EP4175942A1

EP4175942A1 - Special imines and their starting materials, and use during the curing of reactive resins by polyaddition or radical polymerization

Info

Publication number: EP4175942A1
Application number: EP21733107.3A
Authority: EP
Inventors: Christian Weinelt; Martin Vogel
Original assignee: Fischerwerke GmbH and Co KG
Current assignee: Fischerwerke GmbH and Co KG
Priority date: 2020-07-02
Filing date: 2021-06-14
Publication date: 2023-05-10
Also published as: DE102021114890A1; US20230323008A1; WO2022002567A1

Abstract

Imine, obtainable by reacting (i) an amino-functionalized polyoxyalkylene, the polyoxyalkylene chains being a copolymer that consists of oxyethylene- and oxypropylene units, and these polyoxyalkylene chains carry (preferably per molecule two terminal) primary amino groups, and (ii) a ketone and/or aldehyde with one hydrogen atom at the carbon atom in alpha position to the carbonyl carbon. The invention also relates to various inventions based thereon, in particular in relation to coating or adhesive systems.

Description

Special imines and their starting materials, as well as use in curing reactive resins by polyaddition or radical polymerization

The invention relates to a special type of imines which is suitable as part of a curing system for radically polymerizable reactive resins and / or for reactive resins curable by polyaddition in coating and / or adhesive systems.

There are a number of adhesives and coating materials on the market that are based on the one hand on free-radically curable compounds or on the other hand on compounds curable by polyaddition (such as, for example, monomers, oligomers or prepolymers carrying two or more isocyanate groups and / or epoxy groups (per molecule)). The polymerisation (curing) of the adhesives and coating materials mentioned takes place in each case by means of curing systems which, in the first case, comprise free radical initiators and, in the second case, amines bearing two or more amino groups and, if appropriate, further constituents.

Imines and their precursors (amines and ketones or aldehydes) as components of such hardener systems for radically hardenable adhesives are known from WO 2016/206777 A.

The object was to provide further synthetic resin systems that can be replaced in a variety of ways in the field of coating and fastening technology, through which (in the case of fastening anchoring means in boreholes) improved properties - in particular increased reactivity compared to previously known and comparable systems and above all improved bond stresses - are obtained. A further object was to provide an imine which is superior in its labeling to the imines commercially available up to now (namely does not require labeling) and with which very good tensile shear strengths are nevertheless obtained for bonds such as beech to beech.

Surprisingly, it has been found that certain imines, namely those which are obtainable by reacting an amino-functionalized polyoxyalkylene whose polyoxyalkylene chains are a copolymer of oxyethylene and oxypropylene units, these polyoxyalkylene chains (preferably terminal) carrying primary amino groups, with a ketone and / or preferably one Aldehyde with a hydrogen atom on the carbon atom in the alfa position to the carbonyl group (-C (= 0) -, enable such properties to be improved compared to imines known from WO 2016/206777 A1. In addition, these imines can also be used for curing, for example, epoxies or isocyanates for coatings or bonds.

In a first embodiment of the invention, this consequently relates to an imine, obtainable by reacting (i) an amino-functionalized polyoxyalkylene whose polyoxyalkylene chains are a copolymer of oxyethylene and oxypropylene units, these polyoxyalkylene chains (preferably two terminal per molecule) carrying primary amino groups, and ( ii) a ketone and / or (preferably) aldehyde with one (preferably one (= 1) single) hydrogen atom on the carbon atom in the alpha position to the carbonyl carbon.

In a second embodiment, the invention relates to an imine as mentioned above, which by reacting the amino-functionalized polyoxyalkylene (i), which in each case has a primary amino group bonded to the terminal oxyalkylene group, with an alkanaldehyde (ii), in particular a C2-Cs-alkanaldehyde, in particular one which is simply branched in the alfa position to the carbonyl group, for example carries a methyl group there. Isobutyraldehyde is particularly preferred.

In a third embodiment, the invention relates to an imine as defined above, characterized in that the amino-functionalized polyoxyalkylene (i) has two terminal 2-aminopropyloxy groups.

In a fourth embodiment, the invention relates to an imine as defined above, characterized in that the amino-functionalized polyoxyalkylene (i) has the following formula:

NH2-CH (CH3) -CH2- [0-CH2-CH (CH3) -] i (0-CH2-CH2) m [0-CH2-CH _(CH3) -] n NH 2 where I and n each independently on average for 1 to 10, preferably 3 to 4, in particular about 3.6; and m is 1 to 50, preferably 8 to 10, in particular about 9, stand _. In the above formula, I and n mean approximately 3.6 on average and m approximately 9 on average, with “approximately” preferably meaning a range of variation of ± 0.2, in particular of ± 0.1.

In a fifth embodiment, the invention relates to an imine as defined in one of the preceding embodiments, characterized in that it is an average Molecular weight of 2000 g / mol or lower, for example 1000 g / mol or lower.

A sixth embodiment of the invention relates to an imine as defined in one of the preceding embodiments in a (in particular equilibrium) mixture with its starting materials (i) amino-functional polyoxyalkylene and (ii) ketone and / or (preferably) aldehyde. This variant is an option when it comes to radical curing (as a radical initiator).

A seventh embodiment of the invention relates to a mixture of (i) an amino-functional polyoxyalkylene and (ii) an aldehyde and / or ketone, preferably an aldehyde; as each defined in one of the preceding embodiments.

An eighth embodiment of the invention relates to a mixture as defined in the preceding paragraph as a component of a coating system or adhesive system (or adhesive).

A ninth embodiment of the invention relates to a hardener that

- in the case of the radical curable compounds (case A) the following initiator system includes:

(A) at least one activator in the form of a metal salt and, as free radical initiator (b1), an amino-functional polyoxyalkylene (i) as defined in one of the preceding embodiments in a mixture with an aldehyde and / or ketone (ii), preferably an aldehyde, as in each case in one defined by the above embodiments; or

(b2) an imine as defined in one of the preceding embodiments, or a mixture of components (b1) and (b2); or

- in the case of the compounds curable by polyaddition (case B) represents the following constituent: (b2) an imine as defined in one of the preceding embodiments.

