阅读说明：本技术 具有高强度的双组分组合物 (Two-component composition having high strength ) 是由 K·曼耐克 F·肖非特 U·斯塔德尔曼 于 2020-05-28 设计创作，主要内容包括：本发明涉及包含如下的组合物：-至少一种含硅烷基团的聚合物,所述聚合物的硅含量在0.6至2重量％的范围内并且通过至少一种含异氰酸酯基团的聚合物和至少一种氨基硅烷、巯基硅烷或羟基硅烷的反应获得,-至少一种液体环氧树脂,和-至少一种具有至少三个对环氧基团有反应性的胺氢的多胺。所述组合物实现的粘合剂、涂料或浇注料具有良好的储存稳定性,即使在湿或潮的条件下都能迅速固化,具有出人意料的高强度和高可拉伸性、高抗撕裂蔓延性、高耐受性(特别是相对于醇/水混合物)和在许多基材上的高粘合力,其中在用在诸如钢或铝的金属上时所述组合物保护金属免受腐蚀。(The present invention relates to a composition comprising: -at least one polymer containing silane groups, the silicon content of the polymer being in the range of 0.6 to 2 wt.% and being obtained by reaction of at least one isocyanate group-containing polymer and at least one aminosilane, mercaptosilane or hydroxysilane, -at least one liquid epoxy resin, and-at least one polyamine having at least three amine hydrogens reactive towards epoxide groups. The compositions achieve adhesives, coatings or casting materials with good storage stability, cure rapidly even under wet or damp conditions, have unexpectedly high strength and drawability, high tear propagation resistance, high resistance (especially with respect to alcohol/water mixtures), and high adhesion on many substrates, where the compositions protect metals from corrosion when used on metals such as steel or aluminum.)

1. A composition comprising

At least one polymer containing silane groups, the silicon content of which is in the range from 0.6 to 2% by weight and which is obtained by reaction of at least one isocyanate group-containing polymer and at least one aminosilane, mercaptosilane or hydroxysilane,

at least one liquid epoxy resin, and

-at least one polyamine having at least three amine hydrogens reactive with epoxide groups.

2. Composition according to claim 1, characterized in that the silicon content of the polymer comprising silane groups is in the range of 0.7 to 1.5% by weight, in particular 0.8% to 1.2% by weight.

3. Composition according to any one of claims 1 or 2, characterized in that the silane group containing polymer has silane groups of formula (I)

Wherein

n represents 1 or 2 or 3, in particular 2 or 3,

R¹represents a linear or branched monovalent hydrocarbon group having 1 to 5 carbon atoms,

R²denotes a linear or branched divalent hydrocarbon radical having from 1 to 12 carbon atoms, optionally having cyclic and/or aromatic moieties and optionally having one or more heteroatoms, in particular amide, carbamate groupsOr a morpholinyl group, or a salt thereof,

x represents O or S or NR³Wherein R is³Represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 20 carbon atoms, optionally having a cyclic portion, and optionally having an alkoxysilyl group or an ether group or a carboxylate group.

4. Composition according to any one of claims 1 to 3, characterized in that the NCO content of the isocyanate group-containing polymer is in the range from 1.2 to 4% by weight, in particular from 1.2 to 2.8% by weight.

5. Composition according to any one of claims 1 to 4, characterized in that the polymer containing isocyanate groups is obtained from the reaction of at least one polyoxypropylene diol having an OH value in the range from 18 to 58mg KOH/g, in particular from 22 to 40mg KOH/g, optionally having oxyethylene groups at the end, and at least one diisocyanate.

6. Composition according to any one of claims 1 to 5, characterized in that the isocyanate group-containing polymer has aromatic isocyanate groups.

7. Composition according to any one of claims 1 to 6, characterized in that the aminosilane, mercaptosilane or hydroxysilane is an aminosilane, in particular diethyl N- (3-trimethoxysilylpropyl) aminosuccinate, diethyl N- (3-dimethoxymethylsilylpropyl) aminosuccinate or diethyl N- (3-triethoxysilylpropyl) aminosuccinate.

8. Composition according to any one of claims 1 to 7, characterized in that the polyamine is chosen from 1, 5-diamino-2-methylpentane, 2,2(4), 4-trimethylhexamethylenediamine, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminocyclohexane, 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3, 5, 5-trimethylcyclohexylcyclohexaneAlkanes, 2(4) -methyl-1, 3-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,5(2,6) -bis (aminomethyl) bicyclo [2.2.1]Heptane, 1, 3-bis (aminomethyl) benzene, average molecular weight M_nPolyoxypropylene diamines and polyoxypropylenetriamines in the range from 200 to 500g/mol, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, N, N' -bis (3-aminopropyl) ethylenediamine, N, N-dimethylbis (1, 3-propylene) triamine, N-benzyl-1, 2-ethylenediamine, N-benzyl-1, 2-propylenediamine, N-benzyl-1, 3-bis (aminomethyl) benzene, N- (2-phenylethyl) -1, 3-bis (aminomethyl) benzene and 1, 5-diamino-2-methylpentane or adducts of 1, 2-propylenediamine with tolylglycidyl ether.

9. Composition according to any one of claims 1 to 8, characterized in that it comprises a first component and a second component which are prepared, packaged and stored separately, wherein the polyamine and the liquid epoxy resin are not present in the same component.

10. Composition according to any one of claims 1 to 9, characterized in that it further comprises at least one further ingredient chosen from aminosilanes, desiccants, accelerators, water, fillers and plasticizers.

11. Use of a composition according to any one of claims 1 to 10 as an adhesive, sealant, coating or castable, in particular on at least one metal, preferably aluminium.

12. Use according to claim 11, wherein the composition is used for bonding battery cases.

13. Bonding method, characterized in that the mixed composition according to any one of claims 1 to 10 is applied to at least one substrate to be bonded over a pot life and the substrates are adhesively bonded in open time, and then the mixed composition is cured.

14. Method for coating a substrate or for filling cavities, in particular cracks or gaps, characterized in that a mixed composition according to any of claims 1 to 10 is applied to a substrate or filled into a cavity within the pot life and cured in situ.

15. An article obtained by the use according to any one of claims 11 or 12 or the method according to claim 13 or 14.

Technical Field

The invention relates to compositions curable at room temperature, based on a combination of polymers containing silane groups and epoxy resins, and to the use thereof, in particular as viscoelastic adhesives, coatings or casting compounds having high strength, stretchability and resistance.

Background

Adhesives, casting materials and coatings based on polyurethane or epoxy resins are known and used in various ways. Polyurethane-based materials have high stretchability, but the achievable strength is limited. Furthermore, they are sensitive when used in wet or humid environments and have insufficient resistance to alcohol/water mixtures, such as those used as cooling fluids for electric vehicle batteries, and insufficient adhesion to metals under corrosive conditions. Epoxy-based materials can achieve extremely high strength, adhesion and resistance, but have limited stretchability and insufficient adhesion to aluminum under corrosive conditions (e.g., saline loading).

Materials combining silane functional polymers with epoxy resins are also known. Significantly higher strengths are thereby achieved compared to the silane-functional polymer alone. Such compositions based on so-called MS polymers are known, for example those commercially available from the company Kaneka. It is a silane functional polymer obtained by hydrosilylation of a polyol having allyl ether end groups. Such compositions are described, for example, in EP 370'464 or US 6'737' 482. However, only very limited strength can be achieved by the combination of MS polymer and epoxy resin.

Also known are compositions comprising an epoxy resin and a silane-functional polyA composition of compounds derived from the reaction of a polyol with an isocyanatosilane or from the reaction of a polyol with a diisocyanate to form an isocyanate functional polymer which is subsequently further reacted with an aminosilane to form a silane functional polymer. Such systems are described, for example, in US 2017/0292050 or WO 2017/140688. The highest strengths are achieved here by silane-functional polymers derived from polymers containing isocyanate groups and aminosilanes. The polymers containing silane groups used herein are derived from the average molecular weight M_nA long-chain polyether diol of about 12000g/mol and therefore having a low content of silane groups.

However, significantly higher strength is desirable for certain applications, while having high adhesion, high tear propagation resistance and high resistance, such as for battery case adhesion in electric vehicles. In this case, a high resistance to adhesion under corrosive conditions (for example, in particular, salt water loading) on aluminum substrates is required, as well as a high resistance to alcohol/water mixtures, which is difficult to achieve with adhesives based on acrylates, polyurethanes and/or epoxy resins.

