EP3810560A1 - Two-component system for formation of cohesive bonds or for chemical anchoring - Google Patents

Abstract

A two-component system for forming cohesive bonds or for chemical anchoring comprises a curable binder component A and an activator component B. Component A comprises: A-1) an inhibited hydraulic binder selected from calcium aluminate cement, calcium sulfoaluminate cement and mixtures thereof; component B comprises: B-1) a curing activator. At least one of components A and/or B comprises: V-1) an organic binder; and V-2) a filler having a Mohs hardness of at least 5. The system is an aqueous system which is unproblematic from a health point of view. It is easy to process and quickly attains high strengths.

Description

 Two-component system for the formation of integral bonds or for chemical anchoring

description

The invention relates to a two-component system for the formation of cohesive groups or for chemical anchoring and a method for the formation of cohesive groups or chemical anchoring.

In addition to non-positive and positive anchoring, e.g. fasteners are anchored in boreholes, e.g. by means of dowels, in many cases also integral anchors using organic and / or inorganic mortar compounds. Cohesive anchoring of fasteners are used, for example, for fastenings that are critical for distance and / or in the tension zone of components. Another application for integral anchoring using organic and / or inorganic mortar masses is the subsequent attachment of reinforcing iron in concrete. This can be done, for example, during repair work or for subsequent reinforcement of floors or ceilings, or when attaching attachments Built structures may be required. The reinforcing bars are also fastened by means of material anchoring in the case of subsequently staggered connections and the production of lap joints of reinforcing bars in steel and concrete construction.

To do this, a hole drilled in the component or a masonry opening is first filled with a one- or multi-component mortar compound in pasty form, in order to subsequently insert components such as screws, threaded rods, hooks, reinforcing bars, etc. The material anchoring is then carried out by hardening the mortar system. This enables the connection to be adequately secured, even if the load-bearing capacity of the masonry or adjacent components themselves or the pull-out force of conventional dowels in the building envelope (outer walls, roof, building icon, terraces, basement) or in infrastructure buildings such as bridges, tunnel structures, pipeline construction , etc. is not sufficient.

Masonry injection mortars of this type are known from the prior art, for example as two-component (resin component + hardener component based on epoxy, polyurethane, polyester or polymethyl methacrylate) or one-component (cementary) reactive systems for reinforcement connections and heavy-duty fastenings. First, the systems should have sufficient strength for the constructive Provide holding function, on the other hand, take a short curing time to enable rapid construction progress. All of this, if possible, without endangering the health of processors and later users.

Reactive injection mortar systems previously available on the market perform the design tasks well, but due to their reactive components they often pose a health risk for the processor. Volatile monomers, isocyanate or epoxy systems are questionable in the event of skin contact and inhalation. This can be read e.g. on the hazard labeling on the sales containers (CLP), such as H314 - Causes severe skin burns and eye damage, H317 - May cause an allergic skin reaction, H335 - May cause respiratory Irritation, H360F - May damage fertility, Etc.

US 2014/0343194 describes stabilized aqueous quick cement suspensions with high storage stability. They contain a phosphorus-containing compound, such as phosphoric acid, for the passivation of the quick-setting cement. The cement is reactivated by raising the pH.

WO 2017/067952 discloses a two-component system for the refractory chemical anchoring of anchors or subsequent reinforcements. The system comprises a curable binder component A and an activator component B, component A containing an inhibited curable aluminate cement. This purely inorganic system leads to hard connections, but due to embrittlement they are less resistant to vibration loads. In addition, the adherence to fasteners, e.g. made of steel, often inadequate.

The object of the present invention is therefore to remedy the disadvantages of the prior art. Health risks to the user should be largely avoided and all other requirements such as sufficient final strength, hardening under conditions customary on construction sites with regard to temperature and ambient humidity and / or processing methods familiar to the user of such systems should remain fulfilled.

The object is achieved by a two-component system for forming cohesive bonds, such as adhesive joints, or for chemical anchoring, comprising a curable binder component A and an activator component B, component A containing: A-1) an inhibited hydraulic binder selected from calcium aluminate cement, calcium sulfoaluminate cement and mixtures thereof; component B contains:

B-1) a curing activator; and contains at least one of components A and / or B:

V-1) an organic binder; and

 V-2) a filler with a Mohs hardness of at least 5.

Component A contains a hydraulic binder, which is in the form of an aqueous suspension. These are aluminate cements, namely calcium aluminate cement, calcium sulfoaluminate cement or a mixture thereof.

Aluminum cements are combinations of aluminum oxide AI2O3, abbreviated as "A" in the cement nomenclature, with calcium oxide CaO, "C" in the cement nomenclature, in such amounts that C + A make up at least 20% to 100% of the total weight of the cement. Calcium sulfoaluminate cement corresponds to compounds with calcium oxide (CaO, "C"), aluminum oxide (Al2O3, "A") and sulfur oxide ("S") in such amounts that C + A + S make up at least 10% to 100% of the total weight of the cement.

In addition to the aluminate cement, the suspension can also contain other pozzolanic materials such as slag, blast furnace slag, microsilica and fly ash. The amount of other pozzolanic materials must be such that the properties of the binder are not significantly impaired.

So that the hydraulic binder does not harden prematurely or the viscosity of the suspension increases, the hydraulic binder is inhibited by adding a setting inhibitor (blocking agent). The setting inhibitor is used to passivate the hydraulic binder to prevent it from setting prematurely. The setting inhibitor prevents the cement phase from dissolving, which precedes the setting. The suspension of the inhibited hydraulic binder preferably remains liquid at ambient temperature for at least one month, preferably at least six months and particularly preferably at least one year, and does not set. The hardening is triggered in a controlled manner by a hardening activator described below. Suitable setting inhibitors are oxygen acids of phosphorus, such as orthophosphoric acid, meta-phosphoric acid, phosphonic acid (phosphorous acid); Organophosphates, or boron compounds such as borax or boric acid.

