate, N-methyl [3- (trimethoxysilyl) - propyl] carbamate (Geniosil ^® GF 60, Wacker), vinyldimethoxymethylsilane (Geniosil ^® XL 12, Wacker), vinyltris (2-methoxyethoxy) silane (Geniosil ^® GF 58, Wacker) bis (3-triethoxysilylpropyl) amine (Dynasylan ^® 1122, Evonik), bis (3-trimethoxysilylpropyl) amine (Dynasylan ^® 1 124), N- dimethoxy (methyl) silylmethyl-0-methyl-carbamate (Geniosil ^® XL 65, Wacker) or oligomeric vinylsilanes such as Dynasylan ^® 6490 and Dynasylan ^® 6498 (both available from Evonik) alone or mixtures thereof. More preferably, the drying means are selected from vinyl trimethoxysilane (Dynasylan ^® VTMO, Evonik or Geniosil ^® XL 10, Wacker AG), vinyltriethoxysilane (DYNASYLAN ^® VTEO, Evonik or Geniosil ^® GF 56, Wacker). It may furthermore be advantageous if, in addition to or as an alternative to chemical drying, a physical drying agent, such as preferably zeolite, molecular sieve, anhydrous sodium sulfate or anhydrous magnesium sulfate, is used.

The proportion of drying agent in the curable mixtures according to the invention is preferably from greater than 0 to 5 wt .-%, preferably from 0.2 to 3 wt .-% based on the amount of siloxane polyether a1) carrying side-alkoxysilyl groups.

Plasticizers are preferably selected from the group of phthalates, the polyesters, alkylsulfonic acid esters of phenol, cyclohexanedicarboxylic acid esters, benzoates, dipropylene glycol dibenzoates, petroleum distillates or also polyethers which contain no alkoxysilyl groups and no epoxide groups.

If plasticizers are present in the curable mixtures according to the invention, the proportion of plasticizers in the overall composition according to the invention is preferably from greater than 0% by weight to 90% by weight, preferably from 2% by weight to 70% by weight, particularly preferably 5 Wt .-% to 50 wt .-% based on the total composition.

Fillers are preferably precipitated or ground chalk, inorganic carbonates in general, precipitated or ground silicates, precipitated or pyrogenic silicic acids, glass powder, glass bubbles (so-called Bubbles), metal oxides, such as. T1O2, AI2O3, natural or precipitated barium sulphates, quartz flours, sand, aluminum trihydrate, talc, mica, Christobalitmehle, reinforcing fibers such as glass fibers or carbon fibers, long or short fiber wollastonite, cork, carbon black or graphite. Advantageously, hydrophobic fillers can be used, since these products have a lower water input and improve the storage stability of the formulations. If fillers are present in the curable mixtures according to the invention, the

Proportion of the fillers in the curable mixture according to the invention preferably from 1 to 80 wt .-% based on the total composition, wherein for the fillers mentioned here, with the exception of the fumed silicic acid concentrations of 30 to 65 wt .-% are particularly preferred. If fumed silicas are used, a proportion of the fumed silicas of 2 to 20 wt .-% is particularly preferred. As rheological additives, preferably contain, in addition to the filler may be selected from the group of amide waxes, available for example from Arkema under the trade name Crayvallac ^®, hydrogenated vegetable oils and fats, fumed silicas, such as Aerosil ^® R202, Aerosil ^® R974 or Aerosil ^® R805 (Evonik ) or Cab-O- ^Sil® TS 720 or TS 620 or TS 630 (Cabot). If pyrogenic silicas are already used as fillers, the addition of a rheological additive is preferably eliminated.

If rheology additives are present in the curable mixtures according to the invention, the proportion of rheology additives in the curable mixture according to the invention is preferably greater than 0% by weight to 10% by weight, preferably from 2% by weight to 6% by weight, depending on the desired flow behavior. -% based on the total composition.

The curable mixtures of the invention may contain solvents. The solvents may serve, for example, to lower the viscosity of the uncrosslinked mixtures or may favor the application to the surface. Suitable solvents are in principle all solvents and solvent mixtures into consideration. Preferred examples of such solvents are ethers, e.g. t-butyl methyl ether, esters, e.g. Ethyl acetate or butyl acetate or diethyl carbonate, and alcohols, e.g. Methanol, ethanol and the various regioisomers of propanol and butanol or else application-specific selected glycol types. Furthermore, aromatic and / or aliphatic solvents such as benzene, toluene or n-hexane, but also halogenated solvents, such. Dichloromethane, chloroform, carbon tetrachloride, fluorohydrocarbons (FREON) and the like, but also inorganic solvents such as CS2, supercritical CO2 and the like.

If desired, the curable compositions of the present invention may further comprise one or more substances selected from the group consisting of co-crosslinkers, flame retardants, deaerators, curing accelerators for the amine-epoxide reaction, antimicrobials and preservatives, dyes, colorants and pigments, antifreezes, fungicides, and / or reactive diluents and complexing agents, spray aids, wetting agents, fragrances, light stabilizers, radical scavengers, UV absorbers and stabilizers, in particular stabilizers against thermal and / or chemical stress and / or exposure to ultraviolet and visible light.

UV stabilizers are preferably known products based on hindered phenolic systems or benzotriazoles. As light stabilizers z. B. so-called HALS amines can be used. As stabilizers z. As the known to the expert products or product combinations of eg Tinuvin ^® stabilizers (BASF), such as. B. Tinuvin ^® - stabilizers (BASF), for example, Tinuvin ^® 1130, Tinuvin ^® 292 or Tinuvin ^® 400 also preferably, Tinuvin ^® be used in combination with 1130 Tinuvin ^® 292nd Their quantity depends on the degree of stabilization required. Preferably, the curable mixtures of the invention based on the binder mixture (A) 10 to 90 wt .-%, more preferably 20 to 80 wt .-% of compounds (a1), wherein compounds a1) preferably on average between greater than 1 and up to Have 4 trialkoxysilyl functions per silyl polyether of formula (1). More preferably, the curable mixtures of the invention based on the binder mixture (A) 20 to 80 wt .-% of compounds (a1), wherein compounds (a1) preferably on average between greater than 1 and up to 4 triethoxysilyl functions per silyl polyether of the formula (1).