In the case of polyaddition, curing takes place by means of (in the presence of moisture,

(e.g. humidity or moisture in the substrate to be bonded); that is, water) from the amine released from the imine, which adds to an isocyanate and / or epoxy group, preferably isocyanate.

In a tenth embodiment, the invention relates to a coating system or in particular a special adhesive system, including a hardener (initiator system), as described for the ninth embodiment, and as reactive resin either (Aa) a radically polymerizable reactive resin or (Ba) a reactive resin curable by polyaddition, or a mixture of (Aa) and (Ba).

In an eleventh embodiment, the invention relates to a coating system or, in particular, an adhesive system according to the preceding paragraph, in which the reactive resin is a radically curable reactive resin according to (Aa).

A twelfth embodiment of the invention relates to a coating or in particular adhesive system according to the penultimate paragraph, wherein the reactive resin is a reactive resin curable by polyaddition according to (Ba) (as mentioned in the tenth embodiment of the invention), in particular an oligomer containing at least two isocyanate groups and / or prepolymer.

In a thirteenth embodiment, the invention relates to a coating or in particular special adhesive system according to one of the last three paragraphs in the form of a multi-component, in particular two-component system, which is a reactive resin according to (Aa) or (Ba) and in one component other component includes a hardener according to the tenth embodiment.

A fourteenth embodiment of the invention relates to a coating or in particular adhesive system according to the twelfth embodiment in the form of a one-component system, preferably one, in particular in the presence of moisture (water, as such or in an aqueous solution with another solvent or solvent mixture), polyaddition curing lacquer or a polyaddition curing adhesive.

In a fifteenth embodiment, the invention relates to the use of an adhesive system as defined in one of the embodiments ten to fourteen

(a) for gluing objects together or

(b) for adhering an object to a stationary substrate. A sixteenth embodiment of the invention relates to a use according to the preceding paragraph, variant (b), the subject being a swimming pool, room, bathroom or kitchen accessory or an adapter element for receiving such an accessory; a plate or block, preferably made of metal, glass, plastic, concrete or stone; Fibers, in particular high-modulus fibers, preferably carbon fibers, in particular for reinforcing structures, for example walls, pillars, ceilings or floors; a component such as a plate, a disk or a block, for example made of stone, glass or plastic; or - each designed as a flat mat and as a free material or as a composite material or material - a fleece, a woven fabric, a knitted fabric, a flat material obtained by knitting, a material obtained by tufting, preferably each with high-modulus fibers, for example made of glass fiber , Carbon fiber and / or plastic fiber, in the case of a composite material with a plastic matrix, is to be understood; and a substrate is to be understood as a building substrate, in particular a wall, a wall, a ceiling or a floor in the building sector, preferably made of masonry, concrete, free or glazed ceramic, or also made of glass, wood, metal or plastic.

A seventeenth embodiment of the invention relates to a use according to the preceding paragraph of an adhesive system as defined in one of the embodiments ten to fourteen for gluing an anchoring element in a hole or a recess in the substrate, in particular in a borehole.

An eighteenth embodiment of the invention relates to a use after the penultimate paragraph of a coating system as defined in one of the embodiments ten to fourteen for coating a substrate, the substrate preferably being a building substrate.

In a nineteenth embodiment of the invention, this relates to a method for coating a substrate with a coating system as defined in one of the execution forms ten to fourteen, the coating system, if necessary below or after mixing of components thereof which do not harden on their own, is applied and hardened with polymerization.

A twentieth embodiment of the invention relates to a method

(a) for gluing objects together or

(b) for gluing an object to a stationary substrate, with an adhesive system as defined in one of the embodiments ten to fourteen, if necessary under or after the mixing of components thereof which otherwise do not react with one another, to one or more areas to be glued to one or more of the to objects to be bonded are applied and areas to be bonded are brought into contact with one another and the adhesive system is cured with polymerization, the method in particular including the use as in one of the embodiments fourteen to seventeen.

The invention also relates to the subjects of the invention mentioned in the independent and in particular in the dependent claims, which are here preferably to be regarded as being incorporated into the description by reference.

The above and below specific definitions of individual, several or all features of an object of the invention can be used to replace more specific features, which leads to preferred objects of the invention (embodiments of the invention), which are also the subject of the present invention.

Where weight information is given in percent (% by weight), unless otherwise stated or evident, it relates to the total mass of the reactants and additives of all components of the coating or adhesive system (liquid or paste-like in the fully formulated state), i.e. without packaging, ie the (weight) mass of the or all of the associated component parts.

Where the attribute “further” is mentioned, it means that characteristics without this attribute are more preferred. “And / or” means that the features / substances mentioned can each be present alone or in combination of two or more of the features / substances mentioned in each case.

Wherever “average” is mentioned, this refers to the number of the respective groups in relation to the number of molecules that contain an addressed group, i.e. the arithmetic mean.

“Include” or “comprise” or “contain” means that in addition to the components or features mentioned, others may also be present, so it stands for a non-exhaustive list, in contrast to “consisting of”, which is a concluding list of when it is used means listed components or features. In particular embodiments of the subject matter of the invention, the definitive “consisting of” can be used instead of “include” or “comprise”.

Instead of “obtainable” through a reaction, “obtained” through the reaction can in particular be used.

Where “a” or “an” is used, this is to be understood primarily as the indefinite article (unless otherwise indicated, for example by adding “at least”) and includes “a (in numbers: 1) or several “as well as just one (in numbers: 1). In other words, "one" or "an" means "one or more, e.g. two or three or four". “At least one” stands for one or more. Where the plural is used, this also includes the singular.

The phrase "with a hydrogen atom on the carbon atom in alpha position to the carbonyl group" means with at least one hydrogen atom on the carbon atom in the alpha position relative to the carbonyl group, preferably with one (1) or two or further three hydrogen atoms, in particular with exactly one hydrogen atom in said Alpha position (on vicinal carbon to carbonyl carbon).