Suitable setting inhibitors are also derivatives of the oxygen acids of phosphorus, which form these acids in an aqueous medium. Examples include phosphorus pentoxide, phosphorus trioxide, pyrophosphoric acid or tripolyphosphoric acid. Suitable phosphonic acid derivatives are, for example, aminotrimethylenephosphonic acid, aminoethylphosphonic acid, 1-hydroxyethylidene-1, 1-diphosphonic acid, tetramethylenediamine-tetramethylenephosphonic acid, hexaamethylenediaminephosphonic acid, diethylenetriamine-pentamethylenephosphonic acid, phosphonobutanetronicarboxylic acid, phosphonic acid, 2-carboxylic acid, carboxylic acid , Preferred inhibitors are boric acid and orthophosphoric acid.

To prepare the inhibited hydraulic binder, an aqueous solution of the setting inhibitor can be introduced and the hydraulic binder can be introduced into the aqueous solution, advantageously with stirring.

Suspensions of inhibited hydraulic binders based on aluminate cement are commercially available, e.g. B. under the name Exalt® from Kerneos, France.

Component A also preferably contains a retarder for the setting of the aluminate cement. The retarder allows a sufficient processing time to be set as soon as the inhibited hydraulic binder is activated. In embodiments in which the organic binder is contained in component B, a setting retarder is unnecessary.

Suitable retarders are lignosulfonates; Cellulose derivatives, such as hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose; Hydroxycarboxylic acids such as tartaric acid, gluconic acid, gluconates such as sodium gluconate, gluconic acid lactone, heptonic acid, citric acid, gallic acid, pyrogallol, malic acid, tartronic acid, 2,4,6-trihydroxybenzoic acid and alkali salts thereof; synthetic retarders such as 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymers; and inorganic compounds such as ZnO.

A suitable retarder is, for example, the Lohtragon SCI Plus from Dr. Paul Lohmann GmbH, Emmerthal, Germany, available product (trisodium citrate-2-hydrate). At least one of components A and / or B, in particular component B, preferably also contains a hardening accelerator. The hardening accelerator serves for the rapid and complete hardening of the hydraulic binder as soon as the hardening is initiated by adding the hardening activator, if necessary after a processing span that can be set by adding a retarder.

The hardening accelerator is preferably selected from lithium carbonate, lithium sulfate, lithium acetate, lithium silicate, sodium carbonate, sodium sulfate, sodium silicate, sodium aluminate, potassium chloride, potassium silicate, calcium formate, calcium chloride, calcium silicate hydrate, calcium aluminate, and aluminum salts such as aluminum sulfate and mixtures thereof.

Suitable hardening accelerators are, for example, Dr. Lohtragon LCA 261, Lohtragon LCA 332 and Lohtragon LCA 442 from Dr. Paul Lohmann GmbH, Emmerthal, Germany. Peramin AXL 80 from Kerneos, France is also suitable.

At least one of components A and / or B contains an organic binder.

The organic binder gives the hardened composition desirable properties such as improved strength and adhesive properties, flexibility and sealing properties.

The organic binder is a natural or synthetic polymer or copolymer. The polymer or copolymer is preferably composed of ethylenically unsaturated compounds in copolymerized form. These polyaddition compounds are generally prepared by metal complex-catalyzed, anionically catalyzed, cationically catalyzed and particularly preferably by radically catalyzed polymerization of ethylenically unsaturated compounds which are familiar to the person skilled in the art.

The organic binder can be used in the form of an aqueous polymer dispersion which generally contains 30 to 80% by weight, in particular 50 to 75% by weight, of polymer, based on the total amount of the polymer emulsion. However, the organic binder can also be used in the form of a polymer powder.

Aqueous polyurethane dispersions are also suitable as organic binders.

In order to achieve sufficiently strong and resilient connections for hard adhesive joints and chemical anchoring, the organic binder preferably has a glass transition temperature Tg of -20 ° C. or higher, preferably 0 ° C. or higher, especially 15 ° C or higher. The glass transition temperature Tg is the midpoint temperature according to ASTM D 3418-12, determined by differential thermal analysis (DSC; heating rate: 20 K / min) [cf. also Ullmann ^'s Encyclopedia of Industrial Chemistry, page 169, Verlag Chemie, Weinheim, 1992 and Zosel in Farbe und Lack, 82, pages 125 to 134, 1976].

After Fox (TG Fox, Bull. Am. Phys. Soc. 1956 [Ser. II] 1, page 123 and according to Ullmann ^'s Encyclopedia of Industrial Chemistry, Vol. 19, page 18, 4th edition, Verlag Chemie, Weinheim, 1980) the glass transition temperature of at most weakly cross-linked copolymers can be estimated to a good approximation using the following equation

1 / Tg = x ¹ / Tg ¹ + x ² / Tg ² + .... x ⁿ / Tg ⁿ , where x ¹ , x ² , .... x ^{n are} the mass fractions of the monomers 1, 2, ... . n and Tg ¹ , Tg ² , .... Tg ^{n are} the glass transition temperatures of the homopolymers in Kelvin which are composed of only one of the monomers 1, 2, .... n. The glass transition temperatures of these homopolymers of most ethylenically unsaturated monomers are known (or can be determined experimentally in a simple manner known per se) and for example in J. Brandrup, EH Immergut, Polymer Handbook 1st Ed. J. Wiley, New York, 1966, 2nd Ed. J. Wiley, New York, 1975 and 3rd Ed. J. Wiley, New York, 1989, and in Ullmann ^'s Cncyclopedia of Industrial Chemistry, page 169, Verlag Chemie, Weinheim, 1992. The dispersion polymers are particularly advantageously in the form of particles having an average particle diameter of 10 to 1000 nm, advantageously 30 to 600 nm and particularly advantageously 50 to 400 nm, determined by the quasi-elastic light scattering method (ISO standard 13 321; cumulant z-average ), in front. The free-radically catalyzed polymerization of ethylenically unsaturated compounds is familiar to the person skilled in the art and takes place in particular by the method of free-radical bulk, emulsion, solution, precipitation or suspension polymerization, but the free-radically initiated aqueous emulsion polymerization is particularly preferred.