Summary of The Invention

It is therefore an object of the present invention to provide a composition which cures rapidly and reliably at room temperature (even under wet or humid conditions), which composition is capable of achieving high strength, high stretchability, high adhesion, good resistance (in particular to alcohol/water mixtures), and corrosion-resistant adhesion on metals. Surprisingly, the object is achieved by a composition according to claim 1. The composition comprises at least one polymer containing silane groups, the silicon content of the polymer being in the range of 0.6 to 2% by weight and being obtained by reaction of at least one isocyanate group-containing polymer and at least one aminosilane, mercaptosilane or hydroxysilane. Such polymers have not been implemented in the prior art in combination with epoxy resins. The compositions according to the invention surprisingly show a much higher strength and also a high drawability, a very high resistance to tear propagation and an excellent adhesion (especially on metals under corrosive conditions), as well as an excellent resistance to hydrolysis and alcohol/water mixtures, compared to corresponding compositions known in the prior art comprising silane group containing polymers with a lower silicon content.

The binder, coating or castable materials achieved with the composition according to the invention have good storage stability as two-component products, they cure rapidly and substantially without bubbles after mixing (even in the presence of water or moisture), and the materials formed have surprisingly high strength and high drawability, high tear propagation resistance and high resistance (especially to alcohol/water mixtures), have extremely high adhesion on many substrates, even wet or moist substrates, where the composition can protect metals such as steel or aluminium from corrosion when used on these metals. In particular, the composition enables a viscoelastic adhesive with which metals (in particular aluminum) can be bonded without pretreatment, making the bonding durable under corrosive conditions (for example in particular saline loading). Furthermore, the composition enables a coating by means of which metals such as steel or aluminium can be protected against corrosion. Finally, the composition makes it possible to produce casting materials by means of which cracks in concrete, asphalt or bitumen can be permanently filled and repaired, wherein excellent adhesion can occur even on wet substrates. Thus, it is possible to permanently repair in a simple manner those heavily loaded roads or squares which have damage at the surface or kerb, edge or border. Finally, these products are free of isocyanates during processing, which is advantageous for toxicological reasons.

Other aspects of the invention are the subject of other independent claims. Particularly preferred embodiments of the invention are the subject matter of the dependent claims.

Detailed Description

The subject of the invention is a composition comprising

At least one polymer containing silane groups, the silicon content of which is in the range from 0.6 to 2% by weight and which is obtained by reaction of at least one isocyanate group-containing polymer and at least one aminosilane, mercaptosilane or hydroxysilane,

at least one liquid epoxy resin, and

-at least one polyamine having at least three amine hydrogens reactive with epoxide groups.

In the present context, the term "alkoxysilane group" or simply "silane group" denotes a silyl group which is linked to an organic group and has 1 to 3, in particular 2 or 3, hydrolyzable alkoxy groups on the silicon atom.

Accordingly, the term "alkoxysilane" or simply "silane" refers to an organic compound having at least one silane group.

"aminosilane", "mercaptosilane" or "hydroxysilane" means an organosilane having an amino, mercapto or hydroxyl group on the organic group in addition to the silane group.

The "silicon content" of the polymer comprising silane groups means the silicon content of the polymer in% by weight, based on 100% by weight of the polymer. The dilution of the polymer with a solvent or plasticizer is not considered to be a component of the polymer. Also not included in the silicon content of the silane group containing polymer is a silane functional additive (e.g., a tackifying organosilane) which may optionally be additionally included in the composition. Within the scope of the present invention, these materials are not considered to be silane group-containing polymers.

The "NCO content" of a polymer means the isocyanate group content of the polymer in weight%.

An "aromatic" isocyanate group refers to an isocyanate group that is directly bonded to an aromatic carbon atom.

The names of substances, such as polyamines or polyols, headed "poly" denote substances that formally contain two or more functional groups present in their name per molecule.

"amine hydrogen" means the hydrogen atoms of primary and secondary amino groups.

"primary amino" means an amino group bound to only one organic group and bearing two hydrogen atoms; "secondary amino" means an amino group bound to two organic groups (which may also be part of a ring together) and carrying one hydrogen atom; and "tertiary amino" denotes an amino group bound to three organic groups (two or three of which may also be part of one or more rings) and which does not carry a hydrogen atom.

"molecular weight" means the molar mass (in grams/mole) of a molecule or group of molecules. "average molecular weight" means the number average molecular weight (M) of a polydispersed mixture of oligomeric or polymeric molecules or molecular groups_n). It is determined by Gel Permeation Chromatography (GPC) against polystyrene standards, using in particular tetrahydrofuran as mobile phase and refractive index detector.

By "storage stable" or "storable" is meant that a substance or composition can be stored in a suitable container at room temperature for an extended period of time, typically at least 3 months to 6 months and longer, without its application or use properties changing during storage to the extent associated with its use.

"Room temperature" means a temperature of 23 ℃.

All industry standards or specifications mentioned herein relate to valid versions at the time of first filing of the application.

Weight percent (wt.%), unless otherwise specified, refers to the mass content of a polymer or ingredient in a composition, based on the entire polymer or the entire composition. The terms "mass" and "weight" are used synonymously herein.

The dotted lines in the formulae herein each represent a bond between a substituent and the corresponding molecular group.

The polymer comprising silane groups is preferably a liquid at room temperature.

Preferably, the polymers containing silane groups have an average of 1.3 to 4, particularly preferably 1.5 to 3, in particular 1.7 to 2.8 silane groups per molecule. Most preferably, the polymer containing silane groups has an average of 1.7 to 2.3 silane groups per molecule.

Preferably, the polymer comprising silane groups has a silicon content in the range of 0.7 to 1.5 wt.%, in particular 0.8 to 1.2 wt.%. Such compositions enable a particularly advantageous combination of high strength and high stretchability.

Preferably, the polymers containing silane groups have an average molecular weight M in the range from 2000 to 10000g/mol, particularly preferably from 3000 to 8000g/mol, in particular from 4000 to 7000g/mol_n。

Preferably, the polymer containing silane groups has predominantly polyoxyalkylene units, in particular polyoxypropylene units.

The polymers containing silane groups preferably have silane groups of the formula (I)

Wherein

n represents 1 or 2 or 3, in particular 2 or 3,

R¹represents a linear or branched monovalent hydrocarbon group having 1 to 5 carbon atoms,

R²denotes a linear or branched divalent hydrocarbon radical having from 1 to 12 carbon atoms, optionally having cyclic and/or aromatic moieties and optionally having one or more heteroatoms, in particular amide, carbamate or morpholinyl radicals,

x represents O or S or NR³Wherein R is³Represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 20 carbon atoms, optionally having a cyclic portion, and optionally having an alkoxysilyl group or an ether group or a carboxylate group.

n preferably represents 3. Such compositions cure particularly rapidly and enable particularly high strengths to be achieved.

R¹Preferably represents methyl or ethyl or isopropyl.

R¹Particularly preferably represents a methyl group. The polymers containing silane groups are particularly reactive.

R¹It also particularly preferably represents an ethyl group. The polymers containing silane groups are particularly storage-stable and toxicologically advantageous.

X preferably represents O or NR³。

R³Preferably H, butyl, phenyl or having 6 to 20 carbon atomsAnd optionally a branched aliphatic group having an ether group or a carboxylate group.

Most preferably, X represents NR³And R is³To representWherein R is⁴Each represents a methyl or ethyl group, in particular an ethyl group. Such polymers containing silane groups are readily available and enable particularly high strength with high stretchability and resistance.

At X ═ NR³In the case of (1), R²Preferably 1, 3-propylene or 1, 4-butylene, where butylene may be substituted by one or two methyl groups, particularly preferably 1, 3-propylene.

In the case where X is O, R²Preferably represents a divalent hydrocarbon group having 6 to 12 carbon atoms and having an amide group, a carbamate group or a morpholine group, in particular of the formulaA group of (1).

Such preferred silane group containing polymers enable particularly attractive compositions with a combination of high strength and high drawability.

The polymers containing silane groups are obtained from the reaction of at least one polymer containing isocyanate groups and at least one aminosilane, mercaptosilane or hydroxysilane.

The NCO content of the isocyanate group-containing polymer is preferably in the range from 1.2 to 4% by weight, in particular from 1.2 to 2.8% by weight. Such polymers containing isocyanate groups are capable of achieving the silane group content according to the invention when reacted with the preferred silanes.

