EP2356180A1

EP2356180A1 - Polymer blends comprising alkoxysilane-terminated polymers

Info

Publication number: EP2356180A1
Application number: EP09771355A
Authority: EP
Inventors: Wolfgang Ziche; Andreas Bauer; Volker Stanjek
Original assignee: Wacker Chemie AG
Current assignee: Wacker Chemie AG
Priority date: 2008-12-11
Filing date: 2009-12-10
Publication date: 2011-08-17
Also published as: KR20110095394A; CN102272233A; DE102008054541A1; JP2012511607A; WO2010066826A1; US20110257324A1

Abstract

The invention relates to a blend (M), comprising A) 100 parts of an alkoxysilylmethyl-terminated polymer (A) with at least one end group of the general formula (1) -L- (CH2) -SiR2 3-x(OR1) x (1), with L being a double-bond linking group selected from -O-, -S-, -(R3)N-, -O-CO-N(R3)-, -N(R3)-CO-O-, -N(R3)-CO-NH-, -NH-CO-N(R3)-, -N (R3) -CO-N (R3), R1 and R2 are independently hydrocarbon radicals with 1-6 carbon atoms or ?-oxaalkyl-alkyl radicals with a total of 2-20 carbon atoms, R3 is hydrogen, an optionally halogen-substituted cyclic, linear or branched C1 to C18-alkyl or alkenyl radical or a C6- to C18-aryl radical, and x is 2 or 3, B) 0.01 to 10 parts of a curing catalyst (K) that accelerates the curing of the blend (M) in the presence of air humidity, C) 0 to 1000 parts of one or more fillers (F), D) 0 to 50 parts of one or more monomeric silanes (S) as water traps and silane cross-linkers, E) 0 to 200 parts of one or more plasticizers (W) and F) 0 to 50 parts of one or more adhesion promoters (H) and F) optionally other additives, wherein the blend (M) comprises less than 2 parts of one or more compounds with a primary amine function and less than 0.2 parts of one or more catalyst that contains tin.

Description

Alkoxysilane-terminated polymer blends containing polymer

This invention relates to blends (M) containing methyl dialkoxysilylmethyl or trialkoxysilylmethyl-terminated polymers prepared from these blends

Formkorper and the use of blends (M) for bonding workpieces.

Polymer systems that have reactive alkoxysilyl groups have long been known. In the presence of atmospheric moisture, these alkoxysilane terminated polymers are already included

Room temperature able to condense with elimination of the alkoxy groups together. Depending on the salary

Alkoxysilane groups and their structure are formed mainly by long-chain polymers (thermoplastics), relatively wide-meshed three-dimensional networks (elastomers) or highly crosslinked systems (thermosets).

According to the countless possibilities for designing such silantermmierten polymer systems can be both the properties of the uncrosslinked polymers or polymer-containing mixtures (viscosity, melting point, Loslichkeiten etc.) and the properties of the finished crosslinked materials (hardness, elasticity, tensile strength, elongation at break, heat resistance etc.) set almost arbitrarily. Consequently, the possibilities of substitution of such silane-degraded polymer systems are correspondingly diverse. Thus, they can be used, for example, for the production of elastomers, sealants, adhesives, elastic adhesive systems, hard and soft foams, a wide variety of coating systems or for impression compounds. These products can be applied in any form, such as brushing, spraying, pouring, pressing, filling, etc. depending on the composition of the formulations. In addition to the curing of the compositions and the mechanical properties of the vulcanizate, good adhesion to a wide variety of substrates and good elastic properties are required above all in applications in the area of adhesives and sealants. As a rule, formulations of silane-crosslinking polymers show very good properties.

The adhesion profile is often improved or optimized by the addition of organofunctional silanes as adhesion promoters. In particular, silanes with primary amino groups such as 3-aminopropyltrimethoxysilane lead here to a significant improvement in the adhesion properties, which is why this silane is almost included in all adhesives and sealants based on silane-terminated polymers. The application of such silanes is state of the art and in various

Monographs or publications described (eg, silane coupling agents and other, VoI 1-3 Editor KL Mittal VSP, Utrecht, 1992; Silane Coupling Agents, EP Plueddemann 2 ^nd Edition, Plenum Press, New York 1991). In addition, there are also special newly developed primer silanes, as described in EP 997469 A or EP 1216263 A, but also a combination of silanes, as shown in EP 1179571 A is often expedient.