It is known to carry out radically initiated emulsion polymerizations of ethylenically unsaturated compounds (monomers) in an aqueous medium [cf. emulsion polymerization in Encyclopedia of Polymer Science and Engineering, Vol. 8, pages 659 ff. (1987); DC Blackley, in High Polymer Latices, Vol. 1, pages 35 ff. (1966); H. Warson, The Applications of Synthetic Resin Emulsions, Chapter 5, pages 246 ff. (1972); D. Diederich, Chemistry in our time 24, pages 135 to 142 (1990); Emulsion Polymerization, Interscience Publishers, New York (1965); DE-A 40 03 422 and dispersions of synthetic high polymers, F. Hölscher, Springer-Verlag, Berlin (1969)]. The free-radically initiated aqueous emulsion polymerization is usually carried out in such a way that the monomers, generally with the use of dispersing aids, such as emulsifiers and / or protective colloids, are dispersed in an aqueous medium and polymerized by means of at least one water-soluble free-radical polymerization initiator. In the aqueous polymer dispersions obtained, the residual contents of unconverted monomers are frequently reduced by chemical and / or physical aftertreatment, the polymer solids content is adjusted to a desired value by dilution or concentration, or the aqueous polymer dispersion contains other conventional additives, such as, for example, foam or viscosity-modifying additives added.

Suitable monomers are in particular in a simple manner radically polymerizable monomers, such as ethylene, vinyl aromatic monomers such as styrene, a-methylstyrene, o-chlorostyrene or vinyl toluenes, vinyl halides such as vinyl chloride or vinylidene chloride, esters from vinyl alcohol and 1 to 18 carbon atoms containing monocarboxylic acids, such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, esters of a, b-monoethylene-unsaturated mono- and dicarboxylic acids, preferably having 3 to 6 carbon atoms, such as especially acrylic acid, methac - Ryl acid, maleic acid, fumaric acid and itaconic acid, with alkanoias generally having 1 to 12, preferably 1 to 8 and in particular 1 to 4, carbon atoms, such as, in particular, methyl, ethyl, and n-acrylic acid and methacrylic acid. butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and 2-ethylhexyl esters, fumaric and maleic acid dimethyl esters or di-n-butyl esters, nitriles a, b-monoet hylenically unsaturated carboxylic acids, such as acrylonitrile, methacrylonitrile, fumaric acid dinitrile, maleic acid dinitrile and C4-8-conjugated dienes, such as 1, 3-butadiene and isoprene. The monomers mentioned generally form the main monomers which, based on the amount of all ethylenically unsaturated compounds used (total amount of monomers) used to prepare the dispersion polymer, comprise> 50% by weight, preferably> 80% by weight and in particular preferably> 90% by weight. As a rule, these monomers have only moderate to low solubility in water at normal conditions [20 ° C, 1 atm (= 1,013 bar absolute)].

Monomers which have an increased water solubility under the abovementioned conditions are those which have either at least one acid group and / or their corresponding anion or at least one amino, amido, ureido or N- contain heterocyclic group and / or their ammonium derivatives protonated or alkylated on nitrogen. Examples include a, b-monoethylenically unsaturated mono- and dicarboxylic acids and their amides, such as, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, acrylamide and methacrylamide, furthermore vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, Styrenesulfonic acid and its water-soluble salts and N-vinylpyrrolidone, 2-vinylpyridine, 4-vinylpyridine, 2-vinylimidazole, 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-diethylamino) ethyl methacrylate, 2- (N-tert-butylamino) ethyl methacrylate, N- (3-N ', N'-dimethylaminopropyl) methacrylamide and 2 - (1-Imidazolin-2-onyl) ethyl methacrylate. In the normal case, the abovementioned monomers are only present as modifying monomers in amounts of <10% by weight and preferably <5% by weight, based on the total amount of monomers.

Monomers which usually increase the internal strength of the films of the polymer matrix normally have at least one epoxy, hydroxyl, N-methylol, silane or carbonyl group, or at least two non-conjugated ethylenically unsaturated double bonds. Examples include glycidyl methacrylate, acetoacetoxyethyl methacrylate, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, and two monomers containing vinyl residues, two monomers containing vinylidene residues, and two monomers containing alkenyl residues. The di-esters of dihydric alcohols with a, b-monoethylenically unsaturated monocarboxylic acids are particularly advantageous, among which acrylic and methacrylic acid are preferred. Examples of such monomers having two non-conjugated ethylenically unsaturated double bonds are alkylene glycol diacrylates and dimethacrylates, such as ethylene glycol diacrylate, 1, 2-propylene glycol diacrylate, 1, 3-propylene glycol diacrylate, 1, 3-butylene glycol and diacrylate, 1, 3-butylene glycol and diacrylate Ethylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate and divinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl methacrylate, allyl methacrylate, allyl methacrylate, allyl methacrylate, allyl methacrylate, allyl methacrylate, allyl methacrylate, Cyclopentadienyl acrylate, triallyl cyanurate or triallyl isocyanurate. Of particular importance in this context are the methacrylic acid and acrylic acid-Ci-Cs-hydroxyalkyl esters such as n-hydroxyethyl, n-hydroxypropyl or n-hydroxybutyl acrylate and methacrylate as well as compounds such as diacetone acrylamide and acetylacetoxyethyl acrylate or . methacrylate. The abovementioned monomers are frequently used in amounts of <5% by weight, but preferably in amounts of <3% by weight, in each case based on the total amount of monomers.

