EP2449033A2 - Curable composition having a silane-modified reactive thinner - Google Patents

Abstract

Aim of the invention is to implement low viscosity prior to curing along with good elasticity after curing and a broad adhesion spectrum in a solvent-free and water-free curable composition. This aim is achieved by using at least one polymer A, obtainable by converting a polyether and at least one ethylenically unsaturated silane, wherein the ethylenically unsaturated silane has at least one hydrolysable group on the silicon atom, in the presence of a radical starter. The invention further relates to a method for producing a solvent-free and water-free curable composition, characterized in that at least one polymer is produced by converting a polyether and at least one ethylenically unsaturated silane having at least one hydrolysable group on the silicon atom, in the presence of a radical starter, and the polymer so obtained is mixed with further components of the composition. The invention further relates to the use of the curable composition according to the invention, or of a composition produced by means of the method according to the invention, as an adhesive, sealant, or coating agent.

Description

 Hardenable composition with silane-modified reactive diluent

The present invention relates to the field of curable compositions such as those used in adhesives, sealants and coatings. In particular, the invention relates to compositions containing at least one silylfunktionalisiert.es

Polymer is added, and proposes special such polymers. The invention further relates to a process for the preparation of the compositions and their use as adhesive, sealing or Besen ichtungsstoff.

Polymer systems that possess reactive silyl groups are known. In the presence of atmospheric moisture, polymers which have silyl groups with hydrolyzable substituents are capable, even at room temperature, of condensing with elimination of the hydrolyzed radicals. Depending on the content of silyl groups with hydrolyzable

Substituents and the structure of these silyl groups are formed mainly by long-chain polymers (thermoplastics), relatively wide-mesh, three-dimensional networks (elastomers) or highly crosslinked systems (thermosets).

The polymers usually have an organic skeleton which z. B. carries alkoxy or Acyloxysilylgruppen. The organic skeleton may be, for example, polyurethanes, polyesters, polyethers, etc. Such α-ω-silane-substituted polymers are often characterized by high flexibility and cohesion.

In addition, polymers containing randomly distributed silyl groups have been described. These polymers are often based on polyacrylates as the main body and become the

Improvement of adhesive properties used.

Polymers having silyl groups at the termini or in a side chain are described, for example, in EP 1 396 513 B1. The hydrolyzable substituent having silyl groups according to the document by addition of a hydrosilane to terminal double bonds of the backbone polymer, by reaction of isocyanatosilanes with hydroxyl groups of the polymer, by reacting active hydrogen atoms containing silanes with isocyanate-functionalized polymers or by reaction of mercaptosilanes with terminal Introduced double bonds of the polymer. The polymers are part of

Compositions used as adhesives or sealants.

The same methods for introducing reactive silyl groups into polymers are also described in EP 0 918 062 B1. In addition, curable compositions based on such polymers, according to this document, contain another polymer which may be u. a. from the

Polymerization of vinylsilanes can result.

US Pat. No. 4,514,315 describes compositions for inhibiting the corrosion of aluminum which, in addition to water and / or alcohol, contains polyethers which have been initiated by free-radically

Reactions with alkenylsilanes are modified. The molecular weights of the underlying polyethers are between 200 and 100,000. For example, the compositions are intended for use as an additive for vehicle coolant fluids.

In the preparation of curable compositions based on functionalized polymers, a challenge is to keep the viscosity of the compositions low enough to ensure good handleability and processability

To prevent sedimentation phenomena. This can be achieved by the addition of plasticizers or solvents, which, however, are often of concern to health and may also worsen the material properties of the cured composition in view of evaporation or migration after curing.

Another approach is followed, for example, in EP 0 162 588 B1. This patent describes the introduction of polymeric side strands or graft branches into polyether polyols which are useful for the

Further processing to polyurethanes are provided. For this purpose will be

Polyether polyols reacted with olefinic monomers in the presence of radical initiators. Vinyl silanes with reactive Siylgruppen are not mentioned. In addition, a stabilizer is used which results from the reaction of polyols with tri- or tetrafunctionalized silanes. The polyether polyols thus produced create a steric hindrance between the chain strands and thus counteract the agglomeration of polymer particles. According to the examples given have dispersions of the grafted

Polyether polyols have viscosities between 2,000 and 5,500 mPas. Adhesive properties or properties of cured compositions are not apparent from EP 0 162 588.

There is therefore a continuing need for easy-to-handle compositions that meet all the requirements of a modern adhesive, sealant or coating material. Task of It is therefore an object of the present invention to provide compositions with the lowest possible viscosity which, after curing, have high flexibility and elasticity and, moreover, are distinguished by a broad adhesive spectrum.

The solution of the problem arises from the basic idea of the invention, the

Compositions to add silane-modified reactive polyether-based reactive diluents.

A first object of the present invention is therefore a solvent- and water-free curable composition containing at least one polymer A, wherein the polymer A by reacting a polyether with at least one ethylenically unsaturated silane in

Presence of a radical initiator is available, wherein the ethylenically unsaturated silane carries at least one hydrolyzable group on the silicon atom.

In the context of the present invention, a "composition" is understood as meaning a mixture of at least two components, one of which is the at least one contained polymer A. Further possible constituents of a composition according to the invention are listed below in the text Understand that at least the polymer A is able, under the influence of external conditions, in particular under the influence of existing in the environment and / or deliberately supplied moisture to crosslink by a chemical reaction of the reactive groups present in the polymer with other polymer molecules and thereby from a plastically deformable state to a harder state. In general, the crosslinking can be effected by chemical and / or physical influences, in addition to the moisture already mentioned, for example by supplying energy in the form of heat, light or other electromagnetic radiation, but also by simply contacting the composition with air or a reactive component.

The term "solvent-free and anhydrous" is defined in the context of the present invention in that water or solvent can not be deliberately added to the composition, but can be present as an impurity or as a component introduced with the components of the composition in low concentrations the total amount of water and solvents are set at 5% by weight, based on the total weight of the composition.

The term "solvent" is understood to mean inorganic or organic liquids capable of dissolving other gaseous, liquid or solid substances these include the organic solvents known to those skilled in the art, for example alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols

(Ethylene glycol, diethylene glycol), ethers and the like. Glycol ethers (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ethers), ketones (acetone, butanone,

Cyclohexanone), esters (acetic acid esters, glycol esters), amides and the like. a. Nitrogen verb.

(Dimethylformamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur-verb.

(Carbon disulfide, dimethylsulfoxide, sulfolane), nitro-verb. (Nitrobenzene),

Halogenated hydrocarbons (dichloromethane, chloroform, tetrachloromethane, tri-,

Tetrachloroethene, 1,2-dichloroethane, chlorofluorocarbons), hydrocarbons (benzines, petroleum ether, cyclohexane, methylcyclohexane, decalin, terpene-L, benzene, toluene, xylene). Not to be understood by the term "solvent" within the meaning of the present invention, of course, the silane-modified polyether A expressly stated as part of the composition according to the invention.

For the purposes of the present invention, a "polyether" is understood as meaning a polymer whose repeat units are held together by ether functionalities C-O-C. Polymers with pendant ether groups such as cellulose ethers, starch ethers and vinyl ether polymers, as well as polyacetals, do not fall under this definition.

The polyether on which the polymer A is based is preferably a polyalkylene oxide, more preferably polyethylene oxide and / or polypropylene oxide.

Polyethers have a flexible and elastic structure that can be used to make compositions that have excellent elastic properties. Polyethers are not only flexible in their backbone but also stable at the same time. For example, polyethers are not attacked or decomposed by water and bacteria, in contrast to, for example, polyesters.

The molecular weight M _n of the polyether on which the polymer A is based is preferably 2,000 to 100,000 g / mol (dalton), the molecular weight particularly preferably being at least 6,000 g / mol and in particular at least 8,000 g / mol. Molecular weights of at least 2,000 g / mol are advantageous for the polyethers of the present invention because compositions based on polyethers having such a minimum molecular weight have significant film-forming properties. Particularly advantageous viscoelastic properties can be achieved if one

Polyether, which have a narrow molecular weight distribution and thus low polydispersity used. These can be produced, for example, by the so-called double-metal cyanide catalysis (DMC catalysis). Polyethers produced in this way are distinguished by a particularly narrow molar mass distribution, by a high average molecular weight and by a very low number of double bonds at the ends of the polymer chains.

In a specific embodiment of the present invention, the maximum

Polydispersity M _w / M _n of the polymer A on which the underlying polyether therefore 3, more preferably 1, 7 and most preferably 1, 5.

The molecular weight M _n is understood to mean the number average molecular weight of the polymer. This, as well as the weight-average molecular weight M _w , can be determined by gel permeation chromatography (GPC, also: SEC). This method is known to the person skilled in the art. The polydispersity is derived from the average molecular weights M _w and M _n . It is calculated as PD = M _w / M _n .