The isocyanate group-containing polymers are obtained, on the one hand, in particular by reaction of at least one polyol and at least one diisocyanate. The reaction is preferably carried out with exclusion of water at temperatures of from 20 to 160 ℃, in particular from 40 to 140 ℃, optionally in the presence of suitable catalysts.

The NCO/OH molar ratio is preferably in the range from 1.3/1 to 2.5/1.

Suitable as polyols for the preparation of the isocyanate group-containing polymers are polyols which are liquid at room temperature, in particular the following commercially available polyols or any mixtures thereof:

polyether polyols, in particular polyoxyalkylene diols and/or polyoxyalkylene triols, in particular polymerization products of ethylene oxide or 1, 2-propylene oxide or 1, 2-or 2, 3-butylene oxide or oxetane or tetrahydrofuran or mixtures thereof, where they can be polymerized by means of starter molecules having two or three active hydrogen atoms, such as, in particular, water, ammonia or compounds having a plurality of OH-groups or NH-groups, such as, for example, 1, 2-ethanediol, 1, 2-or 1, 3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols or tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1, 3-or 1, 4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1, 1-trimethylolethane, 1,1, 1-trimethylolpropane, glycerol or aniline, or mixtures of the aforementioned compounds.

Preferred polyether polyols are polyoxypropylene diols or triols, or so-called ethylene oxide-capped (EO-capped) polyoxypropylene diols or triols. The latter are polyoxyethylene-polyoxypropylene-mixed polyols, which are obtained in particular by: the polyoxypropylene diol or triol is further alkoxylated with ethylene oxide after the end of the polyoxypropylene reaction and thus is made to have predominantly primary hydroxyl groups.

Preferred polyether polyols have an unsaturation of less than 0.02mEq/g, in particular less than 0.01 mEq/g.

-a polyether polyester polyol.

-polyacrylate polyols and polymethacrylate polyols,

-polyacrylate polyols or polymethacrylate polyols.

Polyhydroxy-functional fats or oils, such as natural fats and oils, in particular castor oil; or polyols obtained by chemical modification of natural fats and oils (so-called oleochemical).

Polyhydrocarbon polyols, also known as oligohydrocarbonols, such as, in particular, polyhydroxyfunctional polyolefins, polyisobutenes, polyisoprenes; polyhydroxy-functional ethylene-propylene-copolymers, ethylene-butylene-copolymers or ethylene-propylene-diene-copolymers, such as those prepared by Kraton Polymers; polyhydroxyl-functional diene (in particular 1, 3-butadiene) polymers, which can in particular also be prepared by anionic polymerization; copolymers of polyhydroxyfunctional dienes (e.g. 1, 3-butadiene) or mixtures of dienes with vinyl monomers (e.g. styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutene or isoprene), in particular polyhydroxyfunctional acrylonitrile/butadiene copolymers, for example acrylonitrile/butadiene copolymers which are terminated, in particular, by epoxides or amino alcohols and carboxyl groups (for example by the nameCTBN or CTBNX or ETBN commercially available from Emerald Performance Materials); or a hydrogenated polymer or copolymer of a polyhydroxy functional diene.

Polyether polyols, in particular polyoxyalkylene diols or triols, are preferred. Particularly preferred are polyoxypropylene diols or triols optionally having oxyethylene groups at the ends.

Preference is given to polyols having an average OH functionality in the range from 1.6 to 3, in particular diols having an average OH functionality in the range from 1.8 to 2.

Preferred are average molecular weights M_nPolyols, in particular diols, in the range from 1000 to 8000g/mol, in particular from 2000 to 6000g/mol, particularly preferably from 3000 to 5000 g/mol.

In the preparation of the polymers containing isocyanate groups, it is also possible to concomitantly use certain amounts of difunctional or polyfunctional alcohols.

The isocyanate group-containing polymer is preferably obtained from the reaction of at least one polyoxypropylene diol having an OH value in the range from 18 to 58mg KOH/g, in particular from 22 to 40mg KOH/g, and optionally having oxyethylene groups at the ends, and at least one diisocyanate.

The preparation of the isocyanate group-containing polymers is optionally accompanied by the use of polyols, in particular polyoxypropylene triols, optionally having oxyethylene groups at least one other end.

Suitable as diisocyanates for preparing the isocyanate group-containing polymers are diisocyanates having aliphatic isocyanate groups, in particular 1, 6-Hexane Diisocyanate (HDI), 2,2(4), 4-trimethyl-1, 6-hexamethylene diisocyanate (TMDI), cyclohexane-1, 3-or-1, 4-diisocyanate, 1-isocyanato-3, 3, 5-trimethyl-5-isocyanato-methylcyclohexane (isophorone diisocyanate or IPDI), perhydro-2, 4 '-or-4, 4' -diphenylmethane diisocyanate (HMDI), 1, 3-or 1, 4-bis (isocyanatomethyl) cyclohexane or m-or p-Xylylene Diisocyanate (XDI).

For the preparation of the isocyanate group-containing polymers, preference is given to diisocyanates having aromatic isocyanate groups, in particular 4,4' -diphenylmethane diisocyanate, optionally with a content of 2,4' -and/or 2,2' -diphenylmethane diisocyanate (MDI), 2, 4-tolylene diisocyanate or mixtures thereof with 2, 6-Tolylene Diisocyanate (TDI), 1, 4-Phenylene Diisocyanate (PDI) or naphthalene-1, 5-diisocyanate (NDI), and also mixtures of the diisocyanates.

Preferably HDI, IPDI, MDI or TDI, especially IPDI, MDI or TDI, most preferably MDI or TDI.

In a preferred embodiment of the present invention, the isocyanate group-containing polymer has aromatic isocyanate groups. The silane group-containing polymers thus obtained enable low-cost compositions having particularly high strength.

In particular, the aromatic isocyanate groups are derived from 4,4' -diphenylmethane diisocyanate, optionally with a content of 2,4' -and/or 2,2' -diphenylmethane diisocyanate (MDI), or 2, 4-toluene diisocyanate or a mixture thereof with 2, 6-Toluene Diisocyanate (TDI).

The diisocyanates are therefore particularly preferably selected from the group consisting of 4,4' -diphenylmethane diisocyanate, 2, 4-tolylene diisocyanate and 2, 6-tolylene diisocyanate.

The aminosilane or mercaptosilane or hydroxysilane used for the reaction with the isocyanate group-containing polymer preferably has the formula (II)

Wherein n and R¹、R²And X has the meaning indicated above.

Suitable aminosilanes for reaction with the isocyanate group-containing polymer are primary or secondary aminosilanes. Preference is given to 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 4-aminobutyltrimethoxysilane, 4-amino-3-methylbutyltrimethoxysilane, 4-amino-3, 3-dimethylbutyltrimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, primary aminosilanes, such as 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane or N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and Michael acceptors, such as acrylonitrile, (meth) acrylates, (meth) acrylamides, maleic or fumaric diesters, and, Citraconic acid diester or itaconic acid diester adducts, in particular diethyl N- (3-trimethoxysilylpropyl) aminosuccinate or diethyl N- (3-dimethoxymethylsilylpropyl) -aminosuccinate. Also suitable are the analogs of the above-mentioned aminosilanes having ethoxy groups instead of methoxy groups on silicon.

Suitable mercaptosilanes for reaction with polymers containing isocyanate groups are, in particular, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane or the analogous of these mercaptosilanes having ethoxy groups on silicon instead of methoxy groups.

Suitable hydroxysilanes for reaction with polymers containing isocyanate groups result in particular from the addition reaction of aminosilanes on lactones, lactides or cyclic carbonates.

Preferred hydroxysilanes of this type are N- (3-triethoxysilylpropyl) -2-hydroxypropionamide, N- (3-trimethoxysilylpropyl) -2-hydroxypropionamide, N- (3-triethoxysilylpropyl) -4-hydroxypentanamide, N- (3-triethoxysilylpropyl) -4-hydroxyoctanamide, N- (3-triethoxysilylpropyl) -5-hydroxydecanamide or N- (3-triethoxysilylpropyl) -2-hydroxypropylcarbamate.

Other suitable hydroxysilanes are obtained from the addition reaction of aminosilanes to epoxides or the addition reaction of amines to epoxysilanes.

Preferred hydroxysilanes of this type are 2-morpholino-4 (5) - (2-trimethoxysilylethyl) cyclohexan-1-ol, 2-morpholino-4 (5) - (2-triethoxysilylethyl) cyclohexan-1-ol or 1-morpholino-3- (3- (triethoxysilyl) propoxy) propan-2-ol.