Aqueous polymer dispersions, the dispersion polymer of which are advantageously used according to the invention 50 to 99.9% by weight of esters of acrylic and / or methacrylic acid with alkanols and / or styrene having 1 to 12 carbon atoms, or

40 to 99.9% by weight of styrene and / or butadiene, or

Contain 50 to 99.9 wt .-% vinyl chloride and / or vinylidene chloride, or 40 to 99.9 wt .-% vinyl acetate, vinyl propionate and / or ethylene in copolymerized form.

Those aqueous polymer dispersions whose dispersion polymers 0.1 to 5% by weight contain at least one a, b-monoethylenically unsaturated mono- and / or dicarboxylic acid and / or their amide having at least 3 to 6 carbon atoms are used particularly advantageously according to the invention, and

50 to 99.9% by weight of at least one ester of acrylic and / or methacrylic acid with alkanols and / or styrene having 1 to 12 carbon atoms, or

0.1 to 5% by weight of at least one a, b-monoethylenically unsaturated mono- and / or dicarboxylic acid and / or its amide having 3 to 6 carbon atoms, and

40 to 99.9% by weight of styrene and / or butadiene, or

0.1 to 5% by weight of at least one a, b-monoethylenically unsaturated mono- and / or dicarboxylic acid and / or its amide having 3 to 6 carbon atoms, and

50 to 99.9% by weight of vinyl chloride and / or vinylidene chloride, or

0.1 to 5% by weight of at least one a, b-monoethylenically unsaturated mono- and / or dicarboxylic acid and / or its amide having 3 to 6 carbon atoms, and

Contain 40 to 99.9 wt .-% vinyl acetate, vinyl propionate and / or ethylene in copolymerized form. The free-radically initiated aqueous emulsion polymerization for the preparation of the dispersion polymers is generally carried out in the presence of 0.1 to 5% by weight, preferably 0.1 to 4% by weight and in particular 0.1 to 3% by weight. based in each case on the total amount of monomers, of a radical polymerization initiator (radical initiator). Free radical initiators are all those which are capable of initiating a free radical aqueous emulsion polymerization. In principle, these can be both peroxides and azo compounds. Of course, redox initiator systems can also be used. In principle, inorganic peroxides, such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfonic acid, such as, for example, their mono- and di-sodium, potassium or ammonium salts or organic peroxides, can be used as peroxides. such as alkyl hydroperoxides, for example tert-butyl, p-menthyl or cumyl hydroperoxide, and dialkyl or diaryl peroxides, such as di-tert-butyl or di-cumyl peroxide. As an azo compound essentially 2,2 ^'azobis (isobutyronitrile), ^2,2'-azobis (2,4-dimethylvaleronitrile), and ^2,2'-azobis (amidinopro- pyl) dihydrochloride (AIBA, corresponding to V-50 from Wako Chemicals). So-called redox initiator systems can of course also be used as radical initiators. The above-mentioned peroxides are essentially suitable as oxidizing agents for redox initiator systems. Sulfur compounds with a low oxidation state, such as alkali sulfites, for example potassium and / or sodium sulfite, alkali hydrogen sulfites, for example potassium and / or sodium hydrogen sulfite, alkali metabisulfites, for example potassium and / or sodium metabisulfite, formaldehyde sulfoxylates, for example potassium and / o- sodium formaldehyde sulfoxylate, alkali metal salts, especially potassium and / or sodium salts, aliphatic sulfinic acids and alkali metal hydrogen sulfides, such as, for example, potassium and / or sodium hydrogen sulfide, salts of polyvalent metals, such as iron (II) sulfate, iron (II ) Ammonium sulfate, iron (II) phosphate, endiols, such as dihydroxymaleic acid, benzoin and / or ascorbic acid, and reducing saccharides, such as sorbose, glucose, fructose and / or dihydroxyacetone.

Usually, dispersion aids are used in the preparation of the dispersion polymers by means of radically initiated aqueous emulsion polymerization, which keep both the monomer droplets and polymer particles dispersed in the aqueous phase and thus ensure the stability of the aqueous dispersions of the dispersion polymers produced. Both the protective colloids usually used to carry out free-radical aqueous emulsion polymerizations and emulsifiers come into consideration as such. Suitable protective colloids are, for example, polyvinyl alcohols, cellulose derivatives or copolymers containing vinylpyrrolidone. A detailed description of further suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, pages 41 1 to 420, Georg-Thieme-Verlag, Stuttgart, 1961. Mixtures of emulsifiers can of course also be used and / or protective colloids can be used. Preferably only emulsifiers are used as dispersing agents, the relative molecular weights of which, in contrast to the protective colloids, are usually below 1000. They can be of anionic, cationic or nonionic nature. Of course, if mixtures of surface-active substances are used, the individual components must be compatible with one another, which can be checked with a few preliminary tests if in doubt. In general, anionic emulsifiers are compatible with one another and with nonionic emulsifiers. The same applies to cationic emulsifiers, while anionic and cationic emulsifiers are usually not compatible with one another. Common emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO grade: 3 to 50, alkyl radical: C ₄ to C12), ethoxylated fatty alcohols (EO degree: 3 to 50; alkyl radical: C8 to C36) and alkali metal - and ammonium salts of alkyl sulfates (alkyl radical: C8 to C12), of sulfuric acid half-esters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C12 to Cie) and ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ to C12), of alkyl sulfonic acids (alkyl radical: C12 to Cie) and of alkylarylsulfonic acids (alkyl radical: Cg to Cis). Further suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, pages 192 to 208, Georg-Thieme-Verlag, Stuttgart, 1961. Compounds of the general formula have also been found to be surface-active substances I