The ratio M _w / M _n , which is also called polydispersity, gives the width of the

Molar mass distribution and thus the different degrees of polymerization of the individual chains in polydisperse polymers. For many polymers and polycondensates, the polydispersity has a value of about 2. Strict monodispersity would be given at a value of 1. A low polydispersity of, for example, less than 1.5 indicates a relatively narrow molecular weight distribution and thus the specific expression of the molecular weight related properties, such. As the viscosity, towards. In particular, therefore, in the context of the present invention, the polyether on which the polymer A is based has a polydispersity (M _w / M _n ) of less than 1.3.

By an "ethylenically unsaturated silane" is meant a non-polymeric silicon compound in which at least one silicon atom is bonded by chemical bonding to at least one organic radical having a carbon-carbon double bond (C = C).

A "hydrolyzable group" is used in the context of the present invention

Substituent understood that can be converted by reaction with water in a hydroxy group (OH). In particular, hydrolyzable groups are alkoxy (also referred to as alkyloxy groups) and acyloxy groups. The polymer A is preferably obtainable by reacting a polyether with at least one ethylenically unsaturated silane of the general formula (I),

R ¹ R ² C = C (R ³ ) -R ⁴ -SiXYZ (I) wherein R ¹ , R ² and R ^{3 are the} same or different and independently of one another

H or an alkyl group having 1 to 6 carbon atoms,

R ^{4 stands} for a chemical bond - which is here to be understood as meaning a single bond - or for a divalent organic group which contains 1 to 10 atoms selected from C (carbon), O (oxygen) and N (nitrogen), and

X, Y and Z are the same or different, at least two of the substituents X, Y and Z are independently a methoxy, ethoxy, propyloxy or butyloxy group and the remaining substituent is one of the above-mentioned alkyloxy groups, an alkyl group having 1 to 6 carbon atoms is an alkenyl group having 2 to 6 carbon atoms or an alkenyloxy group having 2 to 6 carbon atoms.

Most preferably, R ^{4 is} a chemical bond.

As hydrolyzable groups on the silicon atom it is generally preferred to choose alkoxy groups, in particular methoxy, ethoxy, n-propyloxy, isopropoxy, n-butyloxy and isobutoxy groups. This is advantageous because when cured alkoxy groups

containing compositions are not released mucous membranes irritating substances. The alcohols formed are harmless in the released amounts and evaporate. Therefore, such compositions are particularly suitable for the home improvement sector. As hydrolyzable groups but also acyloxy groups, such as a

Acetoxy group -O-CO-CH ₃ , can be used.

The ethylenically unsaturated silane is particularly preferably selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxymethylsilane,

Vinyldiethoxymethylsilane, trans-.beta.-methylacrylic acid trimethoxysilylmethyl ester and trans-.beta.-methylacrylic acid trimethoxysilylpropyl ester.

In general, polymers which contain di- or trialkoxysilyl groups have highly reactive attachment sites which allow rapid curing, high degrees of crosslinking and thus good Allow final strengths. Another advantage of such polymers containing alkoxy groups is that when cured under the influence of moisture alcohols are formed which are harmless in the amounts released and evaporate.

The particular advantage of dialkoxysilyl groups is that the corresponding

Compositions after curing are more elastic, softer and more flexible than

Trialkoxysilyl-containing systems. They are therefore particularly suitable for use as sealants. In addition, they cease even less alcohol when curing and are therefore of particular interest when the amount of alcohol released is to be reduced.

With trialkoxysilyl groups, on the other hand, a higher degree of crosslinking can be achieved, which is particularly advantageous if a harder, stronger mass is desired after curing. In addition, trialkoxysilyl groups are more reactive, ie they crosslink faster and thus possibly reduce the required amount of catalyst, and they have advantages in the "cold flow" - the dimensional stability of a corresponding adhesive under the influence of force and optionally temperature.

Depending on the nature of the alkyl radicals on the oxygen atom, compounds having alkoxysilyl groups have different reactivities in chemical reactions. Within the alkoxy groups, the methoxy group shows the greatest reactivity. It is thus possible to resort to silyl groups of this type if particularly rapid curing is desired. Higher aliphatic radicals such as ethoxy bring about a lower reactivity of the terminal alkoxysilyl group compared to methoxy groups and can advantageously be used for the development of graduated crosslinking rates.

 Interesting design options also open up combinations of both groups. If z. B. for X methoxy and Y ethoxy selected within the same alkoxysilyl group, the desired reactivity of the final silyl groups can be adjusted particularly fine, if only methoxy-bearing silyl groups are perceived as too reactive and the ethoxy-bearing silyl groups for use as too slow.

In addition to methoxy and ethoxy groups, it is of course also possible to use larger radicals than hydrolyzable groups, which naturally have a lower reactivity. This is of particular interest when a delayed curing is desired, for example, for adhesives, even after the application yet Moving the glued surfaces against each other to allow finding the final positions.

The polymer A is obtainable according to the invention by the reaction of a polyether with at least one ethylenically unsaturated silane which carries at least one hydrolyzable group on the silicon atom, in the presence of a radical initiator. Preferably, the

Implementation carried out such that the ethylenically unsaturated silane and the radical initiator at temperatures of more than 50 ⁰ C, more preferably greater than 70 ⁰ C and

especially greater than 90 ° C to the polyether or a mixture of the polyether. A reaction under such conditions leads, to the best of our knowledge, to an attachment of the silane to free-radically initiated reactive sites in the polyether chain whose localization can not be controlled. Preferably, the polymer (s) A have silyl groups with at least one hydrolyzable group on the silicon atom in random distribution.

The viscosity of each polymer A contained in the composition according to the invention is preferably between 300 and 50,000 mPas, more preferably between 500 and 20,000 mPas and in particular between 600 and 10,000 mPas, very particularly preferably between 700 and 7,000 mPas (measured in each case according to Brookfield, 23 ° C. , Sp.7, 100 rpm). The polymer (s) A thus has / have very low viscosities. The polymer A therefore serves as a reactive diluent in a composition according to the invention. A reactive diluent is understood as meaning a component which reduces the viscosity of the composition which has not yet hardened, but the curing is included in the crosslinking by chemical reaction.

The polymer A is preferably obtainable by reacting a polyether with 1 to 50% by weight, more preferably 3 to 25% by weight, of ethylenically unsaturated silane, based in each case on the weight of the polyether.

Preference is / are the / by reaction of a polyether with at least one ethylenically unsaturated silane, which carries at least one hydrolyzable group on the silicon atom, in the presence of a free radical initiator available (s) polymer (s) A in a composition according to the invention in a weight fraction of 5 bis 25 wt .-%, particularly preferably from 10 to 20 wt .-%, each based on the total weight of the composition.

A composition of the invention may contain one or more polymer (s) A as the sole crosslinkable component. In a preferred embodiment contains a composition according to the invention, however, additionally one or more polymer (s) B terminated with at least one reactive silyl group, wherein polymer B is not identical to a polymer A. The polymer B is preferably an alkoxy- and / or acyloxysilane-terminated polymer having at least one end group of the general formula (II)

-A _n -R-SiXYZ (II), where A is a divalent linking group,

 R is a divalent hydrocarbon radical optionally containing a heteroatom, with 1 -

12 C atoms, and

X, Y, Z independently of one another are C ₁ -C ₈ -alkyl-, C ₁ -C ₈ -alkoxy- or C ₁ -C ₈ -acyloxy radicals, where at least one of the radicals is a C ₁ -C ₈ -alkoxy- or C ₁ -C ₈ -alkoxy- or C ₁ -C ₈ -alkoxy radical ₁ - C ₈ - acyloxy group, and n is 0 or 1.

A divalent or divalent bonding group A is a divalent chemical group which links the polymer skeleton of the alkoxy- and / or acyloxysilane-terminated polymer with the radical R of the end group. The divalent linking group A can be formed, for example, in the preparation of the alkoxy- and / or acyloxysilane-terminated polymer, e.g. as a urethane group by the reaction of a hydroxyl-functionalized polyether with an isocyanatosilane. In this case, the divalent binding group of structural features occurring in the underlying polymer skeleton can both

be distinguishable as well as indistinguishable. The latter is, for example, if it is identical to the points of attachment of the repeat units of the polymer backbone.

The variable n is 0 or 1, i. the divalent binding group A links this

Polymer backbone with the radical R (n = 1) or the polymer backbone is directly linked to the radical R or linked (n = 0).

The radical R is a divalent, optionally containing a heteroatom hydrocarbon radical having 1 to 12 carbon atoms. As heteroatom, for example, oxygen (O) or nitrogen (N) may be included. The hydrocarbon radical may be, for example, a straight-chain or branched or cyclic, substituted or unsubstituted alkylene radical. The hydrocarbon radical may be saturated or unsaturated. X, Y and Z in the general formula (II) are independently Ci - C ₈ - alkyl groups, Ci - Ce - alkoxy or Ci - Ce - acyloxy. At least one of the radicals X, Y, Z must be a hydrolyzable group, ie a C 1 -C ₈ -alkoxy group or radical or a C 1 -C ₈ -acyloxy radical or radical. As hydrolyzable groups are preferably

Alkoxy groups, in particular methoxy, ethoxy, propyloxy and butoxy groups, selected.