Most preferred for reaction with the isocyanate group containing polymer is an aminosilane, in particular diethyl N- (3-trimethoxysilylpropyl) aminosuccinate, diethyl N- (3-dimethoxymethylsilylpropyl) aminosuccinate or diethyl N- (3-triethoxysilylpropyl) aminosuccinate.

The composition also includes at least one liquid epoxy resin. Suitable as liquid epoxy resins are the usual industrial epoxy resins which are flowable at room temperature and have a glass transition temperature of less than 25 ℃. Obtained in a known manner and by methods, in particular from compounds having at least two active hydrogen atoms, in particular polyphenols, polyols or amines, by reaction with epichlorohydrin for glycidylation.

Suitable liquid epoxy resins are in particular aromatic liquid epoxy resins, in particular the glycidylation products of:

-bisphenol-a, bisphenol-F or bisphenol-a/F, wherein a represents acetone and F represents formaldehyde, which serve as reactants for the preparation of the bisphenol. In the case of bisphenol-F, it is also possible to have positional isomers which are derived in particular from 2,4 '-or 2,2' -hydroxyphenylmethane.

Dihydroxybenzene derivatives such as resorcinol, hydroquinone or catechol;

other bisphenols or polyphenols such as bis (4-hydroxy-3-methylphenyl) methane, 2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol-C), bis (3, 5-dimethyl-4-hydroxyphenyl) methane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2-bis (4-hydroxyphenyl) butane (bisphenol-B), 3-bis (4-hydroxyphenyl) pentane, 3, 4-bis (4-hydroxyphenyl) hexane, 4, 4-bis (4-hydroxyphenyl) heptane, 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, 2, 4-bis (3, 5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1-bis (4-hydroxyphenyl) cyclohexane (bisphenol-Z), 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane (bisphenol-TMC), 1-bis (4-hydroxyphenyl) -1-phenylethane, 1, 4-bis [2- (4-hydroxyphenyl) -2-propyl ] benzene (bisphenol-P), 1, 3-bis [2- (4-hydroxyphenyl) -2-propyl ] benzene (bisphenol-M), 4,4 '-dihydroxybiphenyl (DOD), 4' -dihydroxybenzophenone, bis (2-hydroxynaphthalen-1-yl) methane, bis (4-hydroxynaphthalen-1-yl) methane, 1, 5-dihydroxynaphthalene, tris (4-hydroxyphenyl) methane, 1,2, 2-tetrakis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) ether, or bis (4-hydroxyphenyl) sulfone;

condensation products of phenols with formaldehyde obtained under acidic conditions, such as phenol-novolaks or cresol-novolaks, also known as bisphenol-F-novolaks;

aromatic amines, such as aniline, P-toluidine, 4-aminophenol, 4 '-methylenediphenyldiamine, 4' -methylenediphenylbis- (N-methyl) amine, 4'- [1, 4-phenylene-bis (1-methylethylidene) ] diphenylamine (diphenylamine-P) or 4,4' - [1, 3-phenylene-bis (1-methylethylidene) ] diphenylamine (diphenylamine-M).

Other suitable liquid epoxy resins are aliphatic or cycloaliphatic polyepoxides, in particular

-a di-, tri-or tetrafunctional C which is saturated or unsaturated, branched or unbranched, cyclic or open-chain₂-to C₃₀Glycidyl ethers of alcohols, in particular ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, octylene glycolDiols, polypropylene glycols, dimethylolcyclohexane, neopentyl glycol, dibromoneopentyl glycol, castor oil, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol or glycerol, or alkoxylated glycerol or alkoxylated trimethylolpropane;

-hydrogenated bisphenol-a-, -F-or-a/F-liquid resins, or glycidylation products of hydrogenated bisphenol-a-, -F-or-a/F;

n-glycidyl derivatives of amides or heterocyclic nitrogen-containing bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin and hydantoin.

Epoxy resins resulting from the oxidation of olefins, such as, in particular, vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1, 5-hexadiene, butadiene, polybutadiene or divinylbenzene.

Preferred are liquid epoxy resins based on bisphenols.

Particularly preferred are liquid epoxy resins based on bisphenol-A-diglycidyl ether, bisphenol-F-diglycidyl ether or bisphenol-A/F-diglycidyl ether, such as those commercially available from Dow, Huntsman or Momentive. These liquid epoxy resins have an easily controlled viscosity and are capable of achieving high strength and resistance. Such liquid resins may also contain a certain content of bisphenol a-solid resin or phenol-novolac.

The weight ratio between the silane group containing polymer and the liquid epoxy resin in the composition is preferably in the range 20/80 to 70/30, in particular 25/75 to 50/50. Such compositions have high strength and good stretchability.

The composition also includes at least one polyamine having at least three amine hydrogens reactive with epoxide groups.

Suitable are, in particular, the following polyamines:

aliphatic, cycloaliphatic or araliphatic primary diamines, in particular 2, 2-dimethyl-1, 3-propanediamine, 1, 3-pentanediamine (DAMP), 1, 5-pentanediamine, 1, 5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethyl-1, 5-pentanediamine(s) (II)C11-neo-diamine), 1, 6-hexanediamine, 2, 5-dimethyl-1, 6-hexanediamine, 2(4), 4-Trimethylhexamethylenediamine (TMD), 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-undecanediamine, 1, 12-dodecanediamine, 1,2-, 1, 3-or 1, 4-diaminocyclohexane, 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3, 5, 5-trimethylcyclohexane (isophoronediamine or IPDA), 2(4) -methyl-1, 3-diaminocyclohexane, N-dimethylformamide, N-dimethylhexamethylenediamine, N-hydroxyformamide, N-2, N-hydroxyformamide, N-hydroxyformamide, N-hydroxyformamide, N-, Bis- (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, bis (4-amino-3-ethylcyclohexyl) methane, bis (4-amino-3, 5-dimethylcyclohexyl) methane, bis (4-amino-3-ethyl-5-methylcyclohexyl) methane, 2,5(2,6) -bis (aminomethyl) bicyclo [2.2.1]Heptane (NBDA), 3(4),8(9) -bis (aminomethyl) tricyclo- [5.2.1.0^{2 ,6}]Decane, 1, 4-diamino-2, 2, 6-Trimethylcyclohexane (TMCDA), 1, 8-menthanediamine, 1, 3-bis (aminomethyl) benzene (MXDA) or 1, 4-bis (aminomethyl) benzene;

aliphatic primary diamines or triamines containing ether groups, in particular 3, 6-dioxaoctane-1, 8-diamine, 4, 7-dioxadecane-1, 10-diamine, 4, 7-dioxadecane-2, 9-diamine, 4, 9-dioxadodecane-1, 12-diamine, 5, 8-dioxadodecane-3, 10-diamine, 4,7, 10-trioxatridecane-1, 13-diamine or higher oligomers of these diamines, bis (3-aminopropyl) polytetrahydrofuran or other polytetrahydrofuran diamines, 3, 9-bis (3-aminopropyl) -2,4,8, 10-tetraoxaspiro [5.5 ]]Undecane, the cycloaliphatic diamine containing an ether group obtained by propoxylation and subsequent amination of 1, 4-dimethylolcyclohexane, may in particular beRFD-270 (from Huntsman), or polyoxyalkylene di-or triamines, especiallyD-230、D-400、D-2000、EDR-104、EDR-148、EDR-176、T-403、T-3000、T-5000 (all from Huntsman), or the corresponding amines from BASF or Nitroil;

polyamines having secondary amino groups and having two primary amino groups, such as, in particular, 3- (2-aminoethyl) aminopropylamine, bis (hexamethylene) triamine (BHMT), Diethylenetriamine (DETA), triethylenetetramine (TETA), Tetraethylenepentamine (TEPA), Pentaethylenehexamine (PEHA) or higher homologues of linear polyethyleneamines, Dipropylenetriamine (DPTA), N- (2-aminoethyl) -1, 3-propanediamine (N3-amine), N, N '-bis (3-aminopropyl) ethylenediamine (N4-amine), N, N' -bis (3-aminopropyl) -1, 4-diaminobutane, N5- (3-aminopropyl) -2-methyl-1, 5-pentanediamine, N3- (3-aminopentyl) -1, 3-pentanediamine, N5- (3-amino-1-ethylpropyl) -2-methyl-1, 5-pentanediamine or N, N' -bis (3-amino-1-ethylpropyl) -2-methyl-1, 5-pentanediamine;

polyamines having tertiary amino groups, such as, in particular, 2-aminoethylpiperazine, 3-Dimethylaminopropylamine (DMAPA), N-dimethylbis (1, 3-propylene) triamine (DMAPAPA), N '-bis (aminoethyl) piperazine, N' -bis (aminopropyl) piperazine, N-bis (3-aminopropyl) methylamine, N-bis (3-aminopropyl) ethylamine;

aliphatic, cycloaliphatic or araliphatic primary triamines, in particular 4-aminomethyl-1, 8-octanediamine, 1,3, 5-tris (aminomethyl) benzene, 1,3, 5-tris (aminomethyl) cyclohexane, tris (2-aminoethyl) amine, tris (2-aminopropyl) amine or tris (3-aminopropyl) amine; or