In addition to a good adhesion adhesives but above all sealants must also have a very good elasticity. Not only the stretching plays a role, but also the relaxation after stretching or compression. These are usually measured as compression set, creep behavior or as restoring behavior. For example, ISO 11600 requires a provision of over 60% or even 70% for elastic sealants.

The elastic behavior is often due to the formulation, but also by the nature of the silane-crosslinking base polymers certainly. Organic silane-crosslinking polymers, especially those with difunctional end groups on the polymer, often show insufficient repulsion. Here the wording is decisive for the properties. For example, US 6576733 describes a way to improve the recovery by a particular catalyst system, but containing tin. Furthermore, it is known that the use of branched polymers causes an increase in the network density and thus an improvement in the elasticity. The disadvantage here, however, associated with the branching reduction of chain lengths between two network points, which usually leads to a significant deterioration of the mechanical properties, in particular the elongation at break but also the tear strength.

DE102006022834 describes the use of

Aminoalkylalkoxysilanes in combination with epoxy-functional silanes to improve the recovery. Disadvantages here are the increase of the modulus and the deterioration of the adhesion.

A particularly interesting type among the silane-terminated polymers is characterized in that the reactive alkoxysilyl groups are separated from an adjacent heteroatom only by a methylene spacer. These so-called α-alkoylsilylmethyl end groups have a particularly high reactivity to atmospheric moisture. Corresponding polymers are described, for example, in WO 03/014226. For sufficiently fast curing, these polymers require no or only very small amounts of toxicologically critical tin catalysts and, if desired, can achieve significantly higher curing speeds. In this respect, the use of such α-alkoylsilylterminierter prepolymers is usually particularly desirable. However, elastomers which can be prepared from this highly reactive α-silane-crosslinking polymer type have the disadvantage of a much lower recovery, which is inadequate for many applications, in comparison to elastomers from conventional silane-crosslinking polymers which crosslink via γ-alkoxysilylpropyl end groups.

The object of the invention is therefore to provide blends based on α ™ silane-crosslinking polymers which have a high recovery in the cured state after stretching.

The invention relates to mixing (M) containing

A) 100 parts of an alkoxysilylmethyl-terminated polymer (A) having at least one end group of the general formula (1)

-L- (CH ₂ ) -SiR ² 3_ _x (ORi) _x (1),

where L is a divalent linking group selected from -O-, -S-,

- (R ³ ) N, -O-CO-N (R ³ ) -, -N (R ³ ) -CO-O-, -N (R ³ ) -CO-NH-,

-NH-CO-N (R ³ ) -, -N (R ³ ) -CO-N (R ³ ) R 1 and R 4 independently of one another are hydrocarbon radicals having 1-6 carbon atoms or ω-oxaalkyl-alkyl radicals having a total of 2 20 carbon atoms,

R ^ is hydrogen, an optionally halogen-substituted cyclic, linear or branched C] _ to C ^ ß-alkyl or alkenyl radical or a Cg to C] _g ~ aryl radical and x is 2 or 3,

B) 0.01 to 10 parts of a curing catalyst (K) which accelerates the curing of the blend (M) in the presence of atmospheric moisture,

C) 0 to 1000 parts of one or more fillers (F), D) 0 to 50 parts of one or more monomeric silanes (S) as water scavengers and silane crosslinkers,

E) 0 to 200 parts of one or more plasticizers (W) and

F) 0 to 50 parts of one or more adhesion promoters (H) and

F) optionally further additives and additives,

characterized,

the mixture (M) contains less than 2 parts of one or more compounds having a primary amine function and less than 0.2 part of one or more tin-containing catalysts.