Preferably, the alkoxy- and / or acyloxysilane-terminated polymer B has at least two end groups of the general formula (II). Each polymer chain thus contains at least two linkage sites at which the condensation of the polymers can take place with elimination of the hydrolyzed radicals in the presence of atmospheric moisture. In this way, a regular and fast crosslinkability is achieved, so that bonds can be obtained with good strength. In addition, can be on the amount and structure of the hydrolyzable groups -. B. use of di- or trialkoxysilyl groups,

Methoxy groups or longer radicals, etc. - the design of the achievable network as a long-chain system (thermoplastics), relatively wide meshed three-dimensional network (elastomers) or highly cross-linked system (thermosets) control, so that, among other things, the elasticity, flexibility and heat resistance of the finished networked

Compositions can be influenced.

Preferably, in polymer B, X is an alkyl group and Y and Z are an alkoxy group, or X, Y and Z are an alkoxy group.

Particularly preferred in a group of the general formula (II) X, Y and Z are each independently a methyl, an ethyl, a methoxy or an ethoxy group. Methoxy and ethoxy groups as relatively small hydrolyzable groups with low steric demand are very reactive and thus allow rapid curing even with low catalyst use. They are therefore particularly interesting for systems in which a rapid curing is desired, such as adhesives, which should have a high initial adhesion. In particular, an embodiment is preferred in which X, Y and Z are a methyl or a methoxy group.

Preferably, R is in a terminal group of general formula (II)

Hydrocarbon radical having 1 to 6 carbon atoms. Over the length of the hydrocarbon radicals, which form the link between the polymer backbone and the silyl radical, the

Curing rate of the composition are influenced, whereby a further design option for the composition of the invention is opened. In particular, R in the general formula (II) is a methylene, ethylene or propylene radical. Methylene and n-propylene radicals are particularly preferably used. Alkoxysilane-terminated compounds having a methylene group as a link to the polymer backbone - so-called α-silanes - have a particularly high reactivity of the final silyl group, which leads to shorter setting times and thus to a very rapid curing of formulations based on such polymers.

 In general, an extension of the connecting hydrocarbon chain leads to a

decreased reactivity of the polymers. In particular, the γ-silanes - they contain the unbranched propylene radical as a link - have a balance between necessary reactivity (acceptable curing times) and delayed curing (open time, possibility of correction after bonding) on.

By consciously combining α- and γ-alkoxysilane-terminated building blocks, the curing rate of the systems can be influenced as desired.

A in the general formula (II) is preferably an amide, carbamate, urea, imino, carboxylate, carbamoyl, amidino, carbonate, sulfonate or sulfinate group or a

Oxygen or nitrogen atom. The binding group A can in the preparation of the

silyl-terminated polymers are formed by reacting the backbone polymer with a reactive compound bearing the -R-SiXYZ sequence. Group A may be both distinguishable and indistinguishable from structural features occurring in the underlying polymer backbone. The latter is, for example, when you with the

Linking points of the repeat units of the polymer backbone is identical. In this case, n would equal the value 0. If the binding group A is of the linking groups in the

Polymer skeleton distinguishable, n corresponds to the value 1.

Several methods are described in the art for linking a reactive silyl group to a polymer backbone. Mention may be made of the polymerization of unsaturated

Monomers having such z. B. alkoxysilyl groups. A suitable monomer of the latter variety would be, for example, vinyltrimethoxysilane. Another method is the grafting of unsaturated monomers such. For example, vinyltrimethoxysilane on thermoplastics, such as polyethylene. Also widely used is the hydrosilylation, the addition of H-silanes such as methyldimethoxysilane to carbon-carbon double bonds under noble metal catalysis. Through this procedure, the the terminal becomes Silyl group-containing radical directly, ie without a further linking group, linked to the polymeric backbone (n = 0 in formula I).

Particularly preferred as the bonding group A in the general formula (II) are urethane and urea groups, which can be obtained by reacting certain functional groups of a prepolymer with an organosilane, which carries a further functional group. Urethane groups can, for. B. arise when either the polymer backbone contains terminal hydroxyl groups and isocyanatosilanes used as a further component, or conversely, when a polymer having terminal isocyanate groups is reacted with a terminal hydroxy-containing alkoxysilane. Similarly, urea groups can be obtained when a terminal primary or secondary amino group - either silane or polymer - is used which reacts with a terminal isocyanate group present in each reactant. That is, either an amino silane having a terminal isocyanate group-containing polymer or a terminal amino group-substituted polymer is reacted with an isocyanatosilane. Urethane and urea groups advantageously increase the strength of the polymer chains and the entire crosslinked polymer because they can form hydrogen bonds.

The alkoxy and / or acyloxysilane-terminated polymer B preferably has a skeleton which is selected from the group consisting of polyurethanes, polyethers, polyesters, polyacrylates,

Poly (meth) acrylates, polyacrylamides, poly (meth) acrylamides, polyvinyl esters, polyolefins, alkyd resins, phenolic resins, vinyl polymers, styrene-butadiene copolymers, as well as copolymers of one or more of the abovementioned basic skeletons. By selecting and specific design of the polymer classes used for the skeleton essential properties of the composition of the invention - such. As viscosity and elasticity, but also the resistance to environmental influences - be determined.

Particular preference is given to using polyacrylates, polyurethanes and polyesters as well as polyethers for the construction of the backbone.

 The use of polyurethanes and polyesters opens up a variety of possible applications, because with both classes of polymer depending on the choice and stoichiometric ratios of

Starting materials very different mechanical properties can be realized. In addition, polyesters can be decomposed by water and bacteria and are therefore of interest for applications where biodegradability is important. Polymers containing polyether as a backbone have a flexible and elastic structure not only at the end groups but also in the polymer backbone. This can be used to produce compositions which have excellent elastic properties. Polyethers are not only flexible in their backbone but also stable at the same time. For example, they are not attacked or decomposed by water and bacteria.

In the context of the present invention, polyethers based on polyethylene oxide and / or polypropylene oxide are particularly preferably used with regard to availability.

The alkoxy- and / or acyloxysilane-terminated polymer B preferably has a molecular weight M _n of 4,000 to 100,000, preferably 8,000 to 50,000, particularly preferably 10,000 to 30,000, in particular 15,000 to 25,000 g / mol. The molecular weight M _n is understood to mean the number average molecular weight of the polymer. This, as well as the weight-average molecular weight M _w , can be determined by gel permeation chromatography (GPC). Such a method is known to the person skilled in the art.

 The indicated molecular weights are particularly advantageous, since with such

Allow polymers in the appropriate compositions a balance of viscosity (ease of processing), adjust strength and elasticity. This combination is very advantageous in a molecular weight range from 12,000 to 20,000, in particular from 14,000 to 18,000, pronounced.

In the context of the present invention, the ratio M _w / M _n in polymer B is preferably less than 1.5. The alkoxy- and / or acyloxysilane-terminated polymer B particularly preferably has a polydispersity (M _w / M _n ) of less than 1.3.

A "free-radical initiator" is understood as meaning a compound which decomposes to form free radicals after thermal or photochemical, preferably thermal, excitation and free radical initiators are azobis (isobutyronitrile) (AIBN) and / or peroxides such as, for example Benzoyl peroxide and / or dicumyl peroxide. Dicumyl peroxide is particularly preferably used.

A composition of the invention may be in addition to the aforementioned silylated

Polymers and other additives and additives that can give them improved elastic properties, improved resilience, sufficiently long processing time, fast curing rate and low residual tack. These auxiliaries and additives include adhesion promoters, catalysts and plasticizers as well as fillers. In addition, the compositions may be used as further additives stabilizers,

Antioxidants, reactive diluents, drying agents, UV stabilizers, anti-aging agents, rheological aids, color pigments or pastes, fungicides or flame retardants.

A plasticizer is understood as meaning a substance which reduces the viscosity of the

Reduces compositions and thus facilitates the processability.

The plasticizer is preferably selected from a fatty acid ester, a

Dicarboxylic acid ester, an ester of OH-groups or epoxidized fatty acids, a fat, a glycolic acid ester, a phthalic acid ester, a benzoic acid ester, a

Phosphoric acid ester, a sulfonic acid ester, a trimellitic acid ester, an epoxidized plasticizer, a polyether plasticizer, a polystyrene, a hydrocarbon plasticizer and a chlorinated paraffin, and mixtures of two or more thereof. Through the specific selection of one of these plasticizers or a specific combination, in addition to a reduction of the viscosity and thus a better processability further advantageous properties of the composition according to the invention, for. B.

Geliervermögen the polymers, cold elasticity or cold resistance or antistatic properties can be realized.

For example, from the group of phthalic acid esters dioctyl phthalate, dibutyl phthalate, diisoundecyl phthalate, diisononyl phthalate or butyl benzyl phthalate, from the adipates dioctyl adipate, diisodecyl adipate, furthermore diisodecyl succinate, dibutyl sebacate or butyl oleate.

Of the polyether plasticizers are preferably endgruppenverschlossene

Polyethylene glycols used, for example, polyethylene or polypropylene glycol di-Ci. ₄ - alkyl ethers, in particular the dimethyl or diethyl ethers of diethylene glycol or dipropylene glycol, and mixtures of two or more thereof.