Diamines having one primary and one secondary amino group, in particular products obtained by reductive alkylation of primary aliphatic polyamines with aldehydes or ketones, such as, in particular, N-benzyl-1, 2-ethylenediamine, N-benzyl-1, 2-propylenediamine, N-benzyl-1, 3-bis (aminomethyl) benzene, N-2-ethylhexyl-1, 3-bis (aminomethyl) benzene, N- (2-phenylethyl) -1, 3-bis (aminomethyl) benzene (styrenated 1, 3-bis (aminomethyl) benzene, may be used as a constituent of240 from Mitsubishi Gas Chemical); or

Adducts of said amines or small-molecule amines (such as in particular 1, 2-ethylenediamine or 1, 2-propylenediamine) with monoepoxides or diepoxides (in particular with cresyl glycidyl ether or bisphenol-a diglycidyl ether); or

Polyamidoamines, in particular reaction products of monocarboxylic or polycarboxylic acids or esters or anhydrides thereof (in particular dimeric fatty acids) with a stoichiometric excess of a polyamine (in particular polyalkylene amines, such as DETA or TETA); or

Mannich bases, in particular phenamine, i.e. the reaction product of phenols (in particular cardanol) with aldehydes (in particular formaldehyde) and polyamines.

Preference is given to aliphatic, cycloaliphatic or araliphatic polyamines.

The polyamine is preferably selected from MPMD, TMD, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminocyclohexane, 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, IPDA, 2(4) -methyl-1, 3-diaminocyclohexane, bis (4-aminocyclohexyl) methane, NBDA, MXDA, average molecular weight M_nIn the range from 200 to 500g/mol of polyoxypropylene diamines and polyoxypropylenetriamines, BHMT, TETA, TEPA, N4-amine, DMAPAPA, N-benzyl-1, 2-ethylenediamine, N-benzyl-1, 2-propylenediamine, N-benzyl-1, 3-bis (aminomethyl) benzene, N- (2-phenylethyl) -1, 3-bis (amino)Methyl) benzene and MPMD or adducts of 1, 2-propanediamine with cresyl glycidyl ether.

Of these, 1, 2-diaminocyclohexane is particularly preferred. A particularly high strength is thereby obtained.

Also particularly preferred among these is IPDA. A particularly low-cost composition with high strength is thereby obtained.

Of these, the average molecular weight M is particularly preferred_nIn the range from 200 to 500g/mol of polyoxypropylenediamines or triamines, in particularD-230、D-400 orAnd T-403. Particularly high elongations are thereby obtained.

Also particularly preferred among these are adducts of 1, 2-propanediamine with cresyl glycidyl ethers, in particular o-cresyl glycidyl ether, in which addition is preferably carried out using an excess of 1, 2-propanediamine relative to cresyl glycidyl ether and the non-added 1, 2-propanediamine is removed by distillation after the reaction. A glossy surface is thus obtained even in humid conditions.

It may be advantageous to use a mixture of two or more polyamines. Preference is given to mixtures comprising at least one polyoxypropylene diamine or triamine and at least one further polyamine.

The polyamine or the mixture of two or more polyamines is preferably present in such an amount that the ratio of the number of amine hydrogens to the number of epoxide groups is in the range from 0.5/1 to 1.5/1, in particular from 0.8/1 to 1.2/1.

The composition according to the invention is preferably a two-component composition and comprises a first component and a second component which are prepared, packaged and stored separately from each other, wherein the polyamine and the liquid epoxy resin are not present in the same component.

In a preferred embodiment of the invention, the composition has a first component comprising

At least one polymer containing silane groups as described above, and

-at least one liquid epoxy resin,

and a second component comprising

-at least one polyamine having at least three amine hydrogens reactive with epoxide groups.

In another preferred embodiment of the invention, the composition has a first component comprising

At least one polymer containing silane groups as described above, and

at least one polyamine having at least three amine hydrogens reactive with epoxide groups,

and a second component comprising

-at least one liquid epoxy resin.

For both embodiments, the components themselves are storage stable with the exclusion of moisture. When the two components are mixed, the primary and/or secondary amino groups react with the epoxy groups present. When contacted with water, the silane groups react while releasing the alcohol.

The composition preferably further comprises at least one additional ingredient selected from the group consisting of: aminosilane, desiccant, accelerator, water, filler and plasticizer.

Suitable aminosilanes are in particular 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -N' - [3- (trimethoxysilyl) propyl ] ethylenediamine and the like which have ethoxy groups instead of methoxy groups on silicon.

The aminosilane is suitably present in the same component as the polyamine.

Preferably, the composition has an aminosilane content in the range of 0.1 to 5 wt.%, in particular 0.2 to 2 wt.%. The composition has a particularly high strength.

Suitable drying agents are, in particular, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane or organosilanes which have a functional group in the alpha position of the silane group, in particular N- (methyldimethoxysilylmethyl) -O-methylcarbamate or (methacryloxymethyl) silane, methoxymethylsilane, orthoformate, and also calcium oxide or molecular sieves.

The composition particularly preferably comprises vinyltrimethoxysilane or vinyltriethoxysilane. Here, vinyltrimethoxysilane is preferred when the silane group-containing polymer has a methoxysilane group, and vinyltriethoxysilane is preferred when the silane group-containing polymer has an ethoxysilane group.

The drying agent is suitably present in the same component as the silane group containing polymer.

Suitable accelerators are in particular substances which accelerate the crosslinking of the polymers containing silane groups. Particularly suitable for this purpose are metal catalysts and/or nitrogen-containing compounds.

Suitable metal catalysts are titanium, zirconium, aluminum or tin compounds, in particular organotin compounds, organotitanates, organozirconates or organoaluminates, wherein these metal catalysts have in particular alkoxy groups, aminoalkoxy groups, sulfonate groups, carboxyl groups, 1, 3-diketonate groups, 1, 3-ketonate groups, dialkylphosphate groups or dialkylpyrophosphate groups. Particularly suitable are dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diacetylacetonate, dioctyltin oxide, dioctyltin dichloride, dioctyltin diacetate, dioctyltin dilaurate or dioctyltin diacetylacetonate, and also organotitanates or organozirconates.

Suitable nitrogen-containing compounds are, in particular, amidines, such as, for example, 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), 6-dibutylamino-1, 8-diazabicyclo [5.4.0] undec-7-ene, or guanidines, such as, for example, tetramethylguanidine, 2-guanidinobenzimidazole, guanidinoacetone, or reaction products of carbodiimides and amines, such as, in particular, polyetheramines or aminosilanes.

Suitable accelerators are also in particular substances which accelerate the reaction of epoxide groups with amino groups. Suitable for this purpose are in particular acids or compounds which can be hydrolyzed to form acids, in particular organic carboxylic acids such as salicylic acid, organic sulfonic acids such as p-toluenesulfonic acid, sulfonic esters, phosphoric acids or nitric salts such as in particular calcium nitrate, or tertiary amines such as in particular 1, 4-diazabicyclo [2.2.2] octane, triethanolamine, imidazoles such as in particular N-methylimidazole, N-vinylimidazole or 1, 2-dimethylimidazole, the amidines or guanidines, phenols or mannich bases such as in particular 2,4, 6-tris (dimethylaminomethyl) phenol, or compounds having mercapto groups.

The composition preferably comprises at least one accelerator selected from the group consisting of: dialkyltin compounds, organotitanates, amidines, guanidines, acids, calcium nitrate and mannich bases.

Particularly preferably, the composition comprises 2,4, 6-tris (dimethylaminomethyl) phenol and at least one further accelerator.