A radically curable reactive resin (Aa) is primarily one which comprises a compound containing non-aromatic unsaturated groups (double bonds), preferably a radically curable unsaturated reactive resin with preferably at least 2 or more reactive non-aromatic unsaturated bonds, or a mixture of two or more such reactive resins. The group of the ethylenically unsaturated compounds, the styrene and derivatives; Vinyl esters, such as (meth) acrylates, urethane (meth) acrylates or itaconates, or epoxy (meth) acrylates; furthermore unsaturated polyesters, vinyl ethers, allyl ethers, dicyclopentadiene compounds and unsaturated fats.

Particularly preferred is or are above all one or more such reactive resins which comprise (radically) curable esters with one or more unsaturated carboxylic acid residues (as described, for example, in DE 102014 103 923 A1); preferably in each case propoxylated or, in particular, ethoxylated aromatic diol, such as bisphenol A, bisphenol F or novolak (especially di) (meth) acrylates; Epoxy (meth) acrylates, especially in the form of reaction products of di- or polyepoxides, for example bisphenol A, bisphenol F or novolak di- and / or poly-glycidyl ethers, with unsaturated carboxylic acids, for example C2-cyalkene carboxylic acids such as, in particular, (meth) acrylic acid; Urethane and / or urea (meth) acrylates - especially urethane (meth) acrylates, which are produced, for example, by reacting di- and / or polyisocyanates (higher-functionality isocyanates) with suitable (meth) acrylic compounds (such as, for example: hydroxyethyl or hydroxypropyl methacrylate ), optionally with the participation of hydroxy compounds which contain at least two hydroxyl groups, as described, for example, in DE 3940309 A1 and / or DE 4111828 A1; or unsaturated polyester resins, or the like, or two or more of these curable unsaturated organic components.

Examples of epoxy (meth) acrylates present or used in particular embodiments of the invention are those of the formula (I) where n stands for a number greater than or equal to 1 (if mixtures of different molecules with different n values are present and are represented by the formula, non-integer numbers are also possible as mean values).

Examples of propoxylated or, in particular, ethoxylated aromatic diol, such as bisphenol A, bisphenol F or novolak (especially di -) (meth) acrylates, which are useful in particular embodiments of the invention are those of the formula (II) where a and b each independently represent a number greater than or equal to 0 with the proviso that preferably at least one of the values is greater than 0, preferably both are 1 or greater (if mixtures of different molecules with different (a and b) values present and represented by the formula, non-integer numbers are also possible as mean values), or in the case of the propoxylated compounds with branched or unbranched oxypropylene groups instead of O-CH2-CH2- in the above formula.

Examples of urethane (meth) acrylates present or used in other special and preferred embodiments of the invention in free-radically curable synthetic resins based on urethane methacrylate (“vinyl ester urethanes”) in coating or adhesive systems according to the invention are those which, on the one hand, result from the reaction of a pre-extended monomeric di- or polyisocyanate and / or, on the other hand, result from the reaction of a polymeric di- or polyisocyanate (eg: PMDI, MDI) with hydroxyalkyl (meth) acrylate, such as hydroxyethyl or hydroxypropyl (meth) acrylate. The manner in which pre-extension reactions are carried out and the large number of possible pre-extension reactions are known to the person skilled in the art and are not all explicitly described here. Reference is made here, for example, to the applications EP 0508183 A1 and EP 0432087 A1.

A particular embodiment relates to those urethane (meth) acrylate resins which are produced by the method briefly outlined below or as described in the examples:

It is a process for the production of vinyl ester urethane resins, in particular urethane (meth) acrylate resins (hereinafter also U (M) A resins), which is characterized in that as a starting material for the production of the vinyl ester urethane, in particular U (M ) A resin is an isocyanate with an average functionality of 2 or lower or in particular more than 2 (which can also be achieved by mixing isocyanates with a functionality below two can be achieved with isocyanates having a functionality greater than 2), for example from 2.0 or in particular 2.1 to 5, for example from 2.2 to 4, advantageously for example from 2.3 to 3.5, with at least one CC Double bond (non-conjugated - olefinic bond) with aliphatic alcohol, in particular a hydroxyalkyl (meth) acrylate, preferably hydroxy-lower alkyl (meth) acrylate, such as hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate or glycerol dimethacrylate or especially hydroxypropyl (meth) acrylate, preferably 2-hydroxypropyl methacrylate (HPMA), is implemented. The technically available HPMA is to be seen as a mixture of 2-hydroxypropyl methacrylate and hydroxyisopropyl methacrylate - other aliphatic alcohols containing an olefinic bond can also be present as technical isomer mixtures or as pure isomers. When using an excess of HPMA, the excess HPMA can also act as a reactive thinner.

An isocyanate with an average functionality of less than 2 or 2 or in particular more than 2, for example from 2.1 to 5, for example from 2.2 to 4, advantageously for example from 2.3 to 3.5, is for example a polyisocyanate with uretdione, isocyanurate, iminooxadiazinone, uretonimine, biuret, allophanate and / or carbodiimide structures (advantageously with a molecular weight distribution such that no single molecular species is more than 50 percent by weight and at the same time more than 50 Percentage by weight of the chains are composed of at least 3 + 1 covalently bound monomer units / reactants (see precise polymer definition according to REACH)) or preferably one (e.g. typically occurring in technical manufacturing processes or subsequently targeted (e.g. by adding and / or distilling off monomers or monomer mixtures) adjusted) mixture of (I) one or more monomeric mono- or, in particular, diisocyanates, such as diphenylmethane diisocyanates at (MDI), in particular 4,4'-diphenylmethyl diisocyanate or 2,2'-diphenylmethane diisocyanate or mixtures of diphenylmethane diisocyanate isomers (with different positions of the isocyanate groups on the phenyl nuclei) such as those just mentioned, with (II) one or more "polymer" Diphenylmethane diisocyanates (PMDI), i.e. preferably crude MDI (crude product of the industrial production of MDI without separation of the individual isomers, e.g. by distillation) with (ie containing) several isomers and higher-functional homologues and, for example, an average molecular weight in the order of 200 to 800 g / mol and a functionality as indicated above, for example with an average molecular weight of 280 to 500, for example 310 to 480 and a functionality of 2.4 to 3.4, for example 3.2. Commercially available PMDIs are preferred which are obtained from the crude MDI itself or from the crude MDI, for example by distilling off and / or adding monomeric MDI and have an average molecular weight of 310-450 and also uretdione, isocyanurate, iminooxadiazinone , Uretonimine, biuret, allo phanate and / or carbodiimide structures can include. Commercially available PMDI with a molecular weight distribution such that no individual molecular species is present at more than 50% by weight is particularly preferred.