Also suitable as plasticizers are, for example, esters of abietic acid, butyric acid esters, acetic acid esters, propionic acid esters, thiobutyric acid esters, citric acid esters and esters based on nitrocellulose and polyvinyl acetate, and mixtures of two or more thereof. Also suitable, for example, are the asymmetric esters of adipic acid monooctyl ester with 2-ethylhexanol (Edenol DOA, Cognis Deutschland GmbH, Dusseldorf). In addition, suitable as plasticizers are the pure or mixed ethers monofunctional, linear or branched C ₄ _i ₆ alcohols or mixtures of two or more different ethers of such alcohols, for example dioctyl ether (available as Cetiol OE, Cognis Germany GmbH, Dusseldorf).

Likewise suitable as plasticizers in the context of the present invention are diurethanes which are suitable, for example, by reaction of diols with

 OH end groups can be prepared with monofunctional isocyanates by the stoichiometry is chosen so that react substantially all free OH groups. Optionally, excess isocyanate can then be removed from the reaction mixture, for example, by distillation. Another method for the preparation of diurethanes is the reaction of monofunctional alcohols with diisocyanates, where possible all of the NCO groups react.

The composition according to the invention contains a reactive diluent in the form of the polymer (s) A. A viscosity of the composition according to the invention which is still too high for certain applications can also be achieved by adding another

Reactive thinner can be reduced in a simple and convenient manner, without causing segregation phenomena (e.g., plasticizer migration) in the cured mass.

Preferably, this further reactive diluent has at least one functional group which, after the application of e.g. B. reacts with moisture or atmospheric oxygen. Examples of such groups are silyl groups, isocyanate groups, vinyl unsaturated groups and polyunsaturated systems.

The viscosity of the reactive diluent is preferably less than 20,000 mPas, particularly preferably about 0.1-6,000 mPas, very particularly preferably 1-1,000 mPas (Brookfield RVT, 23 ^° C., spindle 7, 10 rpm).

As a reactive diluent z. The following substances may be used, for example: polyalkylene glycols reacted with isocyanatosilanes (for example Synalox 100-50B, DOW), alkyltrimethoxysilane,

Alkyltriethoxysilane, such as methyltrimethoxysilane, methyltriethoxysilane and vinyltrimethoxysilane (XL 10, Wacker), phenyltrimethoxysilane, phenyltriethoxysilane, octyltrimethoxysilane,

Tetraethoxysilane, vinyldimethoxymethylsilane (XL12, Wacker), vinyltriethoxysilane (GF56, Wacker), vinyltriacetoxysilane (GF62, Wacker), isooctyltrimethoxysilane (IOtrimethoxy), Isooctyltriethoxysilane (IO triethoxy, Wacker), N-trimethoxysilylmethyl-O-methylcarbamate (XL63, Wacker), N-dimethoxy (methyl) silylmethyl-O-methyl-carbamate (XL65, Wacker),

Hexadecyltrimethoxysilane, 3-octanoylthio-i-propyltriethoxysilane and partial hydrolysates of these compounds.

The composition of the invention may further comprise a coupling agent. An adhesion promoter is understood as meaning a substance which has the adhesive properties of

Adhesive coatings on surfaces improved.

 Conventional adhesion promoters (tackifiers) known to the person skilled in the art can be used alone or as a combination of several compounds. Suitable examples are resins, terpene oligomers, coumarone / indene resins, aliphatic, petrochemical resins and modified

Phenolic resins. Suitable in the context of the present invention, for example

Hydrocarbon resins, as obtained by polymerization of terpenes, mainly α- or .beta.-pinene, dipentene or limonene. The polymerization of these monomers is usually cationic with initiation with Friedel-Crafts catalysts. The terpene resins also include copolymers of terpenes and other monomers, for example styrene, α-methylstyrene, isoprene and the like. The resins mentioned are used, for example, as adhesion promoters for pressure-sensitive adhesives and coating materials. Also suitable are the terpene-phenolic resins prepared by acid catalyzed addition of phenols to terpene or rosin. Terpene-phenolic resins are soluble in most organic solvents and oils and are miscible with other resins, waxes and rubbers. Likewise suitable in the context of the present invention as adhesion promoters in the abovementioned sense are the rosins and their derivatives, for example their esters or alcohols.

Silane coupling agents, in particular aminosilanes, are particularly suitable.

In a further preferred embodiment of the curable invention

Composition, the composition comprises a silane of the general formula (III)

R ^' R ^" NR ⁵ -SiXYZ (III) as a coupling agent, wherein

R ^' and R ^" independently of one another are hydrogen or C 1 -C 6 -alkyl radicals,

R ^{5 is} a divalent hydrocarbon radical optionally containing a heteroatom, with 1 -

12 C atoms, and X, Y, Z independently of each other Ci - C ₈ - alkyl, Ci - C ₈ - alkoxy or Ci - C ₈ - acyloxy radicals, said at least one of a Ci - C ₈ - alkoxy or Ci - C ₈ - Acyloxygruppe is. By nature, such compounds have a high affinity for the binding

Polymer components of the curable composition according to the invention, but also to a wide range of polar and non-polar surfaces and therefore contribute to the formation of a particularly stable adhesion between the adhesive composition and the substrates to be bonded in each case.

The linking group R ⁵ may be, for example, a straight-chain or branched or cyclic, substituted or unsubstituted alkylene radical. Preferably, the linking group R ^{5 is} an n-propylene radical or a methylene radical.

In a curable composition according to the invention, a crosslinking catalyst which may also be referred to as a curing catalyst is preferably present as further constituent. As crosslinking catalysts for controlling the curing rate of the curable compositions of the invention, for example, organometallic compounds such as iron or tin compounds are suitable, in particular the 1, 3-dicarbonyl compounds of iron such. Example, iron (III) acetylacetonate or di- or tetravalent tin such as dibutyltin bisacetylacetonate, the dialkyltin (IV) - dicarboxylates - z. Dibutyltin dilaurate, dibutyltin maleate or dibutyltin diacetate - or the corresponding dialkoxylates, e.g. B. dibutyltin dimethoxide. Especially with the organotin compounds are well-tried and easily accessible catalysts with excellent activity. However, some tin organyls have come under criticism due to physiological and environmental concerns. Therefore, the invention

Composition in another specific embodiment tin-free. Nevertheless, the compositions according to the invention can be cured well and quickly using alternative catalysts without any loss of quality.

Boron halides such as boron trifluoride, boron trichloride, boron tribromide, boron triiodide or mixed boron halides can alternatively be used as curing catalysts. Particularly preferred are boron trifluoride complexes such as e.g. Boron trifluoride diethyl etherate (CAS No. [109-63-7]), which are easier to handle as liquids than the gaseous boron halides.

Further, 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) is useful as a catalyst for the composition of the present invention. In addition, titanium, aluminum and zirconium compounds or mixtures of one or more catalysts of one or more of the groups just mentioned are preferably used as catalysts. On the one hand, the use of tin compounds can be avoided in this way, on the other hand, a better adhesion to normally poorly adhering organic surfaces such. B. reach acrylates. Among the titanium, aluminum and zirconium catalysts, the titanium catalysts are preferably used because they provide the best curing results.

Titanium catalysts are compounds which have hydroxyl groups and / or substituted or unsubstituted alkoxy groups, ie titanium alkoxides of the general formula

Ti (OR ^Z ) ₄ , where R ^{z is} an organic group, preferably a substituted or unsubstituted one

Hydrocarbon group having 1 to 20 carbon atoms and the 4 alkoxy groups -OR ^{Z are the} same or different. Further, one or more of the radicals -OR ^Z by acyloxy groups may - OCOR ^Z to be replaced.

Also suitable as titanium catalysts titanium alkoxides in which one or more alkoxy groups are replaced by halogen atoms.

As titanium catalysts z. B. the following mixed or non-mixed-substituted titanium alkoxides are used:

 Tetramethoxytitanium, tetraethoxytitanium, tetraallyloxytitanium, tetra-n-propoxytitanium,

Tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraisobutoxy titanium, tetra (2-butoxy) titanium, tetra (t-butoxy) titanium, tetrapentoxy (titanium), tetracyclopentoxy titanium, tetrahexoxy titanium,

Tetracyclohexoxy titanium, tetrabenzoxy titanium, tetraoctoxy titanium, tetrakis (2-ethylhexoxy) titanium, tetradecoxy titanium, tetradodecoxy titanium, tetrastearoxy titanium, tetrabutoxy titanium dimer bis (2-ethylhexyloxy) bis (2-ethyl-1,3-hexanediolate), tetrakis (2-chloroethoxy) titanium, tetrakis (2-bromoethoxy) titanium, tetrakis (2-methoxyethoxy) titanium, tetrakis (2-ethoxyethoxy) titanium , Butoxy-trimethoxytitanium, dibutoxydimethoxytitanium, butoxytriethoxytitanium, dibutoxydiethoxytitanium,

Butoxytriisopropoxytitanium, dibutoxydiisopropoxytitanium, tetraphenoxybutane, tetrakis (o-chlorophenoxy) titanium, tetrakis (m-nitrophenoxy) titanium, tetrakis (p-methylphenoxy) titanium,

Tetrakis (trimethylsiloxy) titanium. Furthermore, titanium acylates can be used: triisopropoxy titanium,

 Triisopropoxytitanium methacrylate, diisopropoxytitanium dimethacrylate, isopropoxytitanium trimethacrylate, triisopropoxytitanium hexanoate, triisopropoxytitanium stearate and the like.