In a preferred embodiment of the invention, the composition comprises water or a water-releasing substance. The advantage of such a composition is that the water required for crosslinking of the silane groups need not be absorbed from the environment, or need only be partially absorbed from the environment.

The compositions preferably contain in total up to 5% by weight, in particular up to 2% by weight, of free or releasable water.

Free water is not suitable for being present in the same component as the polymer comprising silane groups.

Suitable fillers are, in particular, ground or precipitated calcium carbonate, optionally coated with fatty acids, in particular stearates, barite (schwerspete), quartz flour, quartz sand, dolomite, wollastonite, calcined kaolin, layered silicates, such as mica or talc, zeolites, aluminum hydroxide, magnesium hydroxide, silica (including highly dispersible silica from pyrogenic processes), cement, gypsum, fly ash, industrially produced carbon black, graphite, metal powders, such as aluminum, copper, iron, silver or steel, PVC powders or lightweight fillers, such as hollow glass spheres or gas-filled hollow plastic spheres (microspheres), in particular under the trade name(from Akzo Nobel).

Preferred are calcium carbonate, calcined kaolin, highly dispersible silica or industrially prepared carbon black.

Suitable plasticizers are, in particular, carboxylic esters, such as phthalic acid esters, in particular diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di (2-propylheptyl) phthalate (DPHP), hydrogenated phthalic acid esters or 1, 2-cyclohexanedicarboxylic acid esters, in particular hydrogenated diisononyl phthalate or diisononyl-1, 2-cyclohexanedicarboxylate (DINCH), terephthalic acid esters, in particular bis (2-ethylhexyl) terephthalate (DOTP) or diisononyl terephthalate (DINT), hydrogenated terephthalic acid esters or 1, 4-cyclohexanedicarboxylic acid esters, in particular hydrogenated bis (2-ethylhexyl) terephthalate or bis (2-ethylhexyl) -1, 4-cyclohexanedicarboxylic acid esters or hydrogenated diisononyl terephthalate or diisononyl-1, 4-cyclohexanedicarboxylate, isophthalate, trimellitate, adipate, in particular dioctyl adipate, azelate, sebacate, benzoate, glycol ether, glycol ester, such as in particular triethylene glycol-bis (2-ethylhexanoate), plasticizer having a polyether structure, in particular polypropylene oxide monols, diols or triols having blocked hydroxyl groups, in particular in the form of acetate groups, organic phosphates or sulfonates, polybutene, polyisobutene or plasticizers derived from natural fats or oils, in particular epoxidized soybean oil or linseed oil.

Preferred plasticizers are phthalates, glycol esters or plasticizers having a polyether structure.

The compositions according to the invention may comprise other admixtures, in particular

Other crosslinking agents, in particular other silanes such as epoxysilanes or mercaptosilanes, or compounds having a mercapto group such as thiol-terminated polysulfide polymers or thiol-terminated polyoxyalkylene ethers;

-a solvent or diluent;

inorganic or organic pigments, in particular titanium dioxide, chromium oxide or iron oxide;

-a dye;

-rheology modifiers, in particular thickeners, in particular phyllosilicates such as bentonite, castor oil derivatives, hydrogenated castor oil, polyamides, polyurethanes, urea compounds, polyvinyl chloride, pyrogenic silica, cellulose ethers or hydrophobically modified polyoxyethylenes;

natural resins, fats or oils such as rosin, shellac, linseed oil, castor oil or soybean oil;

-a non-reactive polymer, in particular a homopolymer or copolymer of an unsaturated monomer, in particular selected from ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or an alkyl (meth) acrylate, in particular Polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene vinyl acetate-copolymer (EVA) or atactic poly-alpha-olefin (APAO);

fibers, in particular glass fibers, carbon fibers, metal fibers, ceramic fibers, polymer fibers, such as polyamide fibers or polyethylene fibers, or natural fibers, such as wool, cellulose, hemp or sisal;

nanofillers such as graphene or carbon nanotubes;

flame-retardant substances, in particular the fillers aluminum hydroxide or magnesium hydroxide described above, and in particular organic phosphates, such as, in particular, triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, isodecyl diphenyl phosphate, tris (1, 3-dichloro-2-propyl) phosphate, tris (2-chloroethyl) phosphate, tris (2-ethylhexyl) phosphate, tris (chloroisopropyl) phosphate, tris (chloropropyl) phosphate, isopropylated triphenyl phosphate, mono-, bis-and tris (isopropylphenyl) phosphates of different degrees of isopropylation, resorcinol-bis (diphenyl phosphate), bisphenol-a-bis (diphenyl phosphate) or ammonium polyphosphate;

additives, in particular emulsifiers, wetting agents, levelling agents, defoamers, deaerators, stabilizers against oxidation, heat, light or ultraviolet radiation or biocides.

It may be advantageous to dry some of the ingredients chemically or physically prior to incorporation into the composition, particularly when stored with the silane group containing polymer.

Preferably, the composition according to the invention comprises a small amount of solvent. It comprises in particular less than 5% by weight, preferably less than 2.5% by weight, of solvent. Most preferably it is substantially free of solvent.

The compositions according to the invention preferably have a content of polymers containing silane groups in the range from 10 to 50% by weight, in particular from 12 to 40% by weight.

The compositions according to the invention preferably have a content of liquid epoxy resin in the range from 10 to 60% by weight, in particular from 20 to 50% by weight.

The compositions according to the invention preferably have a total content of liquid epoxy resin and epoxy group-containing reactive diluent in the range from 20 to 70% by weight, in particular from 25 to 65% by weight.

The composition according to the invention preferably comprises

12 to 40% by weight of a polymer containing silane groups,

-20 to 50% by weight of a liquid epoxy resin,

-0 to 20 wt.% of an epoxy group containing reactive diluent,

5 to 40% by weight of a polyamine,

-from 0 to 50% by weight of a filler,

and optionally other ingredients.

The compositions according to the invention are preferably prepared and used in the form of two-component compositions. Here, the first and second components of the composition are prepared separately from each other and stored in a container impermeable to the moisture. Suitable containers are in particular tubs, bottles, bags, hoppers, pots, magazines or tubes.

To use the composition, the two components are mixed with each other immediately before or during application. The mixing ratio is preferably selected here such that the groups reactive toward epoxide groups are present in a suitable ratio to epoxide groups as described above. The mixing ratio is usually in the range of 1:10 to 10:1 in parts by weight.

Mixing of the two components is carried out by a suitable method; it can be carried out continuously or batchwise by means of static mixers or by means of dynamic mixers. In the case of mixing prior to application, care must be taken that the application is carried out within the pot life of the composition, otherwise disturbances may occur, such as delayed or incomplete build-up of adhesion on the substrate or premature gelling.

By "pot life" is meant herein the time after mixing of the components during which the composition must be applied.

The mixing of the components is preferably carried out at ambient temperature, which is generally in the range of about 0 to 50 ℃, preferably about 5 to 35 ℃.

Curing by chemical reaction is initiated by mixing the two components. In this case, the epoxide groups react with amine hydrogens and the silane groups are hydrolyzed to release alcohols, with silanol groups (Si-OH groups) being formed and siloxane groups (Si-O-Si groups) being formed by subsequent condensation reactions. The reaction and optionally further reactions result in the composition curing to a crosslinked plastic. If water for hydrolysis of silane groups is not present in the composition, the water may come from the air (atmospheric moisture) or the substrate, or the composition may be contacted with the aqueous component, for example, by brushing, spraying, or mixing.

In particular, curing is carried out at a temperature of from 0 to 150 ℃. Curing can in particular be carried out at ambient temperature, wherein curing generally lasts from days to weeks until it is substantially complete under the given conditions. In some cases it may be advantageous to subsequently cure the composition that is partially cured at ambient temperature at an elevated temperature.

The application of the composition is carried out on at least one substrate, wherein the following are particularly suitable:

metals or alloys, such as aluminum, iron, steel, copper, other non-ferrous metals, including surface-treated metals or alloys, such as galvanized or chromed metals;

concrete, mortar, cement, fiber cement, brick, tile, gypsum or natural stone such as granite or marble;

-asphalt or bitumen;

-a coated or painted substrate, in particular a painted tile, a coated concrete, a powder coated metal or alloy or a painted panel;

-repairs or screeds based on PCC (polymer-modified cement mortar) or ECC (epoxy-modified cement mortar);

leather, fabric, paper, wood-based materials combined with resins (for example phenolic, melamine or epoxy resins), resin-fabric-composites or other so-called polymer-composites;

plastics, such as rigid and flexible PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy, phenolic, PUR, POM, TPO, PE, PP, EPM or EPDM, each untreated or surface-treated, for example via plasma, corona or flame;

fiber-reinforced plastics, such as carbon fiber-reinforced plastics (CFK), glass fiber-reinforced plastics (GFK) and Sheet Molding Compounds (SMC);

-glass or glass-ceramic;

insulating foams, in particular made of EPS, XPS, PUR, PIR, asbestos, glass wool or foamed glass (foam glass).