Also more preferred as compounds (a1) are urethanized silyl polyethers, particularly preferably urethanized silyl polyethers, which on average have between greater than 1 and up to 4 trialkoxysilyl functions per silyl polyether of the formula (1). Particularly preferred compounds (a1) are urethanized silyl polyethers, particularly preferably urethanized silyl polyethers, which on average have between greater than 1 and up to 4 triethoxysilyl functions per silyl polyether of the formula (1). The curable mixtures according to the invention preferably have no compounds (a1) which have methoxysilyl functions.

The curable mixtures according to the invention preferably have the following components:

Binder composition (A) from 10 to 85% by weight, based on the total composition, preferably from 15 to 60% by weight and in particular from 20 to 50% by weight,

Hardener mixture (B) from 0.1 to 15% by weight, preferably from 0.5 to 12% by weight and in particular from 1 to 8% by weight, based on the total composition,

Alkoxysilane compound of 0 to 5 wt .-%, preferably 0.5 to 4 wt .-%, particularly preferably 0.8 to 3 wt .-% based on the total composition

Plasticizer from 0 to 30 wt .-%, preferably 5 to 25 wt .-% based on the

Total composition,

Fillers from 1 to 80% by weight, preferably from 5 to 70% by weight, particularly preferably from 10 to 60% by weight, based on the total composition,

Chemical desiccants from 0 to 3.0% by weight, preferably 0.2 to 2.5% by weight, based on the total composition.

An alternative preferred hardenable mixture according to the invention with an increased proportion of epoxide has the following components:

Binder composition (A) of from 30 to 80% by weight, based on the total composition, preferably from 35 to 75% by weight and in particular from 40 to 70% by weight, wherein the binder composition (A) has a proportion of from 20 to 90 Wt .-%, preferably 30 to 80 wt.%, Particularly preferably 40 to 70 wt .-% of epoxy compound a2 to the binder composition (A)

Hardener mixture (B) from 1 to 30% by weight, preferably from 2 to 25% by weight and in particular from 4 to 20% by weight, based on the total composition,

Alkoxysilane compound from 0 to 5% by weight, preferably 0.5 to 4% by weight, particularly preferably 0.8 to 3% by weight, based on the total composition

Plasticizer from 0 to 40% by weight, preferably from 2 to 35% by weight, based on the total composition,

Fillers from 1 to 60% by weight, preferably from 5 to 50% by weight, particularly preferably from 10 to 40% by weight, based on the total composition,

In the case of very particularly preferred curable mixtures, the stated proportions of the formulation constituents are selected such that the total sum of the fractions totals 100% by weight.

A further subject of the invention is the use of the curable mixtures according to the invention comprising the binder mixture (A), the hardener mixture (B) and optionally the alkoxysilane compounds. The curable mixtures of the invention are preferably used as a sealant or adhesive or for the production of a sealant or adhesive.

The curable mixtures according to the invention are preferably used as reactive diluents, primers, primers, barrier sealants, roof coatings.

An advantage of the mixtures according to the invention is that they cure very well even in thicker layers and in large-area applications in a short time.

Another advantage is that the adhesion properties are improved on different substrates such as steel, aluminum, various plastics and mineral substrates such as stone, concrete and mortar, compared to comparable systems without added epoxy. The curable mixtures according to the invention can be used in particular for reinforcement,

Leveling, modification, bonding, for painting, for sealing and / or coating of substrates. Suitable substrates are for. As particulate or laminar substrates, in the construction industry or in vehicle construction, construction elements, components, metals, especially construction materials such as iron, steel, stainless steel and cast iron, ceramic materials, in particular based on solid metal or non-metal oxides or carbides, Aluminum oxide, magnesium oxide or calcium oxide, mineral or organic substrates, in particular cork and / or wood, mineral substrates, chipboards and fibreboards made of wood or cork, composite materials such as wood composites such as MDF boards (medium density fiberboard), WPC articles (Wood Plastic Composites ), Chipboards, cork products, laminated articles, ceramics, but also natural fibers and synthetic fibers (containing substrates) or mixtures of different substrates. The mixtures according to the invention are particularly preferably used for sealing and / or coating particulate or flat substrates, in the construction industry or in vehicle construction, for sealing and bonding construction elements and components, and for coating porous or non-porous, particulate or laminar substrates Coating and modification of surfaces and for applications on metals, in particular on construction materials such as iron, steel, stainless steel and cast iron, for use on ceramic materials, in particular based on solid metal or non-metal oxides or carbides, alumina, magnesium oxide or calcium oxide, on mineral substrates or organic substrates, in particular cork and / or wood, for binding, reinforcement and leveling of uneven, porous or brittle substrates, such as mineral substrates, particleboard and fibreboard made of wood or cork, on composite materials such as beispie For example, on wood composites such as MDF (medium density fiberboard), WPC (Wood Plastic Composites), particle board, cork, laminated articles, ceramics, but also natural fibers and synthetic fibers, or mixtures of different substrates used.

A further advantage of the mixtures according to the invention is that they are also suitable for the bonding of material combinations of the abovementioned substrates.

Another advantage is that it does not matter if the surfaces are smooth or roughened or porous. Roughened or porous surfaces are preferable because of the larger contact area with the adhesive.

The mixtures of the invention are preferably applied in a temperature range of 10 ° C - 40 ° C and cure well under these conditions. Due to the moisture-dependent hardening mechanism, a relative humidity of min. 35% to max. 75% is particularly preferred for good curing. The hardened bond

(Composition) is usable in a temperature range of -10 ° C to 80 ° C.

Storage-stable and user-friendly 1-component systems are obtained when imines according to formula (2) are used instead of the amine hardeners with reactive NH groups. These imines are latent, capped amines, which only after the discharge of the curable mixture of, for example, a cartridge on contact with moisture in the respective amine transition and trigger the epoxy curing reaction. When using imines as compound (b2), all constituents of the mixtures according to the invention may be obtained Exclusion of moisture mixed and filled as ready formulated adhesive / sealant composition eg in cartridges. In the production of these 1-component systems care must be taken to thoroughly dry all feedstocks and equipment.

Preferred within the meaning of the invention and for increasing the storage stability is the use of imine-modified aminosilanes.