As halogenated titanium catalysts, e.g. the following compounds are used: triisopropoxytitanium chloride, diisopropoxytitanium dichloride, isopropoxytitanium trichloride,

Triisopropoxytitanium bromide, triisopropoxytitanium fluoride, triethoxytitanium chloride, tributoxytitanium chloride.

Furthermore, titanium chelate complexes can be used: dimethoxytitanium bis (ethylacetoacetate), dimethoxytitanium bis (acetylacetonate), diethoxytitanium bis (ethylacetoacetate),

Diethoxytitanium bis (acetylacetonate), diisopropoxy titanium bis (ethylacetoacetate),

Diisopropoxy titanium bis (methyl acetoacetate), diisopropoxy titanium bis (t-butyl acetoacetate),

Diisopropoxy titanium bis (methyl 3-oxo-4,4-dimethylhexanoate), diisopropoxy titanium bis (ethyl 3-oxo-4,4,4-trifluorobutanoate), diisopropoxy titanium bis (acetylacetonate), diisopropoxy titanium bis (2, 2,6,6-tetramethyl-3 , 5-heptanedionate), di (n-butoxy) titanium bis (ethylacetoacetate), di (n-butoxy) titanium bis (acetylacetonate), diisobutoxytitanium bis (ethylacetoacetate),

Diisobutoxytitanium bis (acetylacetonate), di (t-butoxy) titanium bis (ethylacetoacetate), di (t-butoxy) titanium bis (acetylacetonate), di (2-ethylhexoxy) titanium bis (ethylacetoacetate), di (2-ethylhexoxy) titanium bis (acetylacetonate), bis (1-methoxy-2-propoxy) titanium bis (ethylacetoacetate), bis (3-oxo-2-butoxy) titanium bis (ethylacetoacetate), bis (3-diethylaminopropoxy) titanium bis (ethylacetoacetate), triisopropoxytitanium (ethylacetoacetate), triisopropoxytitanium (diethylmalonate) .

Triisopropoxytitanium (allylacetoacetate), triisopropoxytitanium (methacryloxyethylacetoacetate), 1,2-dioxyethanitanebis (ethylacetoacetate), 1,3-dioxpropane titanium bis (ethylacetoacetate), 2,4-dioxypentanetitanium bis (ethylacetoacetate), 2,4-dimethyl-2,4-dioxypentanetitan bis (ethylacetoacetate ), Diisopropoxy titanium bis (triethanolaminate), tetrakis (ethyl acetoacetato) titanium,

Tetrakis (acetylacetonato) titanium, bis (trimethylsiloxy) titanium bis (ethylacetoacetate),

Bis (trimethylsiloxy) titanium bis (acetylacetonate).

The following titanium chelate complexes are preferably used, since they are commercially available and have a high catalytic activity:

Diethoxytitanium bis (ethylacetoacetate), diethoxytitanium bis (acetylacetonate),

Diisopropoxytitanium bis (ethylacetoacetate), diisopropoxytitanium bis (acetylacetonate),

Dibutoxytitanium bis (ethylacetoacetate) and dibutoxytitanium bis (acetylacetonate).

Particularly preferred are diethoxytitanium bis (ethylacetoacetate),

Diisopropoxytitanium (ethylacetoacetate) and dibutoxytitanium bis (ethylacetoacetate), most preferred is diisopropoxytitanium bis (ethylacetoacetate). Furthermore, the following titanium catalysts can also be used:

Isopropoxytitanium tris (dioctylphosphate), isopropoxytitanium tris (dodecylbenzylsulfonate),

Dihydroxytitanbislactat.

Aluminum catalysts can also be used as curing catalysts,

e.g. aluminum alkoxides

Al (OR ^Z ) ₃ , where R ^{z is} an organic group, preferably a substituted or unsubstituted

Hydrocarbon radical having 1 to 20 carbon atoms and the three radicals R ^{z are the} same or different.

 Also in the case of the aluminum alkoxides, one or more of the alkoxy radicals can be replaced by acyloxy radicals

-OC (O) R ^{Z be} replaced.

Furthermore, aluminum alkoxides can be used in which one or more alkoxy radicals are replaced by halogen atoms.

 Of the aluminum catalysts described, the pure aluminum alcoholates are preferred in view of their stability to moisture and the hardenability of the mixtures to which they are added. In addition, aluminum chelate complexes are preferred.

As aluminum alkoxides, for example, the following compounds can be used: trimethoxyaluminum, triethoxyaluminum, triallyloxyaluminum, tri (n-propoxy) aluminum, triisopropoxyaluminum, tri (n-butoxy) aluminum, triisobutoxyaluminum, tri (sec-butoxy) aluminum, tri (t-butoxy) aluminum , Tri (n-pentoxy) aluminum, tricyclopentoxyaluminum, trihexoxyaluminum, tricyclohexoxyaluminum, tribenzoxyaluminum, trioctoxyaluminum, tris (2-ethylhexoxy) aluminum, tridecoxyaluminum, tridodecoxyaluminum,

Tristioureaaluminum, dimeric tributoxyaluminum, tris (8-hydroxyoctoxy) aluminum, isopropoxyaluminum bis (2-ethyl-1,3-hexanediolate), diisopropoxyaluminum (2-ethyl-1,3-hexanediolate), (2-ethylhexoxy) aluminum bis (2-ethyl) 1,3-hexanediolate), bis (2-ethylhexyloxy) aluminum (2-ethyl-1,3-hexanediolate), tris (2-chloroethoxy) aluminum, tris (2-bromoethoxy) aluminum, tris (2-methoxyethoxy) aluminum, Tris (2-ethoxyethoxy) aluminum, butoxydimethoxyaluminum, methoxydibutoxyaluminum, butoxydiethoxyaluminum,

Ethoxydibutoxyaluminum, butoxydiisopropoxyaluminum, isopropoxydibutoxyaluminum, Triphenoxyaluminum, tris (o-chlorophenoxy) aluminum, tris (m-nitrophenoxy) aluminum, tris (p-methylphenoxy) aluminum.

For example, aluminum acylates can also be used:

Diisopropoxyaluminum acrylate, diisopropoxyaluminum methacrylate,

Isopropoxyaluminum dimethacrylate, diisopropoxaluminum hexanoate,

Diisopropoxyaluminiumstearat.

Further, aluminum halide compounds can be used, e.g.

Diisopropoxyaluminum chloride, isopropoxyaluminum dichloride, diisopropoxyaluminum bromide, diisopropoxyaluminum fluoride, diethoxyaluminum chloride, dibutoxyaluminum chloride.

Aluminum chelate complexes can also be used as catalysts, for example methoxyaluminum bis (ethylacetoacetate), methoxyaluminum bis (acetylacetonate),

Ethoxyaluminum bis (ethylacetoacetate), ethoxyaluminum bis (acetylacetonate),

Isopropoxyaluminum bis (ethylacetoacetate), isopropoxyaluminum bis (methylacetoacetate), isopropoxyaluminum bis (t-butylacetoacetate), dimethoxyaluminum (ethylacetoacetate),

Dimethoxyaluminum (acetylacetonate), diethoxyaluminum (ethylacetoacetate),

Diethoxyaluminum (acetylacetonate), diisopropoxyaluminum (ethylacetoacetate),

Diisopropoxyaluminum (methylacetoacetate), diisopropoxyaluminum (t-butylacetoacetate), isopropoxyaluminum bis (methyl-3-oxo-4,4-dimethylhexanoate), isopropoxyaluminum bis (ethyl-3-oxo-4,4,4-trifluoropentanoate), isopropoxyaluminum bis (acetylacetonate),

isopropoxyaluminum bis (2,2,6,6-tetramethyl-3,5-heptanedionate), n-butoxyaluminum bis (ethylacetoacetate), n-butoxyaluminum bis (acetylacetonate),

Isobutoxyaluminum bis (ethylacetoacetate), isobutoxyaluminum bis (acetylacetonate), t-butoxyaluminum bis (ethylacetoacetate), t-butoxyaluminum bis (acetylacetonate), 2-ethylhexoxyaluminum bis (ethylacetoacetate), 2-ethylhexoxyaluminum bis (acetylacetonate), 1, 2-dioxyethanaluminum (ethylacetoacetate), 1, 3 -Dioxypropanaluminum (ethylacetoacetate), 2,4-dioxypentanaluminim (ethylacetoacetate), 2,4-dimethyl-2,4-dioxypentanaluminim (ethylacetoacetate), lopropoxyaluminum bis (triethanolaminate),

Aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate),

Aluminum (acetylacetonate) bis (ethylacetoacetate).