In the formula (1), L is preferably -O-CO-N (R ² ) -N (R ² ) -CO-NH-, -NH-CO-N (R ² ) -, and -N (R ² J -CO-N (R ² ) -, more preferably -O-CO-N (R ² ), especially -O-CO-NH.

x is preferably 3.

Examples of R - * -, R ^ and R ^ are alkyl radicals such as the methyl ™, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, isopentyl, neo-pentyl, tert. -Pentyl radical, hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals such as the n-nonyl radical, decyl radicals such as the n-decyl radical, dodecyl radicals such as the n-dodecyl radical; Alkenyl radicals, such as the vinyl and the

allyl; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals; Aryl radicals, such as the phenyl and the naphthyl radical; Alkaryl radicals, such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals; Aralkyl radicals, such as the benzyl radical, the α- and the ß-phenylethyl radical. The radicals RΛ and R ^ are preferably hydrocarbon radicals having 1 to 6 carbon atoms, in particular an alkyl radical having 1 to 4 carbon atoms.

R 2 particularly preferably represents a methyl radical, R 1 particularly preferably represents methyl or ethyl radicals.

The radical R 1 is preferably hydrogen or a hydrocarbon radical having 1 to 6 carbon atoms, more preferably hydrogen, an alkyl radical having 1 to 4 carbon atoms, in particular hydrogen.

Preferably, the blend (M) contains less than 1 part, more preferably less than 0.5 part - especially less than 0.2 part - of one or more compounds having primary amine functionality. Most preferably, the blend (M) is free of any compounds having primary amine functionality.

Preferably, the blend (M) contains less than 0.1 parts, more preferably less than 0.05 parts - especially less than 0.02 parts - of one or more tin catalysts, most preferably the blend (M) is free of any tin-containing catalysts.

The invention is based on the surprising finding that compounds with primary amine function in the provision

Mixtures (M) based on polymers (A) with α-silane functions according to the formula (1) significantly deteriorate. This finding was particularly surprising in that a comparable deterioration of the provision only in blends (M) based on the α-silaπterminierten polymers (A) but not in the well-known and long-known systems based on conventional γ- alkoxysilyproypl-terminated Shows prepolymers. That is obviously quite a new and up to date unknown mechanism of action, which is why primary amines show such an effect in the inventive system.

At the same time, the use according to the invention of only small amounts of primary amines or the complete omission of use of this product group is also not an obvious solution because such compounds - in particular aminosilanes such as aminopropyltrimethoxysilane, N- (2-aminoethyl) -aminoproypl-trimethoxysilane or N- (2-aminoethyl) -aminoproypl- methyldimethoxysilane - typically used in significantly higher amounts in each adhesive and sealant based on silane-terminated polymers as adhesion promoters, water scavengers and / or (co) catalysts.

The blends (M) according to the invention are preferably characterized in that molded articles (F) which consist of the cured blend (M) after a 24-hour elongation of 30% exhibit a repulsion to DIN 53504 of more than 60%, preferably more than 65%, and more preferably more than 70%.

The main chains of the alkoxysilane-terminated polymers (A) that can be used may be branched or unbranched. The middle chain lengths can be arbitrarily adjusted according to the respective desired properties of both the uncrosslinked mixture and the cured mass. They can be composed of different building blocks, usually these are polysiloxanes, polysiloxane-urea / urethane copolymers, polyurethanes, polyureas, polyethers, polyesters, polyacrylates and methacrylates, polycarbonates, polystyrenes, polyamides, polyvinyl esters or polyolefins such as polyethylene, polybutadiene, ethylene Olefin copolymers or styrene-butadiene copolymers. Of course, any mixtures or combinations of polymers with different main chains can be used. For the preparation of polymers (A) with silane derivatives of the general formula (1), a large number of possibilities are known. Especially:

* Copolymerizations involving unsaturated monomers having groups of the general formula (1). Examples of such monomers were (meth) acryloyloxymethyltrimethoxysilane, (meth) acryloyloxymethylmethyldimethoxysilane and the corresponding ethoxysxlyl compounds.