The objects according to the invention are described below by way of example, without the invention being restricted to these exemplary embodiments. Given below are ranges, general formulas or classes of compounds, these should not only include the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by removing individual values (ranges) or compounds can be. If documents are cited in the context of the present description, their content, in particular with regard to the facts in connection with which the document was cited, should form part of the disclosure content of the present invention. Percentages are by weight unless otherwise indicated. If mean values are given below, the weight average is, unless stated otherwise. If subsequently parameters are specified which were determined by measurement, the measurements were carried out, unless otherwise stated, at a temperature of 25 ° C. and a pressure of 101,325 Pa.

Examples

General methods

The viscosity was determined to be shear rate-dependent at 25 ° C with the Antonr MCR301 Rheometer in a plate-and-plate arrangement with a gap width of 1 mm. The diameter of the upper plate was 40 mm. The viscosity at a shear rate of 10 s ^-1 was read and is shown in Tables 2 and 3.

GPC measurements for determination of polydispersity and average molecular weights were carried out under the following measurement conditions: column combination SDV 1000/10000 A (length 65 cm), temperature 30 ° C., THF as mobile phase, flow rate 1 ml / min, sample concentration 10 g / l , Rl detector, evaluation against polypropylene glycol standard (6000 g / mol).

The NCO content in percent was determined by means of back titration with 0.1 molar hydrochloric acid after reaction with dibutylamine in accordance with DIN EN ISO 1 1909.

Pendant polyether alkoxysilylmodifizierte: In the following examples, the following trialkoxysilyl-containing silyl polyether 1 were used, the 2,093,244 B1 catalyzed by the process principle of DMC alkoxylation of 3-glycidyloxypropyltriethoxysilane (Dynasylan ^® GLYEO) from Evonik Degussa GmbH have been prepared according to EP.

Example 1: Syntheses Silyl polyether SP 1 (pendant alkoxysilyl-functional polyether):

In a 5 liter autoclave, 353 g of polypropylene glycol of average molecular weight 2000 g / mol were initially charged and mixed with 150 ppm (based on the total amount) of a zinc hexacyanocobaltate double metal cyanide catalyst. For inerting, the reactor was charged with nitrogen to 3 bar and then expanded to atmospheric pressure. The process was repeated twice more. With stirring, the reactor contents were heated to 130 ° C and evacuated to about 20 mbar to remove volatile components. After 30 minutes, 80 g of propylene oxide were metered into the evacuated reactor to activate the catalyst. The internal pressure initially increased to about 0.8 bar. After about 6 minutes, the reaction started, which was noticeable by a drop in the reactor pressure. Now 1218 g of propylene oxide were metered in continuously within about 50 minutes. It closed a one-hour

Afterreaction during which the temperature was lowered to 95 ° C. At this Temperature was a mixture of 196 g of Dynasylan ^® GLYEO (Evonik) and 1233 g of propylene oxide continuously added so that the temperature remained constant. After another one-hour post-reaction was deodorized by applying a pressure (p <100 mbar) to remove residues of unreacted alkylene oxide. Subsequently, 500 ppm Irganox ^® were 1 135 (BASF) for 15 minutes then stirred in. A colorless, viscous product (12,100 mPas at 25 ° C.) with an average of 4 mol of triethyoxysilyl groups and 2 OH groups per molecule and a polydispersity M _w / M _n of 2.4 was obtained.

Silyl polyether SP 2 (urethane-modified, laterally alkoxysilyl-functional polvether, according to DE 102012203737):

706.8 g of silyl polyether from Example 1 were initially charged and heated to 60.degree. Then 26.68 g of IPDI was added, stirred for five minutes and 0.08 g of TIB Kat 216 (dioctyltin dilaurate) was added. The mixture was stirred for 45 minutes, heated to 80 ° C and 53.5 g of a polyether of the general formula C4H90 [CH 2 CH (CH 3) 0] 5.6H added. The mixture was then stirred for a further 3 h. The product had a viscosity of 72,000 mPas at 25 ° C and a polydispersity M _w / M _n of 5.2.

Silyl polyether SP 3 (pendant alkoxysilyl-functional polyetherester):

In a 5 liter autoclave, 125 g of polycaprolactone (diol) from Perstorp of average molecular weight 1250 g / mol were initially charged and mixed with 100 ppm (based on the total batch) of a zinc hexacyanocobaltate double metal cyanide catalyst. As described in Example SP 1, the reactor was rendered inert and volatile components were removed by degassing. To activate the catalyst, 60 g of propylene oxide were metered into the evacuated reactor at 130.degree. After the reaction had started, 210 g of propylene oxide were continuously metered in over the course of about 65 minutes, and then, after a reaction time of 10 minutes, a mixture of 400 g of propylene oxide and 150 g of ethylene oxide was metered. After one hour post-reaction, the temperature was lowered to 95 ° C. At this temperature, a mixture of 1 1 1, 2 g of Dynasylan ^® GLYEO (Evonik) and 496 g of propylene oxide was added continuously. After one-hour post-reaction was deodorized at p <100 mbar. Subsequently, 500 ppm Irganox ^® were 1 135 (BASF) for 15 minutes then stirred in. A colorless, viscous product (20,600 mPas at 25 ° C.) with an average of 4 mol of triethyoxysilyl groups and 2 OH groups per molecule and a polydispersity M _w / M _n of 2.8 was obtained. Silyl polyether SP 4 (urethane-modified, laterally alkoxysilyl-functional polyether ester, according to DE 102012203737):

640.1 g of silyl polyether SP 3 were initially charged and heated to 60.degree. Then, 22.0 g of IPDI was added, stirred for five minutes, and 0.072 g of TIB Kat 216 (dioctyltin dilaurate) was added. The mixture was stirred for 45 minutes, heated to 80 ° C and 49.2 g of a polyether of the general formula C4H90 [CH2CH (CH3) 0] 5.6H added. The mixture was then stirred for a further 3 h. The product had a viscosity of 74,100 mPas at 25 ° C and a polydispersity

Silylpolyether SP 5 (laterally alkoxysilyl-functional polvetherester):