 The following aluminum chelate complexes are preferably used as catalysts since they are commercially available and have high catalytic activities:

Ethoxyaluminum bis (ethylacetoacetate), ethoxyaluminum bis (acetylacetonate),

Isopropoxyaluminum bis (ethylacetoacetate), isopropoxyaluminum bis (acetylacetonate), Butoxyaluminum bis (ethylacetoacetate), butoxyaluminum bis (acetylacetonate),

Dimethoxyaluminum ethylacetoacetate, dimethoxyaluminum acetylacetonate,

Diethoxyaluminum ethylacetoacetate, diethoxyaluminum acetylacetonate,

Diisopropoxyaluminum ethylacetoacetate, diisopropoxyaluminum methylacetoacetate and

Diisopropoxyaluminum (t-butylacetoacetate).

Particularly preferred are ethoxyaluminum bis (ethylacetoacetate),

Isopropoxyaluminum bis (ethylacetoacetate), butoxyaluminum bis (ethylacetoacetate),

Dimethoxyaluminum ethylacetoacetate, diethoxyaluminum ethylacetoacetate and

Diisopropoxy.

Very particularly preferred are isopropoxyaluminum bis (ethylacetoacetate) and

Diisopropoxy.

Furthermore, z. B. also the following aluminum catalysts are used:

Bis (dioctylphosphato) isopropoxyaluminum, bis (dodecylbenzylsulfonato) isopropoxyaluminum, hydroxyaluminum bislactate.

Suitable zirconium catalysts are:

 Tetramethoxyzirconium, tetraethoxyzirconium, tetraallyloxyzirconium, tetra-n-propoxyzirconium,

Tetraisopropoxyzirconium, tetra-n-butoxyzirconium, tetraisobutoxyzirconium, tetra (2-butoxy) zirconium, tetra (t-butoxy) zirconium, tetrapentoxy (zirconium), tetracyclopentoxyzirconium, tetrahexoxyzirconium, tetracyclohexoxyzirconium, tetrabenzoxyzirconium, tetraoctoxyzirconium, tetrakis (2-ethylhexoxy) zirconium , Tetradecoxyzirconium, tetradoxecyczircon, tetrastearoxyzircon, tetrabutoyzirconium dimer, tetrakis (8-hydroxyoctoxy) zirconium, zirconium diisopropoxy-bis (2-ethyl-1,3-hexanediolate), zirconium bis (2-ethylhexyloxy) bis (2-ethyl -1, 3-hexanediolate), tetrakis (2-chloroethoxy) zirconium, tetrakis (2-bromoethoxy) zirconium, tetrakis (2-methoxyethoxy) zirconium, tetrakis (2-ethoxyethoxy) zirconium, butoxy-trimethoxyzirconium, dibutoxydimethoxyzirconium, butoxytriethoxyzirconium, dibutoxydiethoxyzircon, Butoxitriisopropoxyzirconium, dibutoxydiisopropoxyzirconium, tetraphenoxybutane, tetrakis (o-chlorophenoxy) zirconium, tetrakis (m-nitrophenoxy) zirconium, tetrakis (p-methylphenoxy) zirconium, tetrakis (trimethylsiloxy) zirconium, diisopropoxyzirconium bis (ethylacetoacetate),

Diisopropoxyzirconium bis (acetylacetonate), dibutoxyzirconium bis (ethylacetoacetate),

Dibutoxyzirconium bis (acetylacetonate), triisopropoxyzirconium acetoacetate,

Triisopropoxyzirconium acetylacetonate, tris (n-butoxy) zirconium acetoacetate, tris (n-butoxy) zirconium acetylacetonate, isopropoxyzircontris (ethylacetoacetate), Isopropoxyzircontris (acetylacetonate), n-butoxyzircontris (ethylacetoacetate), n-butoxyzircontris (acetylacetonate), n-butoxyzircon (acetylacetonate) bis (ethylacetoacetate).

Preference is given, for example, to diethoxyzirconium bis (ethylacetoacetate),

Diisopropoxyzirconium bis (ethylacetoacetate), dibutoxyzirconium bis (ethylacetoacetate),

Triispropoxyzirconium (ethylacetoacetate), tris (n-butoxy) zirconium (ethylacetoacetate),

Isopropoxyzircontris (ethylacetoacetate), n-butoxyzircontris (ethylacetoacetate) and n-butoxyzircon (acetylacetonate) bis (ethylacetoacetate).

Very particular preference is given to diisopropoxyzirconium bis (ethylacetoacetate),

Triispropoxyzirkon (ethylacetoacetate) and Isopropoxyzirkontris (ethylacetoacetate) used.

Furthermore zirconacylates can be used for example: triisopropoxyzirconium,

Triisopropoxyzirconium methacrylate, diisopropoxy-zirconium dimethacrylate,

 Isopropoxyzircontrimethacrylate, triisopropoxyzirconium hexanoate, triisopropoxyzirconstearate and the like.

As halogenated zirconium catalysts, the following compounds can be used:

Triisopropoxyzirconium chloride, diisopropoxyzirconium dichloride, isopropoxyzirconium trichloride,

Triisopropoxyzirconium bromide, triisopropoxyzirconfluoride, triethoxyzirconium chloride,

Tributoxyzirkonchlorid.

In addition, zirconium chelate complexes can also be used:

Dimethoxyzirconium bis (ethylacetoacetate), dimethoxyzirconium bis (acetylacetonate),

Diethoxyzirconium bis (ethylacetoacetate), diethoxyzirconium bis (acetylacetonate),

Diisopropoxyzirconium bis (ethylacetoacetate), diisopropoxyzirconium bis (methylacetoacetate),

Diisopropoxyzirconium bis (t-butyl acetoacetate), diisopropoxyzirconium bis (methyl 3-oxo-4,4-dimethylhexanoate), diisopropoxyzirconium bis (ethyl 3-oxo-4,4,4-trifluorobutanoate),

Diisopropoxyzirconium bis (acetylacetonate), diisopropoxyzirconium bis (2,2,6,6-tetramethyl-3,5-heptanedionate), di (n-butoxy) zirconium bis (ethylacetoacetate), di (n-butoxy) zirconium bis (acetylacetonate), diisobutoxyzirconium bis (ethylacetoacetate) , Diisobutoxyzirconium bis (acetylacetonate), di (t-butoxy) zirconium bis (ethylacetoacetate), di (t-butoxy) zirconium bis (acetylacetonate), di (2-ethylhexoxy) zirconium bis (ethylacetoacetate), di (2-ethylhexoxy) zirconium bis (acetylacetonate), Bis (1-methoxy-2-propoxy) zirconium bis (ethylacetoacetate), bis (3-oxo-2-butoxy) zirconium bis (ethylacetoacetate), bis (3-diethylaminopropoxy) zirconium bis (ethylacetoacetate),

Triisopropoxyzirconium (ethylacetoacetate), triisopropoxyzirconium (diethylmalonate),

Triisopropoxyzirconium (allylacetoacetate), triisopropoxyzircon (methacryloxyethylacetoacetate), 1, 2 Dioxyethanesirconium bis (ethylacetoacetate), 1,3-dioxypropanzirconium bis (ethylacetoacetate), 2,4-dioxypentanzirconium bis (ethylacetoacetate), 2,4-dimethyl-2,4-dioxypentanzirconium bis (ethylacetoacetate), diisopropoxyzirconium bis (triethanolaminate),

Tetrakis (ethylacetoacetato) zirconium, tetrakis (acetylacetonato) zirconium,

Bis (trimethylsiloxy) zirconium bis (ethylacetoacetate), bis (trimethylsiloxy) zirconium bis (acetylacetonate).

The following zirconium chelate complexes are preferably used since they are commercially available and have a high catalytic activity:

Diethoxyzirconium bis (ethylacetoacetate), diethoxyzirconium bis (acetylacetonate),

Diisopropoxyzirconium bis (ethylacetoacetate), diisopropoxyzirconium bis (acetylacetonate),

Dibutoxyzirconium bis (ethylacetoacetate) and dibutoxyzirconium bis (acetylacetonate)

Particularly preferred are diethoxyzirconium bis (ethylacetoacetate),

 Diisopropoxyzirconium (ethylacetoacetate) and dibutoxyzirconium bis (ethylacetoacetate), most preferred is diisopropoxyzirconium bis (ethylacetoacetate).

Furthermore, the following zirconium catalysts can also be used:

Isopropoxyzircontris (dioctylphosphate), isopropoxyzircontris (dodecylbenzylsulfonate),

Dihydroxyzirkonbislactat.

In addition, as curing catalysts carboxylic acid salts of metals or a

Mixture of several such salts are used, wherein these are selected from the

Carboxylates of the following metals: calcium, vanadium, iron, titanium, potassium, barium, manganese,

Nickel, cobalt and / or zirconium.

 Of the carboxylates, the calcium, vanadium, iron, titanium, potassium, barium, manganese and zirconium carboxylates are preferred because of their high activity.

 Particularly preferred are calcium, vanadium, iron, titanium and Zirkoniumcarboxylate.

Very particular preference is given to iron and titanium carboxylates.