wherein R ¹ and R ^{2 are} H atoms or C ₄ - to C2 ₄ alkyl and are not simultaneously H atoms, and M ¹ and M ^{2 can be} alkali metal ions and / or ammonium ions, have been found to be suitable. In the general formula (I), R ¹ and R ^{2 are} preferably linear or branched alkyl radicals having 6 to 18 carbon atoms, in particular having 6, 12 and 16 carbon atoms or hydrogen, where R ¹ and R ^{2 are} not both at the same time Are H atoms. M ¹ and M ² are preferably sodium, potassium or ammonium, sodium being particularly preferred is preferred. Compounds (I) in which M ¹ and M ² are sodium, R1 is a branched alkyl radical having 12 C atoms and R ^{2 is} an H atom or R1 are particularly advantageous. Technical mixtures are frequently used which have a proportion of 50 to 90% by weight of the monoalkylated product, such as Dowfax® 2A1 (trademark of the Dow Chemical Company). The compounds (I) are generally known, for example from US Pat. No. 4,269,749, and are commercially available.

Nonionic and / or anionic emulsifiers are advantageously used in the preparation of the dispersion polymers by free-radically initiated aqueous emulsion polymerization.

As a rule, the amount of dispersing aid used is 0.1 to 5% by weight, preferably 1 to 3% by weight, in each case based on the total amount of monomers. It is often expedient for some or all of the dispersing aid to be added to the aqueous reaction medium before the radical polymerization is initiated. In addition, some or all of the dispersing aid can advantageously also be added together with the monomers, in particular in the form of an aqueous monomer emulsion, during the polymerization by means of the aqueous reaction medium.

Free-radical chain-transferring compounds are usually used in order to reduce or to control the molecular weight of the polymers A, dispersion polymers, which are accessible by a free-radically initiated aqueous emulsion polymerization. Essentially aliphatic and / or araliphatic halogen compounds, such as, for example, n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloromethane,

Dibromo dichloromethane, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide, organic thio compounds, such as primary, secondary or tertiary aliphatic thiols, such as, for example, ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethiol, 2-methyl-2- propanethiol, n-pentanethiol, 2-pentanethiol, 3-pentanethiol, 2-methyl-2-butanethiol, 3-methyl-2-butanethiol, n-hexanethiol, 2-hexanethiol, 3-hexane thiol, 2-methyl 2-pentanethiol, 3-methyl-2-pentanethiol, 4-methyl-2-pentanethiol, 2-methyl-3-pentanethiol, 3-methyl-3-pentanethiol, 2-ethylbutanethiol, 2-ethyl-2-butanethiol, n-heptanethiol and its isomeric compounds, n-octanethiol and its isomeric compounds, n-nonanthiol and its isomeric compounds, n-decanethiol and its isomeric compounds, n-undecanethiol and its isomeric compounds, n-dodecanthone and its isomeric Compounds, n-tridecanethiol and its isomeric compounds, substituted thiols, such as 2-hydroxyethanethiol, a aromatic thiols, such as benzenethiol, ortho-, meta-, or para-methylbenzenethiol, and all other im Polymerhandbook 3rd edition, 1989, J. Brandrup and EH Immergut, John Weiley & Sons, Section II, pages 133 to 141, described sulfur compounds, but also aliphatic and / or aromatic aldehydes, such as acetaldehyde, propionaldehyde and / or benzaldehyde, unsaturated fatty acids, such as oleic acid, dienes with non-conjugated double bonds, such as divinyl methane or vinyl cyclohexane, or hydrocarbons with easily abstractable hydrogen atoms, such as toluene, for example. However, it is also possible to use mixtures of the above-mentioned radical chain-transferring compounds which do not interfere with one another. In addition to the seed-free production method, to adjust the polymer particle size, the emulsion polymerization for the preparation of the dispersion polymers P can be carried out by the seed latex process or in the presence of a seed latex prepared in situ. Methods for this are known to the person skilled in the art and can be found in the prior art (see, for example, EP-B 40 419, EP-A 567 812, EP-A 614 922 and 'Encyclopedia of Polymer Science and Technology', vol. 5, page 847 .

John Wiley & Sons Inc., New York, 1966). In the semi-continuous feed process, the prior art recommends that a defined, finely divided seed polymer dispersion be placed in the polymerization vessel and then the monomers polymerized in the presence of the seed latex. Here, the seed polymer particles act as "polymerization nuclei" and decouple the polymer particle formation and the polymer particle growth. During the emulsion polymerization, further seed latex can be added directly to the polymerization reactor. As a result, wide size distributions of the polymer particles are achieved, which are often desirable in particular in polymer dispersions with a high solids content (cf., for example, DE-A 4213965). Instead of adding a defined seed latex, it can also be generated in situ. For this purpose, for example, a subset of the monomers used for the polymerization and the radical initiator are initially introduced together with a subset or the total amount of the emulsifier and heated to the reaction temperature, a relatively finely divided polymer seed being formed. The actual polymerization is then carried out in the same polymerization vessel using the feed process (see also DE-A 4213965).

The dispersion polymers are advantageously prepared by free-radically initiated aqueous emulsion polymerization at a reaction temperature in the range from 0 to 170 ° C., but temperatures from 70 to 120 ° C. and in particular 80 to 100 ° C. are particularly preferred. The radical aqueous emulsion polymerization can be carried out at a pressure of less than, equal to or greater than 1 atm (absolute). Volatile monomers such as ethylene, butadiene or vinyl chloride are preferably polymerized under elevated pressure. The pressure can be 1, 2, 1, 5, 2, 5, 10, 15 bar (Overpressure) or even higher values. If emulsion polymerizations are carried out under reduced pressure, pressures of 950 mbar, often 900 mbar and often 850 mbar (absolute) are set. The radical aqueous emulsion polymerization is advantageously carried out at 1 atm (= atmospheric pressure = 1.013 bar absolute) under an inert gas atmosphere, such as, for example, under nitrogen or argon.