In a 5-liter autoclave 135 g Baycoll ^® CD were 2,084 (polyester diol from Bayer Material Science) presented an average molecular weight 1350 g / mol, and 100 ppm (based on the total mixture) of a zinc hexacyanocobaltate-double metal cyanide catalyst. As described in Example SP 1, the reactor was rendered inert and volatile components were removed by degassing. To activate the catalyst, 60 g of propylene oxide were metered into the evacuated reactor at 130.degree. After the reaction had started, 244 g of propylene oxide were continuously metered in over the course of about 50 minutes, and then, after a reaction time of 10 minutes, a mixture of 385 g of propylene oxide and 223 g of ethylene oxide was metered. After one hour post-reaction, the temperature was lowered to 1 10 ° C. At this temperature, a mixture of 83.4 g Dynasylan ^® GLYEO (Evonik) and 512.5 g of propylene oxide was added continuously. After one-hour post-reaction was deodorized at p <100 mbar. Subsequently, 500 ppm Irganox ^® were 1 135 (BASF) for 15 minutes then stirred in. A colorless, viscous product (14,700 mPas at 25 ° C.) with an average of 3 mol of triethyoxysilyl groups and 2 OH groups per molecule and a polydispersity M _w / M _n of 2.2 was obtained.

Silyl polyether SP 6 (urethane-modified, laterally alkoxysilyl-functional polvetherester: process according to DE 102012203737):

582.0 g of silyl polyether SP 5 were initially charged and heated to 60.degree. Subsequently, 15.76 g of IPDI was added, stirred for five minutes and 0.068 g of TIB Kat 216 (dioctyltin dilaurate) was added. The mixture was stirred for 45 minutes, heated to 80 ° C and 48.7 g of a polyether of the general formula C4H90 [CH 2 CH (CH 3) 0] 5.6H added. The mixture was then stirred for a further 3 h. The product had a viscosity of 52,800 mPas at 25 ° C and a polydispersity Mw / Mn of 6.5. Silyl Polvether SP 7 (laterally alkoxysilyl-functional Polvethercarbonate):

In a 5 liter autoclave, 150 g Desmophen ^® C were added 1 100 (polycarbonate diol from Bayer Material Science) presented an average molecular weight 1000 g / mol and containing 100 ppm (based on the total mixture) was added a zinc hexacyanocobaltate double metal cyanide catalyst. As described in Example SP 1, the reactor was rendered inert and volatile components were removed by degassing. To activate the catalyst, 60 g of propylene oxide were metered into the evacuated reactor at 130.degree. After the reaction had started, a mixture of 885 g of propylene oxide and 370 g of ethylene oxide was continuously metered in over about 160 minutes. After one hour post-reaction, the temperature was lowered to 1 10 ° C. At this temperature, a mixture of 146 g Dynasylan ^® GLYEO (Evonik) and 850 g of propylene oxide was added continuously. After one-hour post-reaction was deodorized at p <100 mbar. Subsequently, 500 ppm Irganox ^® were 1 135 (BASF) for 15 minutes then stirred in. A colorless, viscous product (23,000 mPas at 25 ° C.) with an average of 3.5 mol triethyoxysilyl groups and 2 OH groups per molecule and a polydispersity M _w / M _n of 3.5 was obtained.

Silylpolvether SP 8 (urethane-modified, laterally alkoxysilyl-functional

Polvethercarbonat; according to DE 102012203737): 580.0 g of silyl polyether SP 7 were initially charged and heated to 60.degree. Subsequently, 15.72 g of IPDI was added, stirred for five minutes and 0.068 g of TIB Kat 216 (dioctyltin dilaurate) was added. The mixture was stirred for 45 minutes, heated to 80 ° C and 46.6 g of a polyether of the general formula C4H90 [CH2CH (CH3) 0] 5.6H added. The mixture was then stirred for a further 3 h. The product had a viscosity of 56,500 mPas at 25 ° C and a polydispersity

Silyl Polvether SP 9 (laterally alkoxysilyl-functional Polvetherester):

In a 3 liter autoclave, 214.0 g of polypropylene glycol monoallyl ether (average

Molecular weight 430 g / mol), 278.2 g of 3-glycidyloxypropyltriethoxysilane (DYNASYLAN ^® GLYEO) and 0.225 g of zinc hexacyanocobaltate DMC catalyst under nitrogen. The mixture was heated to 150 ° C, then freed at 30 mbar of any volatile ingredients. After a holding time of 30 min at 150 ° C and successful activation of the DMC catalyst, the reaction mixture was cooled to 130 ° C. Following 348.0 g of propylene oxide in 15 min at max. 1 bar internal pressure fed absolutely. At 130 ° C and max. 1 bar internal pressure absolute were successively 1 14.0 g of ε-caprolactone in 25 min, 216, 1 g of 1, 2-butylene oxide in 15 min, 236.2 g of 3-glycidyloxypropyltrimethoxysilane (DYNASYLAN ^® GLYMO) in 45 min, 120.0 g of styrene oxide in 15 min and finally 290 g of propylene oxide in 40 min. After each addition portion, an approximately 15 minute hold time was maintained at 130 ° C until the next monomer was metered. The post-reaction of the propylene oxide endblock was followed by a post-reaction time of 30 minutes at 130.degree. Finally, it was degassed to remove volatiles.

The obtained slightly yellowish aromatic modified polyether contains on average per molecule, block-like succession, 2 mol DYNASYLAN ^® GLYEO, 12 mol propylene oxide 2 mol ε- caprolactone, 6 mol 1, 2-butylene oxide, 2 moles of DYNASYLAN ^® GLYMO, 2 mol of styrene oxide and 10 mol Propylene oxide as an endblock. The OH number is 18.0 mg KOH / g, the average molecular weight 3120 g / mol. Free epoxide groups are not detectable in the final product.

Silylpolvether SP 10 (laterally alkoxysilyl-functional polyetherester):

375.0 g of polypropylene glycol monobutyl ether (average molecular weight 750 g / mol), 154.0 g of hexahydrophthalic anhydride (HHPSA) and 0.350 g of zinc hexacyanocobaltate-DMC catalyst were placed under nitrogen in a 3 liter autoclave. The mixture was heated to 130 ° C and then freed at 30 mbar of any volatile ingredients. To activate the DMC catalyst, a portion of 58.0 g of propylene oxide was fed. After the reaction (pressure drop) were measured at 130 ° C 418.0 g of 3- glycidyloxypropyltriethoxysilane (DYNASYLAN GLYEO ^®) in 20 min. After a reaction time of 150 minutes at 130-150 ° C, the reaction mixture was cooled to 130 ° C. After addition of 435.0 g of propylene oxide at 130 ° C within 15 min, the degassing step followed to remove volatile components.