You can z. For example, use the following compounds:

 Iron (II) (2-ethylhexanoate), iron (III) (2-ethylhexanoate), titanium (IV) (2-ethylhexanoate),

Vanadium (III) (2-ethylhexanoate), calcium (II) (2-ethylhexanoate) potassium 2-ethylhexanoate,

Barium (II) (2-ethylhexanoate), manganese (II) (2-ethylhexanoate), nickel (II) (2-ethylhexanoate),

Cobalt (II) (2-ethylhexanoate), zirconium (IV) (2-ethylhexanoate), iron (II) neodecanoate,

Iron (III) neodecanoate, titanium (IV) neodecanoate, vanadium (III) neodecanoate,

Calcium (II) neodecanoate, potassium neodecanoate, barium (II) neodecanoate, Zirconium (IV) neodecanoate, iron (II) oleate, iron (III) oleate, titanium tetraoleate, vanadium (III) oleate, calcium (II) oleate, potassium oleate, barium (II) oleate, manganese (II) oleate, nickel (II) oleate, cobalt (II) oleate, zirconium (IV) oleate, iron (II) naphthenate, iron (III) naphthenate, titanium (IV) naphthenate,

Vanadium (III) naphthenate, calcium dinaphthenate, potassium naphthenate, barium dinaphthenate, manganese naphthenate, nickel dinaphthenate, cobalt dinaphthenate, zirconium (IV) naphthenate.

With regard to the catalytic activity, ferrous 2-ethylhexanoate, iron (III) 2-ethylhexanoate, titanium (IV) 2-ethylhexanoate, iron (II) neodecanoate, iron (III) neodecanoate,

Titanium (IV) neodecanoate, iron (II) oleate, iron (III) oleate, titanium (IV) oleate, iron (II) naphthenate, iron (III) naphthenate and titanium (IV) naphthenate, and iron (III) 2- ethyl hexanoate, iron (III) neodecanoate, iron (III) oleate and iron (III) naphthenate.

In view of the non-occurrence of discoloration, preferred are: titanium (IV) 2-ethylhexanoate, calcium (II) 2-ethylhexanoate, potassium 2-ethylhexanoate, barium (II) 2-ethylhexanoate, zirconium (IV) 2-ethylhexanoate, titanium ( IV) neodecanoate, calcium (II) neodecanoate, potassium neodecanoate,

Barium (II) neodecanoate, zirconium (IV) neodecanoate, titanium (IV) oleate, calcium (II) oleate, potassium oleate, barium (II) oleate, zirconium (IV) oleate, titanium (IV) naphthenate, calcium (II) naphthenate, Potassium naphthenate, barium (II) naphthenate and zirconium (IV) naphthenate.

 The calcium carboxylates, vanadium carboxylates, iron carboxylates, titanium carboxylates,

Potassium carboxylates, barium carboxylates, manganese carboxylates, nickel carboxylates,

Cobalt carboxylates and zirconium carboxylates can be used individually or as a mixture of several

Catalysts can be used from one or more of the mentioned groups. In addition, these metal carboxylates can be used in conjunction with tin carboxylates, lead carboxylates, bismuth carboxylates and cercarboxylates.

The catalyst is optionally used in an amount of 0.01 to about 1 wt .-%, based on the total weight of the composition.

It is also possible to use mixtures of several catalysts in order to combine advantageous effects.

Suitable fillers for the composition according to the invention are, for example, chalk, limestone, precipitated and / or fumed silica, zeolites, bentonites, magnesium carbonate, kieselguhr, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder and other ground minerals. Furthermore, organic fillers can be used, in particular carbon black, graphite, wood fibers, wood flour, sawdust, pulp, cotton, pulp, wood chips, chaff, chaff, ground walnut shells and other fiber short cuts. Furthermore, short fibers such as glass fiber, glass filament, polyacrylonitrile, Carbon fiber, Kevlar fiber or polyethylene fibers are added. Aluminum powder is also suitable as a filler.

 In addition, suitable fillers are hollow spheres with a mineral shell or a plastic shell. These may be, for example, glass bubbles, which are among the

Trade names Glass Bubbles® are commercially available. Hollow balls on

Plastic base, e.g. Expancel® or Dualite® are described, for example, in EP 0 520 426 B1. These are composed of inorganic or organic substances, each having a diameter of 1 mm or less, preferably 500 μm or less.

For some applications, fillers are preferred which impart thixotropy to the formulations. Such fillers are also described as rheological aids, eg. B.

hydrogenated castor oil, fatty acid amides or swellable plastics such as PVC. So that they can be pressed out well from a suitable metering device (eg tube), such preparations have a viscosity of 3,000 to 15,000, preferably 4,000 to 8,000 mPas or even 5,000 to 6,000 mPas.

The fillers are preferably used in an amount of 1 to 80 wt .-%, based on the total weight of the composition. A single filler or a combination of multiple fillers may be used.

In a specific embodiment of the composition according to the invention, the filler is a highly disperse silica having a BET surface area of from 10 to 90 m ² / g, in particular from 35 to 65 m ² / g. When used, such a silica does not significantly increase the viscosity of the composition of the present invention, but does contribute to enhancing the cured formulation. About this gain z. B. the

Initial strengths, tensile shear strengths and the adhesion of the adhesive, sealing or

Broom ichtungungsstoffen in which the composition of the invention is used, improved.

Particular preference is given to using a highly disperse silica having a BET surface area of 45 to 55 m ² / g, in particular having a BET surface area of about 50 m ² / g. Such silicas have the additional advantage of being shortened by 30 to 50%

Incorporation time compared to silicic acids with a higher BET surface area. Another advantage is that the mentioned highly dispersed silica in adhesives, sealants or Beschichtungsstoffe based on silane-modified polymers in considerably higher

Concentration without impairing the transparency and the flow properties of the adhesives, sealants or coating materials. Another specific embodiment of the present invention is a composition according to the invention in which the filler is a fumed silica having a mean particle size d _50, measured by laser diffraction, of less than 25 μm, preferably from 5 to 20 μm. Such a filler is particularly well suited when highly transparent, clear compositions are needed for particularly demanding applications.

It is also conceivable to use pyrogenic and / or precipitated silicas having a higher BET surface area, advantageously with 100-250 m ² / g, in particular 1-10-170 m ² / g, as filler. The incorporation of such silicas, however, takes a comparatively long time and is therefore more cost-intensive. In addition, significant amounts of air are introduced into the product, which in turn must be removed cumbersome and tedious. On the other hand, the effect of enhancing the cured composition due to the higher BET surface area can be achieved with a lower silica weight fraction. In this way, further substances can be introduced in order to improve the composition according to the invention with regard to other requirements.

Furthermore, the composition of the invention may contain antioxidants. The proportion of antioxidants in the composition according to the invention is preferably up to about 7% by weight, in particular up to about 5% by weight.

The composition of the invention may further contain UV stabilizers. Preferably, the proportion of UV stabilizers on the inventive

Composition up to about 2 wt .-%, in particular about 1 wt .-%. Particularly suitable as UV stabilizers are the so-called hindered amine light stabilizers (HALS). It is preferred in the context of the present invention, when a UV stabilizer is used, which carries a silyl group and is incorporated in the final product during curing or curing. Particularly suitable for this purpose are the products Lowilite 75, Lowilite 77 (Great Lakes, USA). It is also possible to add benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, sterically hindered phenols, phosphorus and / or sulfur.

It often makes sense to further stabilize the compositions according to the invention against penetrating moisture, in order to increase shelf life even more.

Such an improvement in shelf life can be achieved, for example, by the use of desiccants. As a desiccant are all compounds that are water react to form an inert group to the reactive groups present in the composition, and thereby alter as little as possible their changes

Molecular weight experience. Furthermore, the reactivity of the desiccants to moisture penetrated into the composition must be higher than the reactivity of the end groups of the silyl group-bearing polymer (s) present in the composition.

Suitable drying agents are, for example, isocyanates.

Silanes are also advantageously used as drying agents, for example vinyl silanes such as 3-vinylpropyltriethoxysilane, oxime silanes such as methyl-O, O ^' , O ^" -butan-2-one-trioximosilane or O, O ^' , O ^" , O ^'" -butane-2 tetraoximosilane (CAS Nos. 022984-54-9 and 034206-40-1) or benzamidosilanes such as bis (N-methylbenzamido) methylethoxysilane (CAS No. 16230-35-6) or carbamatosilanes such as carbamatomethyltrimethoxysilane, but also the use of methyl Ethyl- or vinyltrimethoxysilane, tetramethyl- or -ethylethoxysilane is possible, vinyl-trimethoxysilane and tetra-ethoxysilane being particularly preferred in terms of efficiency and cost.

Also suitable as a desiccant are the above-mentioned further reactive diluents, provided that they have a molecular weight (M _n ) of less than about 5,000 g / mol and have end groups whose reactivity to moisture penetration is at least as great, preferably greater, than the reactivity of reactive groups of the

Silyl group-carrying polymer according to the invention.

Finally, it is also possible to use alkyl orthoformates or orthoacetates as desiccants, for example methyl or ethyl orthoformate, methyl or ethyl orthoacetate,

The composition according to the invention optionally contains about 0.01 to about 10% by weight desiccant.