Aqueous polyurethane dispersions consist of polyurethane polymers or polyurethane-polyurea polymers, which are accessible through polyaddition reactions of polyols, polyisocyanates and polyamines. Polyurethane prepolymers are first produced from the polyols and the polyisocyanates, which are then dispersed in the aqueous phase and chain-extended with polyamines to form the polyurethane-polyurea polymers. The polyurethane polymers also contain a sufficient amount of hydrophilic groups, which ensure stabilization in the aqueous phase. These hydrophilic groups are anionic, cationic or non-ionic groups. Polyurethane dispersions are two-phase systems that consist of micelles with polyurethane polymers and an aqueous phase. When the polyurethane dispersions are dried, the micelles coalesce or fuse and the polyurethane polymers film or film.

At least one of components A and / or B also contains a filler with a Mohs hardness of at least 5, in particular at least 6. The Mohs hardness is a relative hardness value of minerals. The Mohs hardness covers a range from 1 to 10 on an ordinal scale. Each mineral classified on this scale scratches the previous one and is scratched by the subsequent ones. The specified Shore hardness is important in order to achieve sufficiently strong and resilient connections for hard adhesive joints and chemical anchoring. Suitably the filler is e.g. selected from sand, corundum, gravel, stone powder, glass powder, glass balls, hollow glass balls, glass fibers, metal fibers and pyrogenic silicon dioxide. , The filler preferably has a weight-average particle size of 1 pm to 100 pm, in particular 5 pm to 50 pm.

Component A and / or component B can also contain additives such as rheology modifiers, in particular thickeners, water repellents, film-forming aids, plasticizers, biocides and / or preservatives or combinations.

Both organic and inorganic thickeners can be used as thickeners. Suitable organic thickeners are selected from cellulose ethers, starch ethers, polyacrylamides and associative thickeners. In a further embodiment, the thickener is selected from polysaccharide derivatives and (co) polymers with a weight average molecular weight Mw of more than 500,000 g / mol, in particular more than 1,000,000 g / mol. In a further embodiment, the thickener is selected from cellulose ethers, starch ethers and (co) polymers which comprise structural units of non-ionic (meth) acrylamide monomers and / or sulfonic acid monomers and, if appropriate, of further monomers.

Suitable cellulose ethers are alkyl celluloses such as methyl cellulose, ethyl cellulose, propyl cellulose and methyl ethyl cellulose; Hydroxyalkyl celluloses such as hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC) and hydroxyethyl hydroxypropyl cellulose; Alkylhydroxyalkylcelluloses such as methylhydroxyethylcellulose (MHEC), methylhydroxypropylcellulose (MHPC) and propylhydroxypropylcellulose; and carboxylated cellulose ethers, such as carboxymethyl cellulose (CMC). Preferred are the non-ionic cellulose ether derivatives, in particular methyl cellulose (MC), 20 hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC) and ethyl hydroxyethyl cellulose (EHEC), and particularly preferred are methyl hydroxyethyl cellulose (MHEC) and methyl hydroxypropyl cellulose (MHPC). The cellulose ether derivatives are each obtainable by appropriate alkylation and alkoxylation of cellulose and commercially.

Suitable starch ethers are nonionic starch ethers, such as H yd roxypropyl starch, hydroxyethyl starch and methyl hydroxypropyl starch. Hydroxypropyl starch is preferred. Suitable thickeners are also microbially produced polysaccharides such as welan gum and / or xanthans and naturally occurring polysaccharides such as alginates, carrageenans and galactomannans. These can be obtained from corresponding natural products by extractive processes, such as 30 from algae in the case of alginates and carrageenans, from carob seeds in the case of galactomannans.

(Co) polymers with a weight average molecular weight MW of more than 500,000 g / mol, particularly preferably more than 1,000,000 g / mol, can (preferably by radical polymerization) be prepared from nonionic (meth) acrylamide monomers and / or sulfonic acid monomers. In one embodiment, the monomers are selected from acrylamide, methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N, N-dimethylacrylamide, N-ethyl acrylamide,

N, N-diethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminoethylacrylamide and / or N-tert-butylacrylamide and / or styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2 - Methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid and / or 2-acrylamido-2,4,4-trimethylpentanesulfonic acid or the salts of the acids mentioned. The (co) polymers preferably contain more than 50 mol% and particularly preferably more than 70 mol% of structural units which are derived from nonionic (meth) acrylamide monomers and / or sulfonic acid monomers. Other structural units that can be contained in the copolymers are, for example, the monomers (meth) acrylic acid, esters of (meth) acrylic acids with branched or unbranched C to CIO alcohols, vinyl acetate, vinyl propionate and / or styrene derived.

In a further embodiment, the thickener is selected from methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl starch, hydroxyethyl starch, methyl hydroxypropyl starch, and (co) polymers which contain structural units which are derived from acrylamide, methacrylamide, N, N-dimethylacrylamide, 2 -Acrylamido-2-methylpropanesulfonic acid and optionally (meth) acrylic acid, esters of (meth) acrylic acids with branched or unbranched C to CIO alcohols, vinyl acetate, vinyl propionate and / or styrene.

Associative thickeners, such as the polyurethane associative thickeners known per se, such as Rheovis® or PURE TH IX, e.g. Rheovis PU 1270. These thickeners are made up of linear and / or branched polyethylene glycol blocks and hydrophobic segments, which are usually linked together via urethane groups.