The colorless polyether obtained contains in statistically mixed sequence, followed by a 30 mol end block of propylene oxide units on average per molecule, 2 moles and 3 moles HHPSA DYNASYLAN GLYEO ^®. The OH number is 23.0 mg KOH / g, the average molecular weight 2440 g / mol. Free epoxide groups are not detectable in the final product.

Silylpolvether SP 1 1 (laterally alkoxysilyl-functional Polvethercarbonat):

375.0 g of polypropylene glycol monobutyl ether (average molar mass 750 g / mol) and 0.16 g of zinc hexacyanocobaltate-DMC catalyst were placed under nitrogen in a 3 liter autoclave. The mixture was heated to 130 ° C and then freed at 30 mbar of any volatile ingredients. To activate the DMC catalyst, a portion of 354.3 g of 3-glycidyloxypropyltrimethoxysilane (DYNASYLAN ^® GLYMO) was fed. Jump after arrival of the reaction and consumption of DYNASYLAN ^® GLYMO of the batch was cooled to 1 10 ° C. Up to an internal pressure of 5 bar absolute, gaseous carbon dioxide is metered into the autoclave. 1740.0 g of propylene oxide were continuously added in 1 10 ° C at 1 10 ° C with cooling while cooling. A pressure drop below 5 bar signaled the reaction of Carbon dioxide. During the propylene oxide metering, carbon dioxide was added in portions to keep the internal reactor pressure between 4 and 5 bar. After 90 min post-reaction at 1 10 ° C and a pressure drop to <2 bar, the mixture was degassed in vacuo to remove volatiles.

The low-viscosity polyether obtained contains a DYNASYLAN ^® GLYMO block (on average per molecule 3 trialkoxysilyl) and a 60 mol of propylene oxide block, are randomly distributed in the carbonate groups. The product has an OH number of 12 mg KOH / g and an average molecular weight of 4675 g / mol. The carbonate content is about 4 wt .-%. Free epoxide groups are not detectable in the final product.

Table 1: Epoxy compounds used:

Epoxy eq.

epoxy

[G / mol]

E 1 Bisphenol A diglycidyl ether (Fa. ABCR) 180 E 2 Bisphenol F diglycidyl ether (Epilox ^® F 17-00, Leuna Harze GmbH) 165

Table 2: used amine hardener and imine hardener:

Amine equivalent

Harder

[G / mol]

H 1 isophoronediamine (IPD Vestamin ^®, Evonik) 42.6

H 2 isophoronediamine methyl isobutyl ketone ketimine 83.7

H 3 Jeffamine ^® D-230 (Huntsman) 57.5

H 4 Jeffamine D-230 methyl isobutyl ketone ketimine 98.6

H 5m-xylylenediamine (Aldrich) 34, 1

H 6 Jeffamine ^® D-400 (Huntsman) 100.0

H 7 Jeffamine D-400 methyl isobutyl ketone ketimine 141, 0

H 8m-xylylenediamine methyl isobutyl ketone ketimine 75, 1

Example 2: Compositions

Example 2.1: Preparation of unfilled 1-component compositions

In all the compositions of Table 3 0.5 g TIB-Kat 223 and 3.0 g of Dynasylan AMEO ^® were used per 100 g of silyl polyether. The components were 600 (Fa. Hausschild) in SPEEDMIXER ^® FVS thoroughly mixed. Immediately after mixing, the test specimens for the overlap bonds (Example 3, Table 5) and the elongation at break (Table 7) produced. The type and amounts of epoxide and hardener (in each case based on 100 g of silyl polyether) are listed in Table 3:

Table 3: Master table for unfilled I-component compositions

Example Silyipolyether Epoxy Hardener

Ref 1 SP 2 - - - -

Ref 2 SP 1 - - - -

1 SP 2 E 1 20 g H 1 4.7 g

2 SP 1 E 1 20 g H 3 5.7 g

3 SP 1 E 1 20 g H 4 10.0 g

4 SP 1 E 1 20 g H 1 4.7 g

5 SP 1 E 1 20 g H 2 9.5 g

6 SP 1 E 1 30 g H 3 8.8 g

7 SP 1 E 1 30 g H 4 15.0 g

8 SP 1 E 1 30 g H 1 6.5 g

9 SP 1 E 1 30 g H 2 13.0 g

10 SP 2 E 1 20 g H 3 5.7 g

1 1 SP 2 E 1 20 g H 4 10.0 g

12 SP 2 E 1 20 g H 1 4.7 g

13 SP 2 E 1 20 g H 2 9.5 g

14 SP 2 E 1 30 g H 3 8.8 g

15 SP 2 E 1 30 g H 4 15.0 g

16 SP 2 E 1 30 g H 1 6.5 g

17 SP 2 E 1 30 g H 2 13.0 g

18 SP 2 E 2 20 g H 1 5, 1 g

19 SP 2 E 2 20 g H 2 10.4 g

20 SP 3 E 1 20 g H 2 9.5 g

21 SP 4 E 1 20 g H 2 9.5 g

22 SP 4 E 1 30 g H 1 7, 1 g

23 SP 5 E 1 20 g H 5 3.2 g

24 SP 5 E 1 20 g H 4 10.0 g

25 SP 6 E 2 20 g H 4 10.9 g

26 SP 6 E 2 20 g H 3 7, 1 g

27 SP 7 E 1 10 g H 1 2.4 g

28 SP 8 E 1 30 g H 2 14.2 g

29 SP 8 E 1 20 g H 4 1 1, 2 g

30 SP 2 E 1 10 g H 1 2.4 g

31 SP 2 E 1 20 g H 5 3.2 g

32 SP 2 E 1 20 g H 6 9.0 g

33 SP 2 E 2 20 g H 1 5, 1 g

34 SP 2 E 2 20 g H 4 10.9 g 35 SP 5 E 1 20 g H 4 1 1, 2 g

36 SP 6 E 2 20 g H 4 12.2 g

37 SP 2 E 1 20 g H 8 7, 1 g

38 SP 2 E 1 20 g H 7 13.0 g

39 SP 2 E 1 20 g H 4 1 1, 2 g

40 SP 2 E 2 20 g H 5 3.2 g

Example 2.2 Preparation of unfilled two-component compositions

The Silyipolyether and the epoxy resin have been used as component A, and - mixing the amine / imine curing agent with the catalyst TIB-Kat 223 and Dynasylan ^® AMEO as component B, respectively in the Speedmixer ^® FVS 600 pre - separately therefrom (Fa house sign.). Components A and B were homogeneous and liquid mixtures. Weighed quantities of both components were homogenized in Speedmixer ^® FVS 600 immediately before application.