• Grafting of unsaturated monomers having groups of the general formula (1) on thermoplastics such as polyethylene. Examples of such monomers were in turn (meth) acryloyloxymethyl-tπmethoxysilane, (meth) acrylic oyloxymethyl-methyldimethoxysilane and the corresponding Ethoxysilylverbmdungen.

Reaction of prepolymers (Al) which have suitable functional groups with one or more organosilanes (A2) of the general formula (2)

B- (CH ₂ ) -SiR ² ₃ _ _x (OR ¹ J _x (2)

in the x, R - "- and R ^, which have the meanings given above, and

B represents a functional group which is reactive with the functional groups of the prepolymers

(Al).

If the prepolymer (Al) itself consists of several building blocks (All, A12 ...), it is not absolutely necessary that these building blocks (All, A12 ...} first, the prepolymer (Al) is prepared _r which is then reacted with the Silaπ (A2) to the finished polymer (A). Thus, a reversal of the reaction steps is also possible here, in which one or more building blocks (All, A12...) Are first reacted with the silane (A2), and the compounds thus obtained are only subsequently reacted with the remaining building blocks (All, A12. ..) are converted to the finished polymer (A).

Examples of prepolymers (Al) consisting of building blocks All, and A12 are OH, NR ™ or NCO-terminated polyurethanes and polyureas, which can be prepared from polyisocyanates (building block All) and polyols (building block A12).

In a preferred preparation of the prepolymers (A) a silane (A2) is used, which is selected from silanes of the general formulas (3)

OCN- (CH ² ) -SiR ² 3 - _x (OR ¹ ) _x (3)

where all variables have the meanings given above.

In the preparation of the prepolymers (A), the concentrations of all participating in samtliche reaction steps isocyanate groups and all isocyanate-reactive groups and the reaction conditions are preferably selected so that react in the course of the polymer synthesis all isocyanate groups. The finished polymer (A) is thus preferably isocyanate-free.

Examples of prepolymers (Al) are polyesters, polycarbonates, polyester carbonates (eg those commercially available under the name "Desmophen 1700" and "Desmophen C-200" from Bayer AG, Germany), polybutenylenes and polybutadienylenes (eg Such kauflich obtainable under the name "Poly bd ^® R-45 HTLO" by the company. Sartonaer Co., Inc., USA or "Kraton ™ Liquid L-2203" by the company. Kraton Polymers US LL C).

Preferred examples of prepolymers (Al) for preparing prepolymers (A) are polyesters, polyethers and polyurethanes. Particularly preferred examples of prepolymers (Al) are divalent polyethers of the general formula (4)

HO- (R ⁴ O) _1n -H (4),

in which

R ^ may be identical or different and optionally substituted hydrocarbon radicals, preferably methylene, ethylene and 1, 2-propylene radicals, and πt is an integer from 1 to 600, preferably 50 to

400, is.

Examples of prepolymers (Al) of the general formula (4) are commercially available under the name "Acclaim 12200", "Acclaim 18000" (both Bayer AG, Germany), "Alcupol 12041LM" from Repsol, Spain and "Poly L 220-10 from Arch Chemicals, USA),

In the polymer blends (M) according to the invention, the proportion of alkoxysilane-terminated polymers (A) is preferably 10-70% by weight, more preferably 15-50% by weight, in particular 20-40% by weight.

The innovative blends (M) contain besides the

Prepolymer (A) preferably one or more secondary or tertiary amines (B) as a curing catalyst (K). Examples are secondary or tertiary ammoalkoxysilanes such as 3- (N-cyclohexylamino) -propyltrimethoxysilane, 3- (N-cyclo ™ hexylamino) -propyltriethoxysilane, 3- (N-phenylamino) -propyl- trimethoxysilane, 3- (N-phenylammo) -propyltnethoxysilane, trimethylammonium, tributylamm, 1, 4-diazabicyclo [2,2,2] octane, N, N-bis (3tf, N-dimethyl-2-ammoethyl) -methylamine, N, N ~ dimethylcyclohexylamine, N, N-dimethylphenylamm, N-ethylmorpholmin.

Particularly preferably, the inventive mixtures (M) in addition to the prepolymers (A) one or more secondary or tertiary Ammoalkyl alkoxysilanes (KS) as a curing catalyst (K).