"Functionality" is to be understood as the number of isocyanate groups per molecule, in the case of diphenylmethane diisocyanate this functionality is (essentially, ie apart from deviations due to contamination) 2, the PMDI is a (usually specified by the manufacturer) average functionality according to the formula

(f = functionality, n, = number of molecules of a functionality /,) can be calculated and is preferably between below 2 or 2 or particularly preferably above 2, for example 2.1 and 5.0 or in the ranges as indicated above.

The process for the production of urethane (meth) acrylate resins takes place preferably in the presence of a catalyst, corresponding catalysts which catalyze the reaction between hydroxyl groups and isocyanate groups are sufficiently known to the person skilled in the art, for example a tertiary amine, such as 1,2- Dimethylimidazole, diazabicyclooctane, diazabicyclononane, or an organometallic compound (for example from K, Sn, Pb, Bi, Al and in particular also from transition metals such as Ti, Zr, Fe, Zn, Cu); as well as mixtures of two or more thereof; for example (based on the reaction mixture) in a proportion of 0.001 to 2.5% by weight; preferably in the presence of stabilizers (inhibitors), such as, for example, phenothiazine, TEMPO, TEMPOL, hydroquinone, dimethylhydroquinone, tert-butyl hydroquinone, hydroquinone monoethyl ether, tert-butylpyrocatechol and / or p-benzoquinone, and mixtures of two or more thereof; e.g. in an amount from 0.0001 to 2.5% by weight, based on the reaction mixture, at preferred temperatures e.g. in the range from 0 to 120 ° C, advantageously from 50 to 95 (or up to 80) ° C.

Examples of suitable catalysts and stabilizers are known to the person skilled in the art, for example such as from “Polyurethane Kunststoff-Handbuch 7” by Becker, GW; Braun, D .; Oertel, G., 3rd edition, Carl Hanser Verlag, 1993, can be seen. The reaction can be carried out without a solvent (the aliphatic alcohol having at least one CC double bond, in particular the hydroxy (lower) alkyl (meth) acrylate itself, then serves as the solvent) or in the presence of a suitable solvent, for example another reactive diluent. “Reactive” here refers to the formulation of the adhesive and its hardening, not to the addition of the alcohol to the isocyanate.

The reaction can also be carried out in such a way that a prepolymer is formed via a pre-extension and only then the remaining isocyanate groups with the aliphatic alcohol having at least one CC double bond, in particular the hydroxy (lower) alkyl (meth) acrylate, as above or implemented as described below.

For the preparation of the prepolymer, in order to achieve an average isocyanate functionality of two or in particular greater than two, the above-mentioned isocyanates and polyols with two or more hydroxyl groups per molecule and / or polyamines with two or more amino groups per molecule or amino groups with two or more more amino and hydroxyl groups per molecule are used, or isocyanates with a functionality of 2 with polyols, polyamines or aminos with an average OH and / or amino functionality of more than 2 are used.

Polyols (di- or higher-functional alcohols) are in particular two- or higher-functional alcohols, for example secondary products of ethylene or propylene oxide, such as ethanediol, di- or triethylene glycol, propane-1,2- or 1-3-diol, Dipropylene glycol, other diols such as 1,2-, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 2-ethylpropane-1,3-diol or 2,2-bis (4-hydroxycyclohexyl) propane, triethanolamine, bisphenol A or bisphenol F or their oxyethylation, hydrogenation and / or halogenation products, higher alcohols, such as glycerol, trimethylolpropane, hexanetriol and pentaerythritol, hydroxyl-containing polyethers, for example oligomers of aliphatic or aromatic oxiranes and / or higher cyclic Ethers, for example ethylene oxide, propylene oxide, styrene oxide and furan, polyethers each with a terminal hydroxyl, which contain aromatic structural units in the main chain, for example those of bisphenol A or F, hydroxyl group-containing polyesters based on the above-mentioned alcohols or pol yethers and dicarboxylic acids or their anhydrides, for example adipic acid, phthalic acid, isophthalic acid, terephthalic acid, tetra- or hexahydrophthalic acid, endomethylene tetrahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, sebacic acid or the like. Particularly preferred are hydroxyl compounds with aromatic structural units which cause chain stiffening, hydroxy compounds with unsaturated components to increase the crosslinking density, such as fumaric acid, or branched or star-shaped hydroxy compounds, in particular three- or. higher functional alcohols and / or polyethers or polyesters which contain their structural units. Lower alkanediols (give divalent radicals -O-lower alkylene-O-) are particularly preferred.

Aminoies (amino alcohols) are compounds which in particular contain one or more hydroxyl and one or more amino groups in one and the same molecule. Preferred examples are aliphatic amino acids, in particular hydroxy lower alkylamines (result in radicals -NH-lower alkylene-O- or -O-lower alkylene-NH-), such as ethanolamine, diethanolamine or 3-aminopropanol, or aromatic amino acids, such as 2-, 3- or 4- Aminophenol.