If desired, the substrate can be pretreated before application, in particular by physical and/or chemical cleaning methods or by applying activators or primers.

The cured composition is obtained after curing of the described composition.

The cured composition has extremely high strength, high drawability, and high tear propagation resistance.

In particular, it has a tensile strength of at least 15MPa, preferably at least 20MPa, and an elongation at break of at least 10%, preferably at least 15%, in particular at least 20%, most preferably at least 25%, determined on dumbbell-shaped test specimens having a length of 75mm, a rod length of 30mm, a rod width of 4mm and a thickness of about 2mm, at a tensile speed of 2mm/min according to DIN EN 53504.

In particular, it has a tear propagation resistance of at least 10N/mm, preferably at least 15N/mm, in particular at least 20N/mm, said tear propagation resistance being determined according to DIN ISO 34 at a stretching speed of 500 mm/min.

The composition also has a high resistance against heat, light and hydrolysis. In particular, the composition also has a high resistance against alcohol/water mixtures, for example used as cooling liquid or antifreeze in automobile or electric vehicle batteries, for example 50% by weight A mixture of konzentrata (from BASF) and 50 wt% water.

The compositions also have very high adhesion on a variety of substrates, particularly wet or damp substrates. In particular, it is possible with the composition according to the invention to bond metals such as aluminum or steel without the use of a primer, wherein the bond is very corrosion resistant, for example in the case of salt water loading. Furthermore, it is possible to permanently bond concrete, asphalt or bitumen without the use of a primer, even under wet or humid conditions.

In addition, the composition has an anti-corrosion effect when used on metals such as aluminum or steel.

The compositions are also particularly advantageous when it is necessary to use products which are free of isocyanate for labour protection and health protection reasons.

The described compositions are preferably used as adhesives, sealants, coatings or casting compounds, in particular on at least one metal, such as, in particular, steel or aluminum, preferably aluminum.

The advantage when used on at least one metal is that the composition protects the metal from corrosion. Thus, even in the case of, for example, loading with salt water, the adhesion is not weakened by metal corrosion. In particular, it is possible to bond unabated aluminum without using a primer, wherein the bonding is not weakened by corrosion even in the case of loading with salt water.

Particularly advantageously, the composition is used as a viscoelastic adhesive. Here, it usually has a liquid or pasty consistency and a textural viscosity after the components have been mixed. Upon application, the mixed adhesive is applied to at least one substrate to be bonded over a pot life and the two substrates are adhesively joined during the open time of the adhesive.

The "open time" of the adhesive means the maximum possible time period for a force-locking connection between the application of the adhesive and the joining of the components to be bonded.

The mixed adhesive is applied or applied, in particular, by means of brushes, rollers, scrapers, spatulas or from tubes, cartridges or metering devices.

The adhesive is particularly suitable for use in the construction industry or for bonding components in the manufacturing industry.

One preferred use is the bonding of battery cases, particularly for electric vehicles. Advantageous here are high strength and high stretchability, high adhesion and high resistance, in particular even for alcohol/water mixtures such as those used as cooling fluids for the batteries. In this case, aluminum components are bonded in particular, corrosion-resistant bonding under saline load being particularly advantageous.

A further subject of the invention is therefore an adhesion process, characterized in that the mixed composition is applied to at least one substrate to be adhered over a pot life and the substrates are adhesively bonded in open time, and then the mixed composition is cured. In this case, preferably at least one substrate is a metal, in particular aluminum or steel, particularly preferably aluminum.

The described compositions are preferably also used as coatings, in particular as coatings for metals, such as in particular steel or aluminum, wherein the compositions protect the metal against corrosion.

The described compositions are preferably also used as casting materials for filling cavities (for example cracks, gaps or holes), wherein the mixed compositions are filled or injected into the cavities and, after curing, fill the cavities and bring about a viscoelastic bonding of the sides of the cavities to one another, wherein excellent adhesion can be produced even in wet environments. Thus, it is possible to permanently repair in a simple manner those roads, squares or platforms and walls or other buildings which have damage at surfaces or kerbs, edges or boundaries, wherein the repaired location is very well resistant even to large loads.

If desired, the cavity can be filled with so-called anchors, such as reinforcing bars, screws or bolts, during filling of the cavity.

A further subject of the invention is therefore a process for coating a substrate or for filling cavities, in particular cracks or gaps, which is characterized in that the mixed composition is applied to the substrate or is filled into the cavity over the pot life and is cured in situ. Optionally, the anchor can be loaded into the cavity while the cavity is being filled, so long as the composition remains flowable.

The article is obtained by applying and curing the composition or by a bonding process or a process of coating a substrate or filling a cavity. The article may be a building or a part thereof, in particular a road, a square, a platform, a kerb, a border or a wall, or may be an industrial or consumable, in particular a vehicle or a part thereof, in particular a vehicle battery compartment.

A further subject of the invention is therefore an article obtained by said use or said method for bonding or filling cavities.

The compositions according to the invention have advantageous properties, in particular good storage stability, fast curing (even under wet or humid conditions), surprisingly high strength and high drawability, high tear propagation resistance, high resistance and high adhesion on many substrates, wherein the compositions protect metals, such as steel or aluminium, from corrosion when used on said metals. The composition is thus capable of achieving reliable adhesion under corrosive conditions on untreated aluminum.

Examples

Examples are described below, which explain the present invention in more detail. The invention is of course not limited to the described embodiments.

"Standard climate" (NK) means a temperature of 23. + -. 1 ℃ and a relative air humidity of 50. + -. 5%.

The chemical reagents used were from Sigma-Aldrich Chemie GmbH, if not otherwise stated.

N- (3-trimethoxyl)Silylpropyl) diethyl aminosuccinate was prepared from the reaction of diethyl maleate and 3-trimethoxysilylpropylamine. Diisodecyl phthalate and its use10-P (from BASF) was used.

The comparative examples are indicated by (Ref.).

Preparation of Polymer containing silane groups:

polymer ST-1

400g of polyoxypropylene diol (c) with continuous stirring with exclusion of moisture4200, OH-value 28mg KOH/g from Covestro) and 52g of 4,4' -diphenylmethane diisocyanate (44MC L from Covestro) to 80 ℃ and left to stand at this temperature until the NCO content reaches a value of 1.85% by weight.

70.7g N- (3-trimethoxysilylpropyl) diethyl aminosuccinate was then added and stirred at 60 ℃ until no more isocyanate was detected by FT-IR spectroscopy. The resulting polymer containing silane groups was cooled to room temperature and stored with exclusion of water. It was clear, liquid at room temperature and had a calculated silicon content of 1.08 wt%.

Polymer ST-2

513.3g of polyoxypropylene diol (c) with continuous stirring with exclusion of moisture4200, OH-value 28mg KOH/g from Covestro), 256.7g of an ethylene oxide-capped polyoxypropylene triol (MD34-02, OH-value 35mg KOH/g, fromShell) and 64.2g of toluene diisocyanate (T80P from Covestro) to 80 ℃ and left at this temperature until the NCO-content reaches a value of 1.5% by weight.

Then 105.8g N- (3-trimethoxysilylpropyl) diethyl aminosuccinate was added and stirred at 60 ℃ until no more isocyanate was detected by FT-IR spectroscopy. The resulting polymer containing silane groups was cooled to room temperature and stored with exclusion of water. It was clear, liquid at room temperature and had a calculated silicon content of 0.90 wt%.

Polymer ST-3

400g of polyoxypropylene diol (c) with continuous stirring with exclusion of moisture4200, OH-value 28mg KOH/g from Covestro), 44.4g of isophorone diisocyanate (R: (R)IPDI from Evonik) and 0.05g of dibutyltin dilaurate were heated to 80 ℃ and left to stand at this temperature until the NCO content reached a value of 1.9% by weight.

74.8g N- (3-trimethoxysilylpropyl) diethyl aminosuccinate was then added and stirred at 60 ℃ until no more isocyanate was detected by FT-IR spectroscopy. The resulting polymer containing silane groups was cooled to room temperature and stored with exclusion of water. It was clear, liquid at room temperature and had a calculated silicon content of 1.15 wt%.