Table 4: Two-component compositions

Component A Component B1 Component B2

100 g of silylpolyether SP 2 47 g of hardener H1 95 g of hardener H 2

20 g of epoxide E1 30 g of Dynasylan AMEO ^® 30 g of Dynasylan AMEO ^®

5 g TIB Cat 223 5 g TIB Cat 223

Example 2.3: Preparation of filled 1-component compositions

25.9 wt .-% of the mixtures according to Example 2.1 consisting of the silyl polyether, the epoxy compound and the amine or imine hardener according to Table 3, were mixed with 18.1 wt .-% of diisoundecyl phthalate, 51, 1 wt. % of a precipitated chalk (Socal ^® U1 S2, Solvay), 0.5 wt .-% of titanium dioxide (Kronos ^® 2360, Kronos), 1, 4 wt .-% adhesion promoter (Dynasylan AMMO ^®, Evonik), 1, 1 wt. -% desiccant (Dynasylan ^® VTMO, Evonik), 1, 5 wt .-% of an antioxidant stabilizer mixture (ratio Irganox ^® 1 135: Tinuvin ^® 1 130: Tinuvin ^® 292 = 1: 2: 2 and 0, 4 wt .-% of the curing catalyst (TIB ^® KAT 223, TIB) in the mixer (Speedmixer ^® FVS 600, house sign) intensively mixed.The finished formulation was transferred into PE cartridges and immediately afterwards applied at room temperature.

Example 3: Technical Applications Example 3.1 Determination of the Zuqscherfestiqkeit of overlap bonds unfilled 1-

Component compositions based on DIN EN 1465

Overlapping bonds were made with the curable compositions of Example 2.1. In each case two identical substrates (ABS, PMMA, bright aluminum) were glued together. The area of overlap bonding was 12.5 cm ² . The curing of the bonds was carried out at 23 ° C and 50% relative humidity. After 21 days, the bonds were clamped in a universal testing machine (Shimadzu) and a force was applied to the bond at a constant speed (10 mm / min) until the bond broke. The breaking force was determined. Table 5: Tensile shear strengths of one-component systems (DIN EN 1465)

Example Silylpoly Epoxide Hardener Tensile shear strength [N / mm ² ]

ethers

ABS PMMA aluminum

Ref 1 SP 2 - - - - 0,1 0,5 0,5

30 SP 2 E 1 10g H 1 2.4 g 0.4 0.9 0.9

1 SP 2 E 1 20 g H 1 4.7 g 0.9 1.09 0.8

31 SP 2 E 1 20 g H 5 1.6 g 0.7 1.1 -

32 SP 2 E 1 20 g H 6 9.0 g 0.5 1.1

13 SP 2 E 1 20 g H 2 9.5 g 1.0 1.0 1.3

4 SP 1 E 1 20 g H 1 4.7 g 0.8 1.0 -

33 SP 2 E2 20 g H 1 2.6 g 1.01 1.0 0.9

19 SP 2 E 2 20 g H 2 10.4 g 10.0 1.1 1.1

20 SP 3 E 1 20 g H 2 9.5 g 0.8 0.9 0.9

21 SP 4 E 1 20 g H 2 9.5 g 010 1.1 1.2

22 SP 4 E 1 30 g H 1 7.1 g 10, 1.2 1.3

23 SP 5 E 1 20 g H 5 3.2 g 0.8 0.9

35 SP 5 E 1 20 g H 4 11.2 g 0.7 10.0 1.0

36 SP 6 E2 20 g H 4 12.2 g 1.02 1.1 1.2

26 SP 6 E2 20 g H 3 7.1 g 1.0 1.1 1.3

27 SP 7 E 1 10g H 1 2.4 g 0.5 0.8 0.9

28 SP 8 E 1 30 g H 2 14.2 g 1.0 1.2 1.3

29 SP 8 E 1 20 g H 4 11.2 g 1.01 1.1 1.3

Example 3.2 Determination of the tensile shear strength of overlap bonds of unfilled 2-component compositions in accordance with DIN EN 1465

ABS and PMMA specimens were bonded after mixing the components as described in Table 4 of Example 2.2, as described above, and after 21 days of curing at 23 ° C. and 50% relative humidity in the universal testing machine (Shimadzu) Tensile shear strength tested.

Table 6: Tensile shear strengths of two-component systems (DIN EN 1465)

Example Comp. A Comp. B1 Comp. B2 Tensile shear strength [N / mm ² ]

ABS PMMA

1 120 g 8, 1 g - 0.9 1, 0

2 120 g - 13.0 g 1, 0 1, 0

Example 3.3: Determination of breaking strength and elongation at break of unfilled 1-component compositions in accordance with DIN 53504:

The compositions of Example 2.1 were knife-coated with a layer thickness of 2 mm on a polyethylene surface. The films were stored and cured for up to 28 days at 23 ° C and 50% relative humidity. Subsequently, S4 shoulder bars were punched out of the films using a cutting die and a toggle press. The shoulder bars were clamped in a universal testing machine (Shimadzu) for testing, and the breaking load and elongation at break were determined at constant speed (200 mm / min) when the specimens were stretched:

Table 7: Breaking strength and elongation at break of unfilled, hardened 1

Component compositions (DIN 53504):

Example silyl polyether Elongation at break [%] Breaking stress [N / mm ² ]