Polyamines (di- or higher functional amines) are organic amino compounds containing 2 or more amino groups, especially hydrazine, N, N ^{'-Dimethylhydrazin,} aliphatic diamines or polyamines, in particular Niederalkandiamine (yield radicals -NH-lower alkyl-NH-) such as ethylenediamine, 1,3-diaminopropane, tetra- or hexamethylenediamine or diethylenetriamine, or aromatic di- or polyamines, such as phenylenediamine, 2,4- and 2,6-toluenediamine, or ^{4,4'-diaminodiphenylmethane,} polyether diamines (polyethylene oxides having terminal amino groups) or Polyphenyl / polymethylene polyamines, which can be obtained by condensing anilines with formaldehyde.

The ratio of free isocyanate groups of the isocyanate (s) to hydroxyl groups of the hydroxy lower alkyl (meth) acrylate (s) is advantageously selected such that the isocyanate groups are converted rapidly and completely, i.e. the molar amount of the hydroxyl groups (and thus the correlated molar amount of hydroxy lower alkyl (meth) acrylate) is greater than the molar amount of isocyanate groups, for example 1.03 to 5 times as large, such as 1.05 to 4 times as large or 1.1 to 3 times as large. Excess hydroxy lower alkyl (meth) acrylate serves as a reactive diluent.

The U (M) A resins obtainable by means of the process are those which represent urethane (meth) acrylate resins which can be used or are present according to the invention as reactive resins based on urethane (meth) acrylate.

The coating and adhesive systems according to the invention can, in addition to the constituents mentioned above, also contain other customary constituents (for example additives or other constituents mentioned above or below). These further constituents can, for example, be present in a total amount of up to 80, preferably between 0.01 and 65% by weight. Such customary components are also possible where “on the basis” is not expressly mentioned. The only preferred synthetic resin is free-radically curable (Reactive resin) a urethane methacrylate or in particular a (meth) acrylate as described above is present.

Examples of further ingredients (additives) of reactive resins in coating or adhesive systems with radically polymerizable reactive resins, in particular urethane (meth) acrylates or compounds of the formula (II), or coating and adhesive systems containing these are metal salt-based or preferably amine accelerators , Inhibitors, non-reactive thinners, reactive thinners, thixotropic agents, fillers and / or other additives, or mixtures of two or more of these ingredients.

As aminic accelerators, those with sufficiently high activity come into question, such as in particular (preferably tertiary, in particular hydroxyalkylamino group-substituted) aromatic amines selected from the group consisting of epoxyalkylated anilines, toluidines or xylidines, such as ethoxylated or propoxylated toluidine, aniline or xylidine, for example N, N-bis (hydroxypropyl- or hydroxyethyl) -toluidines or dipropoxy-p-toluidine or -xylidines, such as N, N-bis (hydroxypropyl- or hydroxyethyl) -p-toluidine, N, N-bis (hydroxyethyl) -xylidine and very particularly corresponding more highly alkoxylated technical products are selected. One or more such accelerators are possible. The accelerators preferably have a proportion (concentration) of 0.005 to 10, in particular 0.1 to 5% by weight.

Non-phenolic (anaerobic) and / or phenolic inhibitors, for example, can be added as inhibitors.

Phenolic inhibitors (which are often provided as an already mixed component of commercially available radical curing reaction resins, but may also be absent) come (non-alkylated or alkylated) hydroquinones, such as hydroquinone, and also mono-, di- or trimethylhydroquinone, (non-alkylated or alkylated) phenols, such as 4,4 ^{'methylene-bis-di-tert} 3.5 (2,6-di-tert-butylphenol), 1, 3,5-t rimethyl-2,4,6-tris ( -butyl-4-hydroxy- ^, benzyl) -benzene, (non-alkylated or alkylated) pyrocatechols such as tert-butylpyrocatechol, 3,5-di-tert-butyl-1,2-benzene diol, or mixtures of two or more thereof, in question. These preferably have a proportion of up to 1% by weight, in particular if present between 0.0001 and 0.5% by weight, for example between 0.01 and 0.1% by weight.

Preferred non-phenolic or anaerobic (ie, in contrast to the phenolic inhibitors, also effective without oxygen) inhibitors are phenothiazine or organic nitroxyl radicals into consideration. Organic nitroxyl radicals that can be added are, for example, those described in DE 199 56509, which is incorporated herein by reference in particular with regard to the compounds mentioned therein, in particular 1-oxyl-2,2,6,6-tetramethylpiperidine-4 -ol ("4-OH-TEMPO" or "TEMPOL"). The weight fraction of the non-phenolic inhibitors (if present) is preferably, based on the reaction resin formulation, in the range from 1 ppm (weight based) to 2% by weight, in particular, for example, in the range from 5 ppm to 1% by weight.

As non-reactive diluents, for example, vegetable oils, such as castor oil, or also bioalcohols and fatty acids and their esters, or mixtures of two or more thereof, for example in a proportion of 3 to 60% by weight, for example from 4 to 55% by weight, can be added. -%.

Customary rheological aids that cause thixotropy can be used as thixotropic agents, such as fumed silica or (e.g. with silanes) surface-treated silica. For example, they can be added in a weight proportion of from 0.01 to 50% by weight, for example from 0.5 to 20% by weight.

Usual fillers with a larger medium grain size, in particular chalk, gypsum, quicklime, sand, such as quartz sand, quartz flour, corundum, glass (also as hollow spheres), porcelain, ceramics, silicates, clays or barite, which are available as powder in granular form or in Can be added in the form of molded bodies, or others, such as kernel meal or shell meal from plants, which increases the biogenic carbon content, such as olive meal, coconut shell meal or walnut shell meal, or mixtures of two or more thereof, the fillers also or in particular can also be silanized. The fillers can be present in one or more components of a multi-component synthetic resin fastening system according to the invention, for example one or both components of a corresponding two-component kit; the proportion of fillers is preferably 0 to 90% by weight, for example 10 to 50% by weight (whereby the covering material destroyed when anchoring elements are introduced (e.g. shattered glass or shattered plastic), for example shards from cartridges, are also included as fillers can). In addition or as an alternative to one or more of the mentioned fillers, hydraulically hardenable fillers such as gypsum, quicklime or cement (eg clay or Portland cement), water glasses or active aluminum hydroxides, or two or more thereof, can also be added. Fillers can be contained in one or, in the case of multi-component compositions, in several components of a synthetic resin fastening system according to the invention, for example in the form of a multi-component kit (in particular two-component kit). Their proportion is preferably 0 to 80% by weight, in particular 5 to 80, for example 40 to 70% by weight.