Preferred ammoalkylalkoxysilanes (KS) are those of the general formula (5)

(R ⁵ R ⁶ N- (CR ⁷ 2) -Si (R ² ) 3- _J ¹ (OR ¹ ) _x (5)

in the

R 1, R 'is hydrogen or an alkyl, cycloalkyl, alkenyl or aryl radical having 1-10 carbon atoms which may optionally be substituted by halogen atoms and / or organic functions,

R *> is an alkyl, cycloalkyl, alkenyl or aryl radical having 1-10 carbon atoms, which may optionally be substituted by halogen atoms and / or organic functions _{r is} a bivalent alkyl, cycloalkyl, alkenyl or aryl radical having 1-10 carbon atoms , which may optionally be substituted by halogen atoms, and all other variables have the meanings given above.

wherein the Ammoalkyl-alkoxysilane (KS) has no primary Ammofunktion. R ~> is preferably a hydrogen atom or an alkyl, cycloalkyl or aryl group having 1-10 carbon atoms, more preferably a hydrogen atom or a

Alkyl group with 1-8 carbon atoms. R *> preferably represents an alkyl, cycloalkyl or aryl radical having 1-10

Carbon atoms, with phenyl radicals, cyclohexyl radicals or alkyl radicals having 1-8 carbon atoms are particularly preferred. κ7 is preferably hydrogen.

Particular preference is given to ominoalkyl-alkoxysilanes (KS) of the general formula (5) in which

R ^{3 is} methyl,

R ^, R6 is hydrogen, R *> cyclohexyl or phenyl.

In the novel polymer blends (M), the proportion of aminoalkylalkoxysilane (KS) is preferably 0.1-10% by weight, more preferably 0.1-5% by weight, in particular 0.2-3% by weight. based on the total weight of the mixture.

The novel polymer blends (M) may comprise further condensation catalysts (K), for example titanate esters, such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetraacetylacetonate titanate or even acid catalysts, such as phosphoric acid or phosphoric acid esters, toluenesulfonic acids, mineral acids. The various catalysts can be used both in pure form and as mixtures.

These further condensation catalysts are preferably used in concentrations of 0.01-10% by weight, more preferably 0.1-2 % By weight, based on the total weight of the blend, of the polymer blends (M).

In addition, the blends (M) according to the invention may also contain tin compounds, such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetylacetonate, dibutyltin oxide or corresponding dioctyltin compounds within the above-indicated concentration limits as curing catalysts (K). However, the blends (M) according to the invention are preferably tin-free.

Furthermore, the blends (M) according to the invention may also contain primary amines, in particular primary osilminosilanes such as 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane, within the above-indicated concentration limits as curing catalysts (K). Preferably, however, the blends (M) according to the invention are free of primary amines.

The polymer blends according to the invention preferably further comprise fillers (F), for example calcium carbonates in the form of natural ground chalks, ground and coated crayons, precipitated crayons, precipitated and coated crayons, clay minerals, bentonites, kaolins, talc, titanium dioxides, aluminum oxides, aluminum trihydrate,

Magnesium oxide, magnesium hydroxide, carbon blacks, precipitated or pyrogenic, hydrophilic or hydrophobic silicas.

Preference is given to using calcium carbonates and precipitated or pyrogenic, hydrophilic or hydrophobic silicic acids, more preferably pyrogenic, hydrophilic or hydrophobic silicic acids, in particular pyrogenic, hydrophilic silicic acids. The fillers (F) are preferably added to the polymer blends (M) in concentrations of 10-70% by weight, more preferably 30-60% by weight, based on the total weight of the blend.