Suitable inorganic thickeners are, for example, layered silicates, such as montmorillonite, hectorite, attapulgite or smectite. Suitable layered silicates are e.g. Laponite RD (Deutsche Solvay GmbH); Optigel SH; SKS-20 / Saponite; Attagel 50; SKS-21 / hectorite. Fumed silicas such as Aerosil types (Evonik Resource Efficiency GmbH) are also suitable as thickeners.

In addition, natural or synthetic fibers can also be added, for example for reinforcement. Intumescent or fire-retardant fillers can also be added, such as expanded graphite or aluminum hydroxide or magnesium hydroxide. Other suitable flame retardants are brominated flame retardants, such as octabromodiphenyl ether, decabromodiphenyl ether, chlorinated flame retardants such as tetrabromobisphenol A, organophosphorus flame retardants (which may be halogenated), such as tris (2-chloroisopropyl) phosphate tris (1, 3-dichloroisopor) , or antimony trioxide. Components A and B are produced by mixing the components using conventional mixing techniques and mixing devices.

Component A generally has a solids content of 10 to 90% by weight, preferably 40 to 85% by weight. Component A generally has a pasty consistency.

Based on the solids content, the two-component system (after mixing components A and B) contains the hydraulic binder A-1) and the organic binder V-1) generally in a weight ratio of 10: 1 to 1:10, preferably 5: 1 to 1: 5, in particular 1: 2 to 2: 1.

In relation to the solids content, the two-component system (after mixing components A and B) generally contains:

15 to 50% by weight, preferably 20 to 40% by weight, filler V-2)

Regarding the solids content, the two-component system generally contains:

0 to 8 wt .-%, preferably 1 to 5 wt .-%, curing accelerator.

Based on the solids content, component A generally contains:

0 to 2% by weight, preferably 0 to 0.5% by weight, retarder.

To initiate curing, component A is mixed with activator component B containing the curing activator. The hardening activator is in particular an alkalizing agent (pH trigger). For example, alkali and alkaline earth metal hydroxides, oxides and carbonates or Portland cement or mixtures thereof are suitable for this. Alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide or mixtures thereof are preferred. Sodium hydroxide or potassium hydroxide or a mixture thereof are particularly preferred. The alkalizing agents can be used in the form of an aqueous solution, for example a 10 to 30% solution, or in solid form. Other suitable alkalizing agents are ammonia and amines, such as triethanolamine, dimethylethanolamine, methyldiethanolamine and the like. The hardening activator serves to activate the hardening and drying. It is therefore only mixed with component A immediately before use. "Immediate" is less than 10 minutes here. understand before use. The amount of alkalizing agent is chosen so that the pH rises to at least 8, preferably to at least 9, but preferably not above 11.5. Higher pH values may require labeling. The processing time can be regulated in a wide range via the amount of alkalizing agent or the resulting pH value and, if appropriate, the amount of the curing accelerator.

The invention also relates to a method for forming cohesive bonds or for chemical anchoring, in which a) component A and component B of a two-component system according to the invention are mixed,

b) the mixture is introduced into a recess in a substrate or a space between substrates, and

c) if appropriate, an anchoring element or reinforcing element is introduced into the recess or the intermediate space.

The substrate is, for example, concrete, stone, brick, plaster, plasterboard, wood, glass, aluminum, plastic or bitumen.

The recess is preferably a hole, blind hole, a joint, a crack or a groove.

The method serves e.g. for sealing and / or filling joints, seams, cracks in one substrate or between different substrates, e.g. to form adhesive joints or crack bonds.

The anchoring element is e.g. selected from screws, threaded rods, hooks, reinforcing bars, metal slats or the like.

The two-component system according to the invention is stable in storage in that the activator component B is kept separate from the component A until use.

Any type of two-component container is conceivable for mixing and dispensing, which keeps the two components separate until use and enables homogeneous mixing at the time of application. Containers, barrels, buckets, mugs, bags, hoses, cans, syringes, cannulas, tubes, etc. Bottles, etc. with two different sized chambers. The chambers do not necessarily have to be connected in one structural unit, they can also be present separately. The containers can be equipped with a suitable mixing unit, such as static or dynamic mixers, or they can be mixed separately in one of the two component containers or entirely outside of the component containers. The containers are made of a suitable material that meets the requirements for permanent tightness, chemical resistance, product safety, handling, transport law and the like. Sheet metal, plastic or glass is usually used for this.

The invention also relates to a device for mixing and dispensing the two-component system with

 a first chamber with component A,

 a second chamber with component B,

 a mixing chamber which comprises at least a first inlet opening which is connected to the first chamber, at least a second inlet opening which is connected to the second chamber and with at least one outlet opening for the exit of the material from the mixing chamber, and

 - An actuating means for conveying the first and second components into the mixing chamber.

Both components can e.g. be introduced into commercially known two-component cartridges with a mixed discharge tip which are known per se. With this packaging method, the provision and use of the two-component system according to the invention is particularly simple and safe.

For the filling of boreholes and masonry openings with injection mortar masses, manually or motor-operated extrusion devices are often used. The borehole is backfilled correctly from the bottom of the borehole with the masonry injection mortar, which at the beginning was still pasty, but after hardening, it is high-strength. To ensure that the borehole is evenly filled with the mortar, the user has to pull the extruder evenly according to the progress of the backfilling. When retrofitting, for example, reinforcing irons, the boreholes have a relatively large depth. To backfill these deep boreholes, the dispensers are provided with extension tubes or hoses so that backfilling can be carried out from the bottom of the borehole in accordance with regulations. Inclusions of air and uneven backfilling with this type of material anchoring of fasteners in boreholes are to be avoided in principle, as this can have a negative effect on the holding values of the subsequently attached fastening element.