Further additives can also be added, such as non-reactive diluents, flexibilizers, stabilizers, rheological aids, wetting and dispersing agents, coloring additives such as dyes or especially pigments, for example for different coloring of the components for better control of their mixing, or also plasticizers, or Mixtures of two or more of them. Such further additives can preferably be added in total in proportions by weight of a total of 0 to 90%, for example from 0 to 40% by weight.

One or more radically hardening unsaturated reactive thinners in biogenic or non-biogenic form can be added as “reactive thinners”, which are primarily to be understood as those that are organic as free-radically hardening (which includes “hardenable (e.g. before addition of hardener”) components) Contain compounds with unsaturated (e.g. olefinic) radicals or in particular consist of such compounds, e.g. in particular (meth) acrylate or (meth) acrylamide monomers, such as acrylic acid and / or methacrylic acid or preferably their esters (referred to as (meth) acrylates) or amides, in particular (meth) acrylates such as mono-, di-, tri- or poly (meth) acrylates (including hydroxy-lower alkyl (meth) acrylates, which are also obtained from the U (M) A resin production according to the invention even in excess as reactive diluents can be included, such as hydroxypropyl (meth) acrylate or hydroxyethyl (meth) acrylate, alkyl (meth) acrylates with 1 to 10 (meth) acrylate groups, such as mono-, di-, tr i-, tetra-, penta-, hexa- or poly (meth) acrylates, e.g. alkyl di or tri (meth) acrylates, such as 1,2-ethanediol di (meth) acrylate, butanediol di (meth) acrylate, such as 1,3- or in particular 1,4-butanediol di (meth) acrylate, hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, diethyl glycol di (meth) acrylate, particularly preferably oligoalkylene glycol di (meth) acrylates, as in DE 102014 109355 A1, which is incorporated herein by reference, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, polyglycerol poly (meth) acrylate, polyethylene glycol di (meth) acrylate, the reaction product of the acylation of glycerol formal (an equilibrium mixture of 5 -Hydroxy-1,3-dioxane and 4-hydroxymethyl-1,3-dioxolane) with methacrylic acid or its reactive derivatives (known as GLYFOMA from Evonik), cycloalkyl, bicycloalkyl or heterocyclyl (meth) acrylates, in which cycloalkyl or Bicycloalkyl can also be substituted and has 5 to 7 ring carbon atoms and is hetero cyclyl has 5 or 6 ring atoms, can also carry substituents and 1 or 2 ring heteroatoms selected from N, O and S, such as tetrahydrofurfuryl (meth) acrylate or isobornyl (meth) acrylate, or acetacetoxyalkyl (meth) acrylate; or also styrenes, such as styrene, α-methylstyrene, vinyltoluene, tert-butylstyrene and / or divinylbenzene; or mixtures of two or more thereof, for example (if present) in a weight fraction of 0.1 to 90% by weight, for example between 10 and 80% by weight, 30 to 70% by weight or 40 to 60% by weight %, in each case based on the total weight of the mixture of synthetic resin and reactive thinner without fillers, but possibly with other additives.

The free-radically curable oligoalkylene glycol di (meth) acrylates mentioned are in particular those of the formula I, in which the radicals R independently of one another represent C CyAlkyl, in particular methyl, and in which n is on average from 2.5 to 13, preferably from 3.5 to 10, in particular from 4 to 8 and especially from 4.2 to 7, in particular stands for 4,5 and 6.

Examples of corresponding compounds are, in particular, triethylene glycol di (meth) acrylate (TIEGDMA), tetraethylene glycol di (meth) acrylate (TTEGDMA), polyethylene glycol 200 di (meth) acrylate (PEG 200DMA) (mean value n «4.5) (most preferred), polyethylene glycol 400 - Di (meth) acrylate (PEG400DMA) (mean value n = 9), also polyethylene glycol 600 di (meth) acrylate (PEG600DMA) (mean value n = 13).

In a special and advantageous embodiment of the invention, the curable components (including reactive resin and the associated hardener (hardener component) according to the invention) of a coating or adhesive system according to the invention are stored separately from one another in a two- or further multi-component system or kit before they are used are mixed with one another at the desired location (for example at or in a hole or gap, such as a borehole). A multicomponent system is in particular a two- or (further) multicomponent kit (preferably a two-component kit) comprising one (or in the case of the two-component system consisting of one) component (K1) which contains one or more reactive resins, as described above and below, and the respective associated hardener as component (K2) as defined above and below, whereby further additives can be provided in one or both of the components, preferably a two- or further multi-chamber device, to be understood in which the mutually reactive components (K1) and (K2 ) and, if necessary, further separate components are contained in such a way that their components do not come into contact with each other during storage before use, but this allows components (K1) and (K2) and possibly other components to be attached to the desired location , for example directly in front of or in a hole, to be mixed and requiredfa lls to be brought in so that the hardening reaction can take place there. Cartridges are also suitable, for example cartridges nested in one another, such as ampoules; as well as in particular multi-component or in particular two-component cartridges (which are also particularly preferred), in whose chambers the several or preferably two components (in particular (K1) and (K2)) of the coating or adhesive system according to the invention with compositions mentioned above and below for storage are included before use, a static mixer preferably also belonging to the corresponding kit. The chambers of the multi-component or, in particular, two-component cartridges can be constructed purely from plastics or as foil bags (in particular multilayer foil bags).