The novel polymer blends (M) may contain, in addition to the optionally used as catalyst (K) silanes (including the silanes (KS) according to the formula (5)) also further silanes (S) with or without additional organofunction. These are preferably water scavengers and / or silane crosslinkers, for example alkylsilanes such as methyltrimethoxysilane, vinylsilanes such as vinyltrimethoxy, vinyltriethoxy, Vxnylmethyldimethoxysilan or organofunctional silanes such as O-Methylcarbamatomethyl methyldiraethoxysilane, O-Methylcarbamatomethyl-trimethoxysilane, 0 ™ Ethylcarbarnatomethyl ~ methyldiethoxysilane, O-ethylcarbamato Methyl-triethoxysilane, glycidoxypropyltrimethoxysilane, etc. All the silanes mentioned as catalysts (K) can also serve as water scavengers and / or crosslinkers.

The water scavengers and / or Silanvernetzer serving silanes (S) are preferably in concentrations of 0.1 to 10 wt .-%, particularly preferably 0.5 to 2 wt .-%, based on the total weight of the mixture, the Polymerabmischungen (M) added.

All silanes (S) as well as the silanes used as catalyst (K) (including the silanes (KS) according to the formula (5)) can simultaneously serve as adhesion promoters (H). In addition, the blends (M) according to the invention may of course also contain further adhesion promoters (H).

The novel polymer blends may contain plasticizers (W), for example phthalate esters, such as Dioctyl phthalate, Dusooctylphthalat, Diundecylphthalat, Adipmsaureester, such as Dioctyladipat, benzoic acid esters, glycol esters, phosphoric acid esters, sulfonic acid esters, polyesters, polyethers, polystyrenes, polybutadienes, polyisobutenes, paraffinic hydrocarbons, higher, branched hydrocarbons, etc.

The plasticizers (W) are preferably added to the polymer blends (M) in concentrations of up to 40% by weight, based on the total weight of the blend.

The polymer mixtures (M) according to the invention may also contain thixotropic agents, for example hydrophilic pyrogenic silicic acids, coated fumed silicas, precipitated silicas, polyamide monoxide, hydrogenated ricinols, stearate salts or precipitated chalks. Also, the above fillers can be used to adjust the flow properties.

The thixotropic agents are preferably added in concentrations of 1-5 wt .-%, based on the total weight of the blend, the polymer blends (M).

The inventive polymer blends can furthermore light stabilizers _r such as so-called HALS stabilizers,

Fungicides, flame retardants, pigments, etc., as they are known for use m conventional alkoxy-crosslinking emkomponentigen compositions.

To produce the respective desired property profiles of both the uncrosslinked polymer blends and the cured masses, the above additives are preferably used. Preferably, in the preparation of the polymer blends (M) according to the invention, a mixture of polymer (A) and filler is first prepared, and then aminoalkylalkoxysilane (BS) is added.

Shaped bodies (F), e.g. Adhesive joints which can be produced by curing the mixtures (M) according to the invention are likewise provided by the invention. The moldings (F) preferably have a 30% elongation after a 24-hour stretch

Restocking according to DIN 53504 of more than 60%, preferably more than 65% and particularly preferably more than 70%.

There are countless different applications in the field of adhesives, sealants and joint sealants, surface coatings as well as in the production of impression compounds and moldings for the novel polymer blends.

The novel polymer blends are available for countless different backgrounds such as e.g. mineral substrates, metals, plastics, glass, ceramics, painted surfaces, etc. suitable.

All the above symbols of the above formulas each have their meanings independently of each other. In all formulas, the silicon atom is tetravalent.

In the following examples, unless otherwise stated, all amounts and percentages are by weight. Examples

Examples 1

Formulations with a silane-terminated polyether with methylene-trimethoxysilyl end groups (alpha-trimethoxy)

35 g of a silane-terminated polyether obtainable according to EP 1,534,940 B from Acclaim Polyol 12200S (Bayer Material Science AG) and isocyanatomethyltrimethoxysilane be in a Speedmixer Fa. Hauschild (D-59065 Hamm) at about 25 ⁰ C with 25 g PPG 2000 { Fa. Dow Chemical) and 3 g of methylcarbamatotrimethoxysilane, available under the name GENIOSIL® XL63 (Wacker Chemie AG), mixed for 2 minutes at 200 rpm. Thereafter, 1.50 g of a hydrophilic, fumed silica HDK® N20 (170-230 m ² / g) (Wacker Chemie AG) is stirred until it is homogeneously distributed. Subsequently, 60.4 g of chalk Carbital HOS (Imerys) are introduced and the filler digested with stirring for one minute at 600 U / min. After incorporation of the chalk, 0.1 g of cyclohexylaminomethyltriethoxysilane {GENIOSIL® XL926 - Wacker Chemie AG) is distributed for 1 minute at 200 rpm. Homogenized for 2 minutes at 600 rpm and 1 minute at 200 rpm in a partial vacuum (about 100 mbar) and stirred bubble-free. The formulation is filled in 310 ml PE cartridges and stored for one day at 25 ⁰ C.