In a further preferred embodiment of the composition according to the invention contains these

 From 3 to 50% by weight of at least one silane-modified polyether A,

 From 5 to 50% by weight of at least one silane-terminated polymer B,

 0 to 65% by weight of a filler,

 0 to 40% by weight of a plasticizer,

 0.1 to 10% by weight of an adhesion promoter,

0.01 to 1% by weight of a curing catalyst, and 0 to 10 wt .-% of other auxiliaries such as pigments, stabilizers, UV absorbers,

Anti-aging agents, antioxidants, rheological aids, thinners or

Contains reactive diluents and fungicides and flame retardants, wherein the proportions of the ingredients add up to 100 wt .-% and each on the total weight of

Composition are related.

Another object of the present invention is a process for preparing a solvent- and water-free curable composition, characterized in that at least one polymer A is prepared by reacting a polyether having at least one ethylenically unsaturated silane, which carries at least one hydrolyzable group on the silicon atom Presence of a radical starter and

the polymer thus obtained is mixed with the further constituent (s) of the composition.

Preference is given to drying the polyether before the reaction at a temperature of at least 60 ^° C., preferably at least 70 ^° C., for at least 40 minutes, and then to a

Temperature of at least 100 ⁰ C, preferably at least 130 ⁰ C, heated.

The addition of the ethylenically unsaturated silane / silanes is preferably carried out at a temperature of at least 50 ° C, more preferably of at least 70 ° C and

in particular of more than 90 ⁰ C.

Another object of the invention is the use of a curable composition of the invention or a composition prepared according to the above

described inventive method as adhesive, sealing or Besen ichtungsstoff. The composition shows a wide adhesion spectrum. Preference is given to the use as an adhesive for bonding plastics, metals, glass, ceramics, wood, wood-based materials, paper, paper materials, rubber and textiles. In such applications, the

Due to their low viscosity, the composition according to the invention processes and applies well and allows good adhesion and strength after curing. In addition, a composition of the invention advantageously has a good elasticity with high tear resistance.

In principle, in the present invention, all features listed in the context of the present text, in particular those described as preferred and / or specifically designated embodiments, share ranges, constituents and other features, the Composition according to the invention, the method according to the invention and the use of the invention in all possible and not mutually exclusive

exclusive combinations.

Examples:

Preparation of Polymer A - General Procedure:

80 g of a polypropylene glycol are dried at 80 ^° C. for one hour and then heated to 150 ^° C. At a temperature of 100 ⁰ C, 20 g of vinyl silane and 0.5 to 2 g

Free radical initiator (eg dicumyl peroxide) added. After the radical start reaction is stirred for 2 hours, the batch is mixed with stabilizers, bottled and airtight

locked.

Preparation of Polymer B1:

282 g (15 mmol) of polypropylene glycol 18000 (OHN = 6.0) were dried in a 500 ml three-necked flask at 100 ° C in vacuo. Under a nitrogen atmosphere, 0.1 g of catalyst was added at 80 ° C., followed by the addition of 7.2 g (32 mmol) of 3-isocyanatopropyltrimethoxysilane (NCO content = 18.4%). After stirring for one hour at 80 ° C, the resulting polymer was cooled and then treated with 6 g of vinyltrimethoxysilane. The product was stored moisture-tight under a nitrogen atmosphere in a glass jar. The viscosity is 28,425 mPas.

Preparation of polymer B2:

280 g (35 mmol) of polypropylene glycol 8000 (OHZ = 13.6) and ethylhexanol 0.6 g (4.5 mmol) are dried in a 500 ml three-necked flask at 80 ^° C. in vacuo. Under

Nitrogen atmosphere is added at 80 ⁰ C 0.07 g of dibutyltin dilaurate. Subsequently, 4.6 g (27 mmol) of TMXDI (tetramethylxylylene diisocyanate) are added and after stirring for one hour, 4.4 g (21 mmol) of isocyanatopropyltrimethoxysilane (% NCO = 19.6) are added and the mixture is stirred at 80 ° C. for a further hour. The resulting prepolymer mixture is cooled and treated with 6.0 g of vinyltrimethoxysilane. The product is stored moisture-tight under a nitrogen atmosphere in a glass jar before it is further processed according to the general procedure into a curable preparation. The viscosity is 208,000 mPas. Preparation of polymer B3:

260 g (65 mmol) of polypropylene glycol 4000 (OHN = 28), are dried in a 500 ml three-necked flask at 80 ⁰ C in vacuo. Under nitrogen atmosphere at 80 ⁰ C 0.07 g

Dibutyltin dilaurate added. Subsequently, 19 g (86.5 mmol) of IPDI are added. After reaching the calculated CO value N 1 1 g (47.5 mmol) was added Dynasilan 1189 and stirred for another hour at 80 ⁰ C. The resulting prepolymer mixture is cooled and treated with 5.0 g of vinyltrimethoxysilane. The product is stored moisture-tight under a nitrogen atmosphere in a glass jar before it is further processed according to the general procedure into a curable preparation. The viscosity is 45,425 mPas.

The preparation of the polymers B was carried out in a speed mixer, z. SpeedMixer DAC 400 FVZ (Hauschild Engineering). In this case, first the liquid components were mixed (without crosslinking catalyst), then the filler was added and then admixed the catalyst.

The results are summarized in Table 1 (data - unless otherwise stated)

reported - in% by weight, based on the total weight of the composition).

Determination of viscosity:

The viscosities were determined using a Brookfield viscometer type RVDVII +, spindle no. 7, 100 rpm at 23 ° C.

Table 1

Table 1 (continued)

The examples show that compositions containing the silane-modified polyether A have significantly reduced viscosities and concomitantly significantly improved processability. Moreover, it is possible to adapt the elastic properties of the composition over a wide range to the respective requirements.

Claims

claims

Solvent-free and water-free curable composition containing at least one polymer A, wherein the polymer A is obtainable by reacting a polyether with at least one ethylenically unsaturated silane in the presence of a radical initiator, wherein the ethylenically unsaturated silane carries at least one hydrolyzable group on the silicon atom.

2. A curable composition according to claim 1, characterized in that the polymer A is obtainable by reacting a polyether with at least one ethylenically unsaturated silane of the general formula (I),

R ¹ R ² C = C (R ³ ) -R ⁴ -SiXYZ (I) in which R ¹ , R ² and R ^{3 are} identical or different and independently of one another represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

R ^{4 is} a chemical bond or a divalent organic group containing 1 to 10 atoms selected from C, O and N, and

X, Y and Z are the same or different, at least two of the substituents X, Y and Z are independently a methoxy, ethoxy, propyloxy or butyloxy group and the remaining substituent is one of the above-mentioned alkyloxy groups, an alkyl group having 1 to 6 carbon atoms , an alkenyl group of 2 to 6

 Carbon atoms or an alkenyloxy group having 2 to 6 carbon atoms.

3. A curable composition according to claim 2, characterized in that in the general formula (I) R ^{4 is} a chemical bond.

4. A curable composition according to any one of claims 1 to 3, characterized

in that the polymer A is obtainable by reacting a polyether with 1 to 50% by weight, based on the weight of the polyether, of ethylenically unsaturated silane.

5. A curable composition according to any one of claims 1 to 4, characterized in that the molecular weight M _{n of} the polyether is 2,000 to 100,000 g / mol.

6. A curable composition according to any one of claims 1 to 5, characterized

 in that the viscosity of each polymer A contained is between 300 and 50,000 mPas (Brookfield, 23 ° C, column 7, 100 rpm).

7. A curable composition according to any one of claims 1 to 6, characterized

in that the maximum polydispersity is M _w / M _{n of} the polyether 3.

8. A curable composition according to any one of claims 1 to 7, characterized

 in that the composition contains one or more polymers (s) B terminated with at least one reactive silyl group, wherein polymer B is not identical to a polymer A.

9. A curable composition according to any one of claims 1 to 8, characterized

 in that a crosslinking catalyst is contained.

10. A curable composition according to any one of claims 1 to 9, characterized

 in that the polymer A contains silyl groups with at least one

 hydrolyzable group on the silicon atom in random distribution.

11. A curable composition according to any one of claims 1 to 10, characterized

 characterized in that the composition

 From 3 to 50% by weight of at least one silane-modified polyether A,

 5 to 50% by weight of at least one polymer B,

 0 to 65% by weight of a filler,

 0 to 40% by weight of a plasticizer,

 0.1 to 10% by weight of an adhesion promoter,

 0.01 to 1 wt .-% of a curing catalyst and

 0 to 10 wt .-% further auxiliaries

 contains, wherein the proportions of the ingredients add up to 100 wt .-%.

12. A process for preparing a solvent- and water-free curable

Composition, characterized in that at least one polymer is produced is carried out by reacting a polyether with at least one ethylenically unsaturated silane, which carries at least one hydrolyzable group on the silicon atom, in the presence of a radical initiator and

 the polymer thus obtained is mixed with the other constituents of the composition.

13. Use of a curable composition according to any one of claims 1 to 11 or a composition prepared by a process according to claim 12 as an adhesive, sealant or coating material.