Polymer ST-4

500.0g of polyoxypropylene diol (c) with continuous stirring with exclusion of moisture2000L, OH-value 55.5mg KOH/g from Dow) and 88.7g of toluene diisocyanate (T80P from Covestro) to 80 ℃ and left at this temperature until the NCO-content reaches a value of 3.4% by weight.

167.5g N- (3-trimethoxysilylpropyl) diethyl aminosuccinate was then added and stirred at 60 ℃ until no more isocyanate was detected by FT-IR spectroscopy. The resulting polymer containing silane groups was cooled to room temperature and stored with exclusion of water. It was clear, liquid at room temperature and had a calculated silicon content of 1.8 wt%.

Polymer ST-5(Ref.)

250.0g of polyoxypropylene diol (c) with continuous stirring with exclusion of moisture2000L, OH value 55.5mg KOH/g from Dow), 250.0g of polyoxypropylene diol (C) (P1010, OH-value 110mg KOH/g from Dow) and 130.4g of toluene diisocyanate (C)T80P from Covestro) to 80 ℃ and left at this temperature until the NCO-content reaches a value of 4.9% by weight.

258.5g N- (3-trimethoxysilylpropyl) diethyl aminosuccinate was then added and stirred at 60 ℃ until no more isocyanate was detected by FT-IR spectroscopy. The resulting polymer containing silane groups was cooled to room temperature and stored with exclusion of water. It was clear, liquid at room temperature and had a calculated silicon content of 2.3 wt%.

Polymer ST-6(Ref.)

1000g of polyoxypropylene diol (c) with continuous stirring with exclusion of moisture12200 from Covestro; OH value 11.0mg KOH/g), 122.8g diisodecyl phthalate, 43.6g isophorone diisocyanate (IPDI from Evonik) and 0.12g of dibutyltin dilaurate were heated to 90 ℃ and left to stand at this temperature until the NCO content reached a value of 0.63% by weight.

61.8g N- (3-trimethoxysilylpropyl) diethyl aminosuccinate was then added and stirred at 90 ℃ until no more isocyanate was detected by FT-IR spectroscopy. The obtained silane group-containing polymer (90% by weight in diisodecyl phthalate) was cooled to room temperature and stored with exclusion of water. It is clear, liquid at room temperature and has a calculated silicon content of 0.45% by weight (calculated on 100% by weight of polymer, without diisodecyl phthalate).

The polymers ST-1 to ST-4 have a silicon content according to the invention. The polymer ST-5(Ref.) has a higher silicon content than the present invention, and the polymer ST-6(Ref.) has a lower silicon content than the present invention. Which was used for comparison.

Preparation of the two-component composition:

examples Z-1 to Z-7:

for each composition, the ingredients of component-1 specified in table 1 were mixed in the specified amounts (parts by weight) by a centrifugal mixer (speedmixertmac 150, FlackTek Inc.) and stored with the exclusion of water.

Likewise, the ingredients of component-2 given in Table 1 were processed and stored.

The two components of each composition were then processed by a centrifugal mixer into a homogeneous liquid at a given mixing ratio (0.6/1 by weight) and immediately tested in the following manner:

to determine the pot life, an amount of 300g of freshly mixed composition was stirred with a spatula in a 500ml beaker at 5 minute intervals until the composition was perceived to be sufficiently viscous to no longer be easily processed.

To determine the mechanical properties, the mixed composition was cast as a film with a thickness of 2mm on a PTFE-coated film and stored under standard climates. After 1 day dumbbell-shaped samples with a length of 75mm, a rod length of 30mm and a rod width of 4mm were punched out of the film and stored in a standard climate for a further 6 days. The tensile strength (breaking force), the elongation at break and the modulus of elasticity at 0.5 to 1% elongation (E-modulus 0.5-1%) and 0.5 to 5% elongation (E-modulus 0.5-5%) are then determined at a tensile speed of 2mm/min as described in DIN EN 53504. Several test specimens were likewise punched and stored to determine the tear propagation resistance and tested at a tensile speed of 500mm/min according to DIN ISO 34.

The appearance of all membranes was assessed visually after 7 days under NK. All films were black after curing, absolutely tack-free and had a silky matte surface, uniform and bubble-free. Such films are noted as "aesthetic".

The results are shown in Table 2.

Examples Z-1 to Z-3 and Z-5 to Z-6 are examples according to the invention in which the polymer comprising silane groups has a silicon content according to the invention. Example Z-4 is a comparative example in which the polymer containing silane groups has a lower silicon content than the invention. Example Z-7 is a comparative example in which the polymer containing silane groups has a higher silicon content than the invention.

Table 1: compositions of examples Z-1 to Z-7.

¹ DCH-99 (from Invista)

²3-aminopropyltrimethoxysilane (from Momentive)

³2,4, 6-Tris (dimethylaminomethyl) phenol (from Evonik)

⁴Irganox 1010 (from BASF)

⁵ GY 250 (from Huntsman)

⁶ DY-H (from Huntsman)

⁷Weight ratio of component-1/component-2

Table 2: properties of examples Z-1 to Z-7.

In addition, the composition of example Z-1 was tested for corrosion resistance or stability under saline loading to bond two aluminum panels (alloy 5754, AlMg3, blank). As a comparison, the same test was performed using a commercially available two-component epoxy adhesive (2K epoxy adhesive) (═ impact-resistant structural adhesive 07333 from 3M).

To this end, a plurality of bonded test specimens were prepared by applying freshly mixed adhesive between two blank aluminum plates (AlMg3, 100x25x1mm) degreased with heptane, in a layer thickness of 0.3mm and an overlapping bonding surface of 10x25 mm. After a storage time of 7 days in a standard climate, the tensile shear strength is determined in accordance with DIN EN 1465 at a tensile speed of 10 mm/min. The value is reported in table 3 as "week 0" (starting value).

Other such samples were subjected to different saline loading cycles as described below. The first day the samples were placed in saline solution (5 wt% NaCl in deionized water) at room temperature for 15 minutes, then hung under standard climate for 95min and drip-dried, then stored in a climatic chamber at 50 ℃/90% relative humidity for 22h (═ 1 cycle). The same procedure was then continued for 4 days and then placed in a climatic cabinet at 50 ℃/90% relative humidity for 48h (weekend). This resulted in a storage time of 1 week with 5 cycles of saline load. The specimens were stored in this manner for 2 weeks (10 cycles) or 4 weeks (20 cycles) or 6 weeks (30 cycles) and then the tensile shear strength was determined as described above, respectively. After the tensile shear strength test was performed, the fracture pattern of the test piece and the state (appearance) of the aluminum plate under adhesion were visually evaluated. "cf" means cohesive failure (cohesive failure) and "af" means adhesive failure (adhesive failure). "No corrosion" means that the gloss of the bonded aluminum plates is unchanged. "2-3 mm corrosion" means that the aluminum under the bond exhibits a matte-white discoloration in the range of 2-3mm from the edge. All panels showed a matte-white mottled discoloration after saline loading in the areas not covered by the adhesive.

The results are shown in Table 3.

Table 3: example Z-1 pulling after saline loading compared to 2K epoxy adhesive (07333, from 3M)

Tensile shear strength and appearance.

The adhesion of the composition of example Z-1 on dry and wet concrete and asphalt was also determined. To this end, 3 concrete slabs (500x500x40mm) and 3 asphalt slabs (about 300x200x30mm) were provided. Both plates were coated with freshly mixed compositions in the dry state in a layer thickness of about 3 to 4mm each. The third plate was placed in deionized water for 24h and then coated with freshly mixed composition in the wet state of the surface residual water, likewise in a layer thickness of about 3 to 4 mm. A plurality of acetone-cleaned steel cylinders, each having a diameter of 20mm, were applied to the freshly coated plates, so that a bond was formed between the steel cylinders and the composition (coating). After storage of the coated panels for 7 days in a standard climate, the adhesion strength values were determined on one of the two dry panels and on the wet panel, respectively. The other plates coated in the dry state were placed in deionized water for 7 days to allow the surfaces to dry before the adhesion strength values were determined. The adhesion strength value is determined as follows: the bonded steel cylinder was pulled at a test speed of 2mm/min according to DIN EN 4624 until the plate broke.

The results are shown in Table 4.

Table 4: bond Strength results on concrete and asphalt for the composition of example Z-1