Plastics can be used as the material for a film bag that can be used according to the invention, such as compostable plastics, e.g. based on starch, polyester, polyesteramides, polyurethanes, polyvinyl alcohols, cellulose, lignocellulose, polylactic acid, polyhydroxyalkanoates, or mixtures of two or more such materials. Preference is given to materials impermeable to water, moisture and water vapor, in particular those which are metallized (e.g. by vapor deposition) and / or are composite foils made from a plastic and a metal, in particular aluminum, foil.

As an alternative (or in the case of mixed systems (hybrid systems) in addition to) to free-radically curable synthetic resins (Aa), the coating or adhesive systems according to the invention can comprise, as synthetic resin, those which contain compounds curable by polyaddition (Ba), especially those which (preferably per molecule contain at least an average of two or more epoxy groups (Ba1) or in particular isocyanate groups (Ba2). It is assumed, without this assumption being binding, that upon contact with moisture, for example in aqueous solvents or with atmospheric humidity, imines according to the invention are split into the associated amines and ketones or aldehydes with absorption of water, the amino groups then react with reaction with the epoxy or isocyanato groups with polyaddition.

Thus, the hardeners and imines according to the invention can also be included or used for hardening compounds curable by polyaddition such as synthetic resins (Ba2) containing isocyanate groups in particular, and in particular in coating or adhesive systems according to the invention.

The reactive synthetic resins based on epoxy (Ba1) (reactive synthetic resins with epoxy groups) that can be used in coating or adhesive systems used according to the invention contain, as epoxy components, those based on glycidyl compounds, for example those with an average glycidyl group functionality of 1.5 or greater, in particular of 2 or greater, for example from 2 to 10, which can optionally contain further glycidyl ethers as reactive diluents. The epoxides of the epoxy component are preferably poly (including di) glycidyl ethers of at least one polyhydric alcohol or phenol, such as novolak, bisphenol F or bisphenol A, or mixtures of such epoxides, for example obtainable by reacting the corresponding polyhydric alcohols with Epichlorohydrin. Examples are trimethylolpropane triglycidyl ether, novolak epoxy resins, bisphenol A epichlorohydrin resins and / or bisphenol F epichlorohydrin resins, for example with an average molecular weight of <2000 Da. The epoxy resins can, for example, have an epoxy equivalent of 120 to 2000, preferably 150 to 400, such as in particular 155 to 195, for example 165 to 185. The proportion of the total mass of the reactants and additives of the injection synthetic mortar system is preferably 5 to less than 100% by weight, in particular 10 to 80% by weight, 10 to 70% by weight or 10 to 60% by weight. Mixtures of two or more such epoxy components are also possible. Suitable epoxy resins, reactive thinners and hardeners can also be found in the standard work by Lee H and Neville K, "Handbook of Epoxy Resins" (New. York: McGraw-Hill), 1982 (these compounds are incorporated herein by reference).

The reactive synthetic resins which can be used in the coating or adhesive systems used according to the invention and which contain isocyanate groups (Ba2) are preferably those in which the isocyanates are defined as above for an “isocyanate with an average functionality of 2 or more than 2”. Particularly preferred are those reactive resins which meet the REACH condition as defined above, and some contain a low content of the monomeric isocyanate groups to be avoided as far as possible, including prepolymers.

Isocyanate prepolymers according to the invention or to be used according to the invention are, in particular, by reaction with polyols with polyfunctional, in particular di-functional isocyanates (“monomers”, which have a production-related residual content (e.g. 5% by weight or less, in particular 1% by weight) .-% or less) of oligomers) such as, for example, MDI, particularly preferably TDI which can be or are produced.

The polyols used here are polyols, in particular difunctional polyols such as polyester polyols or, particularly preferably, polyalkylene glycol polyols such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol polyols.

The isocyanate prepolymers can preferably be prepared or in particular prepared by reacting the polyols with a molar excess of isocyanates, in a molar ratio of NCO: OH groups of preferably 1.2 to 3: 1, particularly preferably close to 2: 1, thereafter Distilling off excess isocyanate monomers to a content of <1%, for example 0.5% and very particularly preferably <0.1%, for example by high vacuum or thin-film distillation. The reaction preferably takes place (as a further distinction to the multi-stage reaction in DE 10055 786 A1) in one reaction stage without further reaction, ie the reaction product “isocyanate prepolymer” is not (with prior removal of residual isocyanate monomers still present) in a second Reaction of some of the isocyanate groups still present with di- or polyol to form a further prepolymer with fewer isocyanate groups.

Important examples of possible further ingredients (constituents or additives) for a component comprising epoxy or isocyanate groups containing reactive resin (Ba) and the hardener component are in particular accelerators, inhibitors, stabilizers, reactive thinners, thixotropic agents, fillers and other additives.

Suitable accelerators are those with a sufficiently high activity, such as heavy metal salts, organic tin, titanium, bismuth and antimony compounds or the like; or (especially in the case of reactive hearts containing epoxy groups) amine accelerators. One or more such accelerators are possible. The accelerators preferably have a proportion (concentration) of 0.005 to 10, in particular 0.1 to 5% by weight. DABCO (1,4-diazabicyclo [2.2.2] octane), dibutyltin dilaurate or DBU are particularly preferred. HALS stabilizers as described in “Polyurethane, Kunststoff Handbuch”, Chapter 3.4.8 Antioxidants, p. 121, 3rd edition, 1993, ed. Gerhard W. Becker and Dietrich Braun, Carl Hanser Verlag Munich Vienna, such as in particular 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol ("4-OH-TEMPO"), or sterically hindered phenols ( 4,4'-di-octyl-diphenylamine) such as cresols (2,6-di-tert-butyl-p-cresol). The proportion by weight of the stabilizers is preferably in the range from 0.1 ppm to 2% by weight, preferably in the range from 1 ppm to 1% by weight.

Customary rheological aids which cause thixotropy can be used as thixotropic agents, such as pyrogenic silica (if necessary surface-treated with hydrophobization) or hydrogenated (solid at room temperature) or modified castor oils. For example, they can be added in a weight proportion of from 0.01 to 50% by weight, for example from 1 to 20% by weight.