With the aid of the two-component system according to the invention, it is possible to combine the advantages of reactive masonry injection mortar and conventional pasty assembly adhesive systems. For example, the mechanical properties, in particular the pull-out force and curing speed, are achieved and, at the same time, the level of handling of paste-like, aqueous assembly adhesive systems that is harmless to health is provided. The hydraulic fast-curing binder system, which was only activated during mixing, further reduces the usual shrinkage of aqueous adhesive formulations without sacrificing the tensile strength of reactive systems. Thus, already after 24 hours the tensile bond strength of a glued to the inventions to the invention two-component system threaded rod (Steel 4.8 blank M6 according to DIN 975) in immersion depth 40mm> 1 N / mm ^2, preferably> 1, 5 N / mm ^2. The value for a commercially available reactive system (Hilti HIT-1) is approximately 3.0 N / mm ² .

In addition, the two-component system according to the invention shows good curing times, even in the case of high atmospheric humidity (80-100%) or residual moisture in the borehole. It can be produced without a great deal of mixing effort, since the mixture can be produced in situ directly during use by means of a suitable packaging method.

The two-component system according to the invention hardens with a high pH which is able to passivate structural steel. Steel anchors glued to it are also protected against rust in addition to secure anchoring.

The two-component system according to the invention is particularly suitable for producing a permanent fastening of holding elements in an on-site subsurface. Worth mentioning here, for example, are the materially anchoring of fastening elements such as screws, threaded rods, structural steels, expansion anchors, tenons and the like in drill holes and masonry openings on the building envelope (roof, building icon, terraces, cellars, walls, ceilings, floors) and on infrastructure - door buildings such as bridges, roads and tunnels.

The following examples illustrate the invention.

test methods The pull-out force was determined based on ISO 6922.

The curing time was determined by observing when the two-component system changes from the plastic to the solid state after components A and B have been mixed.

Example 1 Masonry injection mortars of the composition given in Table 1 were produced; the percentages by weight relate to the total weight of the two-component system. The following ingredients were used:

- Suspension from passivated quick cement: Slurry 2 of US 2014/0343194 with a cement content of about 60%;

 Polymer 1 (Tg = 24 ° C): pure acrylate copolymer, solids content 50% by weight;

 Polymer 2 (Tg = -43 ° C): pure acrylate copolymer, solids content 70% by weight;

The formulations were standardized to the same polymer content.

- pigment distributor: Dispex AA 4030, BASF SE;

 Emulsifier: Lutensol AT 18, BASF SE;

 Inorganic thickener: Attagel 50;

 Thickener: Rheovis PU 1270, BASF SE;

 Filler: quartz sand F36 (Mohs hardness 7);

 Talc (Mohs hardness 1);

 Accelerator: Peramin AXL 80, Kerneos, Paris, France;

Retarder: sodium gluconate, BASF SE.

Table 1 :

^* Comparative test For comparison, the pull-out force of a market product based on epoxy is 2760 N.

The examples show that the system according to the invention can quickly build up high strengths. The use of a filler with insufficient Mohs hardness (test 5) leads to a deterioration in the pull-out strength. A composition without cement (test 2) slowly hardens. The use of an organic binder with a high Tg (Tg higher than -20 ° C; test 1 vs. test 4) is advantageous for high pull-out strength. The system according to the invention is an aqueous system which is harmless to health.

Claims

claims 1. Two-component system for forming cohesive composites or for chemical anchoring, comprising a curable binder component A and an activator component B, component A containing: A-1) an inhibited hydraulic binder selected from calcium aluminate cement, calcium sulfoaluminate cement and mixtures thereof; component B contains: B-1) a curing activator; and contains at least one of components A and / or B: V-1) an organic binder; and  V-2) a filler with a Mohs hardness of at least 5. 2. Two-component system according to claim 1, wherein the hydraulic binder is inhibited by means of a setting inhibitor, which is selected from boric acid, oxygen acids of phosphorus and salts thereof. 3. Two-component system according to claim 1 or 2, wherein component A also contains: A-2) a retarder. 4. Two-component system according to claim 3, wherein the retarder is selected from lignosulfonates, cellulose derivatives, hydroxycarboxylic acids, synthetic retarders, and inorganic compounds and mixtures thereof. 5. Two-component system according to one of the preceding claims, wherein at least one of components A and / or B contains: V-3) a curing accelerator. 6. Two-component system according to claim 5, wherein the curing accelerator selected from lithium carbonate, lithium sulfate, lithium acetate, lithium silicate, sodium carbonate, sodium sulfate, sodium silicate, sodium aluminate, potassium chloride, Potassium silicate, calcium formate, calcium chloride, calcium silicate hydrate, calcium aluminate, and aluminum salts and mixtures thereof. 7. Two-component system according to one of the preceding claims, wherein the filler is selected from sand, corundum, gravel, stone powder, glass powder, Glass balls, hollow glass balls, glass fibers, metal fibers and pyrogenic silicon dioxide. 8. Two-component system according to one of the preceding claims, wherein the organic binder has a glass transition temperature Tg of -20 ° C or higher. 9. Two-component system according to one of the preceding claims, wherein the curing activator is an alkalizing agent. 10. A method for forming cohesive composites or for chemical anchoring, in which a) component A and component B of a two-component system according to one of the preceding claims are mixed,  b) the mixture is introduced into a recess in a substrate or a space between substrates, and  c) if necessary, an anchoring element or reinforcing element is introduced into the recess or the intermediate space. Device for mixing and dispensing the two-component system according to one of claims 1 to 9, with  a first chamber with component A,  a second chamber with component B,  a mixing chamber which comprises at least a first inlet opening which is connected to the first chamber, at least a second inlet opening which is connected to the second chamber and with at least one outlet opening for the exit of the material from the mixing chamber, and  - An actuating means for conveying the first and second components into the mixing chamber.