7 d 28 d 7 d 28 d

Ref 1 SP 2 30 31 0.08 0, 18

1 SP 2 36 35 0.43 0.47

2 SP 1 34 33 0, 18 0.25

3 SP 1 40 27 0.24 0.29

4 SP 1 34 40 0, 18 0.29

5 SP 1 27 18 0, 15 0, 17

6 SP 1 36 33 0.24 0.25

7 SP 1 47 35 0.30 0.31

8 SP 1 39 31 0.20 0.32

9 SP 1 29 23 0.32 0.33

10 SP 2 45 41 0.27 0.33

1 1 SP 2 44 37 0.21 0.24

12 SP 2 36 35 0.43 0.47

13 SP 2 43 35 0.30 0.47

14 SP 2 49 43 0.34 0.37

15 SP 2 61 45 0.32 0.45

16 SP 2 47 46 0.68 0.68

17 SP 2 42 36 0.41 0.45

18 SP 2 38 34 0.42 0.46

19 SP 2 40 37 0.34 0.43

20 SP 3 38 35 0.25 0.29

21 SP 4 40 37 0.39 0.46

22 SP 4 45 43 0.62 0.68

23 SP 5 37 32 0.26 0.30

24 SP 5 40 36 0.22 0.28

25 SP 6 41 40 0.35 0.42

26 SP 6 30 35 0.39 0.45

27 SP 7 44 42 0.26 0.30

28 SP 8 38 38 0.55 0.61

29 SP 8 36 38 0.43 0.52 The combination according to the invention of polyethers carrying side-chain alkoxysilyl groups with epoxides and amine or ketimine hardeners causes a significant increase in the tensile strength.

Example 3.4: Determination of Breaking Force and Elongation at Break Based on DIN 53504 for filled 1-component compositions:

The formulations prepared in Example 2.3 were knife-coated with a layer thickness of 2 mm on a PE surface. The films were stored for 7 days and 28 days at 23 ° C and 50% relative humidity. Subsequently, S2 shoulder bars were punched out of the films using a cutting die and a toggle press. The shoulder bars were clamped in a universal testing machine (Shimadzu) for testing, and the breaking load and elongation at break of the test specimens were determined at a constant speed (200 mm / min).

Table 8: Breaking strength, breaking elongation and Shore A hardness of filled, hardened 1

Component Zusmmensetzungen

Example Elongation at break [%] Breaking stress [N / mm ² ] Shore A after 15 s

7 d 28 d 7 d 28 d 7 e 28 d

Ref 1 214 208 1, 7 1, 8 31 34

Ref 2 21 1 214 1, 2 1, 2 26 32

1 76 67 2, 1 2.3 61 64

13 79 67 2.2 2.3 65 68

10 99 92 2.0 2.3 57 61

1 1 88 75 1, 9 1, 9 58 62

19 78 70 2.2 2.2 65 67

34 89 79 2.0 2, 1 60 63

20 69 71 1, 9 2.0 61 63

21 81 77 2.3 2.4 67 70

22 71 67 2.4 2.5 70 75

23 70 68 1, 9 2, 1 63 66

24 75 72 1, 7 2.0 60 63

25 92 87 2.2 2.4 66 67

26 98 90 2, 1 2.3 69 73

27 125 1 19 1, 4 1, 5 42 44

28 70 65 2.3 2.5 70 73

29 99 95 2,3 2,3 69 71

17 84 77 1, 8 2, 1 58 64

37 96 75 1, 8 2, 1 53 57

38 60 56 2.0 2.3 66 72 The combination according to the invention of polyethers carrying epoxides and amine or ketimine hardeners carrying lateral alkoxysilyl groups causes a significant increase in the tensile strength and Shore A hardness with decreasing extensibility. The inventive curable compositions are therefore particularly suitable for those applications in which high-strength adhesive compounds are required, which are not achievable with silyl polymers alone.

EXAMPLE 3.5 Determination of the Adhesive Strength of Overlap Adhesions of Filled 1-Component Compositions Based on DIN EN 1465: Overlapping bonds were produced with the adhesive / sealant formulations according to Example 2.3. In each case two identical substrates (ABS, PMMA and steel of class V2A) were used. The area of overlap bonding was 12.5 cm ² . The curing of the bonds was carried out at 23 ° C and 50% relative humidity. After 21 days, the bonds were clamped in a universal testing machine (Shimadzu) and a force was applied to the bond at a constant speed (10 mm / min) until the bond broke. The breaking force was determined.

Table 9

Example Silylpoly Epoxide Hardener Tensile shear strength [N / mm ² ]

ethers

ABS PMMA V2A

Ref 1 SP 2 - - - - 0.22 1, 14 1, 24

Ref 2 SP 1 - - - - n.b. n.d. 0.90

1 SP 2 E 1 20 g H 1 4.7 g 0.84 1, 21 2.20

13 SP 2 E 1 20 g H 2 9.5 g 1, 30 1, 40 1, 46

10 SP 2 E 1 20 g H 3 5.7 g 1, 30 1, 50 1, 29

39 SP 2 E 1 20 g H 4 1 1, 2 g 1, 10 1, 20 1, 60

32 SP 2 E 1 20 g H 6 9.0 g 0.75 1, 10 1, 24

38 SP 2 E 1 20 g H 7 13.0 g 1, 20 1, 37 1, 23

40 SP 2 E 2 20 g H 5 3.2 g 1, 48 1, 42 1, 54

37 SP 2 E 1 20 g H 8 7, 1 g 1, 31 1, 23 1, 32

Claims

claims:

1. Curable mixtures containing at least one binder composition (A)

containing

Compound (a1) at least one silyl polyether having at least two and up to 10 alkoxysilyl groups on the side, and

Compound (a2) at least one epoxide compound

and at least one hardener mixture (B) containing

Compound (b1) at least one curing catalyst for crosslinking the pendant alkoxysilyl groups polymer and

Compound (b2) at least one hardener for the epoxy compound and

optionally one or more alkoxysilane compounds.