Comparative Example Ib is prepared analogously, but aminopropyltrimethoxysilane (GENIOSIL® GF96 - Wacker Chemie AG) is used instead of cyclohexylaminomethyltriethoxysilane.

Examples 2

Formulations with a silane-terminated polyether with methylene-triethoxysilyl end groups (alpha-triethoxy)

35 g of a silane-terminated polyether obtainable from EP 1.534.940 B from Acclaim Polyol 18200S (Bayer Material Science AG) and isocyanatomethyltriethoxysilane are mixed in a Speedmixer from Hauschild (D-59065 Hamm) at 25 ° C. with 25 g of PPG 2000 ( Dow Chemical) and 3 g of methylcarbamatotrimethoxysilane, available under the name GENIOSIL® XL63 (Wacker Chemie AG), mixed for 2 minutes at 200 rpm. Thereafter, 1.50 g of a hydrophilic. Fumed silica HDK® N20 (170-230 m ² / g) (Wacker Chemie AG) is stirred until it is homogeneously distributed. Subsequently 60.4 g of chalk Carbital HOS (Imerys) are introduced and the filler digested with stirring for one minute at 600 U / min. After incorporation of the chalk, 0.1 g of cyclohexylaminomethyltriethoxysilane (GENIOSIL® XL926 - Wacker Chemie AG) is distributed for 1 minute at 200 rpm. Homogenized for 2 minutes at 600 rpm and 1 minute at 200 rpm in a partial vacuum (about 100 mbar) and stirred bubble-free.

The formulation is filled in 310 ml PE cartridges and stored for one day at 25 ⁰ C.

Example 2b is prepared analogously, but the hydrophilic, fumed silica HDK® H15 (170-230 m ² / g, Wacker Chemie AG) is used instead of the HDK® N20.

Examples 3

Formulations with a silantenαinierten polyether with methylene-Dimethoxysilylendgruppen (alpha-dimethoxy) 35 g of a silantermlnierten polyether, available after EP 1.534.940 B from Acclaim Polyol 12200S {Bayer Material Science) and isocyanatomethyldimethoxysilane in a Speedmixer Fa. Hauschild (D-59065 Hamm) at 25 ^° C. with 25 g of PPG 2000 (from Dow Chemical) and 3 g of methylcarbamatotrimethoxysilane, available under the name GENIOSIL® XL63 (Wacker Chemie AG), for 2 minutes at 200 rpm. Thereafter, 1.50 g of a hydrophilic, fumed silica HDK® N20 (170-230 m ² / g) (Wacker Chemie AG) is stirred until it is homogeneously distributed. Subsequently, 60.4 g of chalk Carbital HOS (Imerys) are introduced and the filler digested with stirring for one minute at 600 U / min. After incorporation of the chalk, 0.1 g of cyclohexylaminomethyltriethoxysilane (GENIOSIL® XL926 - Wacker Chemie AG) is distributed for 1 minute at 200 rpm. Homogenized for 2 minutes at 600 U / min and 1 minute at 200 U / min in a partial vacuum (about 100 mbar) and stirred bubble-free.

Comparative Example 3b is prepared analogously, but aminopropyltrimethoxysilane (GENIOSIL © GF96 - Wacker Chemie AG) is used instead of cyclohexylaminomethyl-triethoxysilane.