2. Hardenable mixtures according to claim 1, characterized in that the lateral alkoxysilyl-carrying silyl polyether is a compound of the formula (1)

Formula 1 )

in which

a is an integer from 1 to 3, preferably 3,

c is an integer from 0 to 22, preferably from 1 to 12, more preferably from 2 to 8, most preferably from 3 to 4,

d is an integer greater than 1 up to 500, preferably 2 to 100, especially

preferably greater than 2 up to 20 and particularly preferably 3 to 10,

f is an integer from 0 to 1000, preferably 0 to 100, particularly preferably 0 to

50 and in particular 0 to 30,

g is an integer from 0 to 1, 000, preferably 1 to 200, particularly preferably 2 to

100 and especially 3 to 70, h, i and j independently of one another are integers from 0 to 500, preferably 0 to 300, particularly preferably 0 to 200 and in particular 0 to 100,

n is an integer between 2 and 8, preferably 5,

k is an integer from 1 to 6, preferably 2 to 4,

R is one or more identical or different radicals selected from linear or branched, saturated, mono- or polyunsaturated alkyl radicals having 1 to 20, in particular 1 to 6 carbon atoms or haloalkyl groups having 1 to 20 carbon atoms. R preferably corresponds to methyl, ethyl, propyl, isopropyl, n-butyl and sec-butyl groups, especially methyl and ethyl, in particular ethyl R is a hydroxyl group or a k-functional radical, preferably a saturated or unsaturated linear, branched or cyclic or further substituted oxyorganic radical having 1 to 1,500 carbon atoms, wherein the chain may also be interrupted by heteroatoms such as O, S, Si and / or N, or a

oxyaromatic system-containing radical or an optionally branched silicone-containing organic radical which has an oxygen for binding to the fragment with the index k,

R ² or R ³ , and R ⁵ or R ^{6 are the} same or independently H or a

saturated or optionally monounsaturated or polyunsaturated, also further substituted, optionally mono- or polyvalent hydrocarbon radical, preferably a methyl, ethyl, propyl or butyl, vinyl, allyl radical or phenyl radical, especially methyl, ethyl or phenyl, particularly preferably methyl .

R ⁷ and R ⁸ are independently either hydrogen, alkyl, alkoxy, aryl or

aralkyl,

with the proviso that the fragments with the indices d, e, f, and / or h are mutually freely permutable, that is interchangeable within the polyether chain and optionally present randomly and thus in the sequence are interchangeable within the polymer chain, is used ,

A curable mixture according to claim 2, characterized in that compounds of the formula (1) in which the sum of the indices d, e, f, g, h, i to j is 10 to 10,000, preferably 20 to 5000, more preferably 30 to 1000 is.

4. A curable mixture according to any one of claims 1 to 3, characterized in that compounds (a1) are urethanized side alkoxysilyl-modified silyl polyethers.

A curable mixture according to any one of claims 3 or 4, characterized in that urethanized side alkoxysilyl-modified silyl polyethers can be prepared as

Reaction products of the reaction of

x1) at least one silyl polyether of the formula (1),

x4) optionally in the presence of further reactive with the reaction products

Components, in particular those which have functional groups with protic hydrogen, preferably alcohols, amines, thiols, polyetherols, alkoxysilanes and / or

Water. 6. Hardenable mixture according to one of claims 1 to 5, characterized in that

Compound (a2) derived from epichlorohydrin glycidyl ether, glycidyl ester and

Glycidylamines or epoxide compounds of unsaturated hydrocarbons and unsaturated fats or fatty acids or oligomeric and polymeric epoxide compounds are selected from epoxide-bearing polyolefins and siloxanes or

Epoxide compounds that are formed by a chain extension from

Diglycidyl ethers with OH-functional compounds.

A curable mixture according to any one of claims 1 to 6, characterized in that the compound (a1) and the compound (a2) are present in a mass ratio of 100/1 to 1/100, preferably 100/5 to 20/100.

A curable mixture according to any one of claims 1 to 7, characterized in that the catalysts used as compound (b1) are selected from hydrolysis / condensation catalysts for alkoxysilanes, organic tin compounds,

Tetraalkylammonium compounds, guanidine compounds, guanidine-siloxane compounds and bismuth catalysts,

A curable mixture according to any one of claims 1 to 8, characterized in that compound (b2) is an amine or an imine.

10. A curable mixture according to claim 9, characterized in that imines as compound (b2) have at least one structural element of the formula (2),

Formula (2)

in which

Ai and A2 are independently hydrogen, or an organic radical, wherein the radicals Ai and A2 preferably from the condensation reaction (ie a reaction with elimination of one equivalent of water) of an amine-functional compound B-NH2 with a carbonyl compound and thus preferably correspond to the radicals of the carbonyl compound used, wherein in the event that the radicals derived from a compound having a keto function, both radicals A1 and A2 are each an organic radical and in the event that the radicals from a compound which has an aldehyde function, at least one of the two radicals A1 and A2 is an organic radical and the other radical is hydrogen, and B is any organic radical or an organomodified siloxane or silane radical , A1 and A2 may be part of a ring and linked to each other via an organic radical. 1 1. A curable mixture according to any one of claims 1 to 10, characterized in that the molar ratio of epoxide groups of the compounds a2) to reactive NH groups of the compounds (b2) between 2: 1 to 1: 3, preferably between 1, 5: 1 to 1: 2, particularly preferred are approximately stoichiometric ratios of 1, 2: 1 to 1: 1.5. 12. A curable mixture according to any one of claims 1 to 1 1, characterized in that in addition to the components (A) and (B) and optionally alkoxysilane further additives selected from the group of plasticizers, fillers, solvents, adhesion promoters, rheology additives, stabilizers, catalysts, Solvent and

Desiccant, in particular chemical moisture-drying agent are included.

13. A curable mixture according to any one of claims 1 to 12, characterized in that it comprises 10 to 90 wt .-%, more preferably 20 to 80 wt .-% of compounds (a1) based on the binder mixture (A), wherein the compounds (a1) preferably have on average between greater than 1 and up to 4 trialkoxysilyl functions per silyl polyether of the formula (1).

14. A curable mixture according to any one of claims 1 to 12, characterized in that as compounds (a1) urethanized silyl polyether having on average between 1 and up to 4 triethoxysilyl functions per silyl polyether of formula (1).

15. Use of the curable compositions according to any one of claims 1 to 14 as a sealant or adhesive or for producing a sealant or adhesive.