Determination of mechanical properties

The samples were spread on gilled Teflon plates with 2 mm depth and 2 weeks at 23 ⁰ C, 50% rel. Humidity healed. The mechanical properties were according to DIN 53504

(Tensile test) and DIN 53505 (Hard Shore A) determined. The

Measurement of the recovery took place after 2 weeks and 4 weeks

Pre-storage of S2 ~ Prufkorper (DIN 53504) at 23 ⁰ C, 50 rel.

Humidity. The specimens were stretched by 30% for 24 hours. The determination of the recovery took place after 1 h relaxation

23 ^° C, 50% rel. Humidity.

Claims

claims

1. Blend (M) comprising A) 100 parts of an alkoxysilylmethyl-terminated polymer (A) having at least one end group of the general formula (1)

-L- (CH ₂ ) SiSiR ² ₃ _ _x (ORI) _x (1),

in which

L is a divalent linking group selected from -O-, -S-,

- (R ³ ) N, -O-CO-N (R ³ ) -, -N (R ³ ) -CO-O-, -N (R ³ ) -CO-NH-,

-NH-CO-N (R ³⁾ -, -N (R ³⁾ -CO-N (R ³⁾

R! and R 2 independently of one another are hydrocarbon radicals having 1-6 carbon atoms or ω-oxaalkyl-alkyl radicals having a total of 2-20 carbon atoms, R 3 is hydrogen, an optionally halogen-substituted cyclic, linear or branched C 1 - to C] -alkyl or alkenyl radical or a Cg - to C] _ß-aryl radical and x is 2 or 3,

B) 0.01 to 10 parts of a curing catalyst (K) which accelerates the curing of the mixture (M) in the presence of atmospheric moisture,

C) 0 to 1000 parts of one or more fillers (F),

D) 0 to 50 parts of one or more monomeric silanes (S) as water catchers and silane crosslinkers,

E) 0 to 200 parts exnes or more plasticizers (W) and

F) 0 to 50 parts of one or more adhesion promoters (H) and

F) optionally further additives and additives, characterized,

in that the blend (M) contains less than 2 parts of one or more compounds having a primary amine function and less than 0.2 part of one or more tin-containing catalysts.

2. blend (M) according to claim 1, characterized in that in the trialkox.ysilylmethylterminierten polymer (A) having at least one end group of the general formula (1) -L is a -O-CO-N (H) group.

3. blend (M) according to claim 1 or 2, characterized in that one or more secondary or tertiary amines (B) are included as a curing catalyst

4. blend (M) according to claim 3, characterized in that as the one or more secondary or tertiary amines (B), sxnd contain one or more secondary or tertiary aminoalkyl alkoxysilanes (BS) as a curing catalyst.

5. blend (M) according to claim 4, characterized in that the aminoalkyl-alkoxysilanes (BS) are those of the general formula (4)

(R ⁴ R ⁵ N- (CR ⁶ ₂ ) -Si (R ³ ) 3-χ (OR ¹ ) _χ 4),

in the

R 1 is an alkyl, alkenyl or aryl radical having 1-10 carbon atoms,

R ⁴ , R ^{6 is} hydrogen or an alkyl, cycloalkyl, alkenyl or aryl radical having 1-10 carbon atoms, the optionally substituted with halogen atoms and / or organic functions,

R.5 is an alkyl, cycloalkyl, alkenyl or aryl radical having 1-10

Carbon atoms which may optionally be substituted by halogen atoms and / or organic functions, a bivalent alkyl, cycloalkyl, alkenyl or aryl radical having 1-10 Kohlenstoffatoraen, which may optionally be substituted by halogen atoms, and x is a number from 1 to 3 represents,

wherein the aminoalkyl-alkoxysilane {BS} has no primary

Amino function features.

6. blend (M) according to claim 5, characterized in that in the aminoalkyl-alkoxysilanes (BS) of the general formula (4)

R ^{3 is} methyl,

R ⁴ _f R ^{6 is} hydrogen,

R5 is cyclohexyl or phenyl and x is 2 or 3.

7. Formkorper, characterized in that it contains a blend according to one or more of claims 1 to 6.

8. Shaped body according to claim 7, characterized in that they have a provision according to DIN 53504 of more than 70% after a 24-hour elongation of 30%.