Customary fillers, in particular cements (e.g. Portland cements or high-alumina cements), chalks, sand, quartz sand, aluminum silicates, quartz flour or the like, which can be added as powder, in granular form or in the form of shaped bodies, are used as fillers, or others, such as mentioned in WO 02/079341 and WO 02/079293 (which are hereby incorporated by reference in this regard), or mixtures thereof, wherein the fillers can furthermore or in particular also be silanized. The fillers can be present in one or more components of an adhesive system according to the invention, for example one or both components of a corresponding two-component kit. Additionally or alternatively, hydraulically hardenable fillers such as gypsum (e.g. anhydrite), quicklime or cement (e.g. high alumina or Portland cement), water glasses or active aluminum hydroxides, or two or more of them, can be added as fillers. The fillers can be in any form, for example as powder or flour, or as shaped bodies, for example in cylindrical, ring, spherical, hollow spherical, platelet, rod, saddle or crystal form, or also in fiber form, and the corresponding base particles preferably have a maximum diameter of 0.0001 to 10 mm. The proportion of fillers is preferably 0 to 90% by weight, for example 10 to 90% by weight.

Other additives can also be added, such as drying agents (e.g. zeolite) to increase the storage stability of the moisture-sensitive component, plasticizers such as phthalic or sebacic acid esters, non-reactive diluents (e.g. solvents such as lower alkyl ketones, e.g. acetone, di-lower alkyl-lower alkanoylamides , how Dimethylacetamide, lower alkylbenzenes, such as xylenes or toluene, or paraffins, or water), flexibilizers, stabilizers, rheological aids, wetting agents, pigments or dyes, or mixtures of two or more of these additives, or the like. Such further additives can preferably be added in total in proportions by weight of a total of 0 to 90%, for example from 0 to 40% by weight.

According to the invention, in the case of radical polymerization, none of the otherwise customary initiators of radical polymerization, for example radical-forming peroxides, for example organic peroxides such as diacyl peroxides, for example dibenzoyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide or cyclohexanone peroxide, or alkyl peresters such as tert-butyl perbenzoate, Inorganic peroxides such as persulfates or perborates, azides, azo compounds or photoinitiators are added, ie the subject matter of the invention manages without such compounds (they are free of them). It cannot be ruled out that occasional peroxides arise incidentally during storage or the reaction (for example also through reaction with atmospheric oxygen), but there is no intentional active addition "from outside".

According to the invention, the hardener for a free-radically polymerizing system consists of an initiator system comprising

(A) at least one activator in the form of a metal salt and as a free radical initiator

(b1) an amino-functional polyoxyalkylene (i) as in any one of the preceding

Embodiments defined as a mixture with an aldehyde and / or ketone (ii) as defined in one of the preceding embodiments; or

(b2) an imine as defined in one of the preceding embodiments, or a mixture of components (b1) and (b2).

In the case of the compounds curable by polyaddition, the hardener (b2) contains an imine as defined in one of the preceding embodiments.

The aldehydes, ketones, amines, aldimines or ketimines contained or used according to the invention are known or can be prepared / obtainable by processes known per se or are preferably obtained thereafter, see also WO 2016/206777 A1 in this regard.

In the case of an amino-functionalized polyoxyalkylene whose polyoxyalkylene chains are a copolymer of oxyethylene and oxypropylene units, it is preferably either one where the oxyethylene and oxypropylene (which in particular is 2-methyl- oxyethylene means) randomly distributed in the polyoxyalkylene chain and / or as blocks. It is particularly preferred to use compounds with a poly (oxyethylene) portion which is bound with oligo (propyleneoxy) radicals (in particular oligo (2-methyl) at both ends - ethyleneoxy) and is "endcapped" at the outer chain ends with a primary amino group.

These are particularly preferably compounds of the formula (III)

NH2-CH (CH3) -CH2- [0-CH2-CH (CH3) -] i (0-CH2-CH2) m [0-CH2-CH _(CH3) -] n NH 2 (III) wherein I and n in each case independently of one another on average for 1 to 10, preferably about 3.6; and m stands for 1 to 50, preferably for 8 to 10, in particular for about 9, where in particular I and n stand for approximately 3.6 on average and m stands for approximately 9 on average, with preferably “approximately” a range of variation of ± 0.2, in particular of ± 0.1, means.

The aldehydes and / or ketones are compounds which have at least one or more (primary and / or secondary) hydrogen atoms on the a-carbon atom to the carbonyl group. Aldehydes are preferred over ketones. Examples of such aldehydes are propanal, valeraldehyde, isovaleraldehyde, or methoxyacetaldehyde, or 3,7-dimethyl-6-octenal (citronellal) or 3,7-dimethyl-7-hydroxyoctanal (hydroxycitronellal). As corresponding ketones, methyl isobutyl ketone, acetone, or methyl ethyl ketone or 6-methyl-5-hepten-2-one may also be mentioned here by way of example.

The aldehydes (which are preferred over ketones) and / or ketones are particularly preferably compounds which have a double bond and / or branch on the a-carbon atom to the carbonyl group. As a result, the particularly preferred aldehydes and / or ketones only have one (tertiary) hydrogen atom on the a-carbon atom attached to the carbonyl group. Examples of particularly preferred aldehydes are isobutyraldehyde (very particularly preferred), 2-ethylhexanal, 2-methylbutanal, 2-ethylbutanal, 2-methylvaleraldehyde, 2,3-dimethylvaleraldehyde, cyclohexylcarboxaldehyde, or 3,7-dimethyl-2,6-octadienal (Citral ), 3- (4-tert-butylphenyl) -2-methylpropanal (Lilial, Lysmeral), tetrahydrofuran-3-carboxaldehyde, tetrahydro-2-furancarboxaldehyde, 4-formyltetrahydropyran, tetrahydro-2H-pyran-2-carbaldehyde or tetrahydropyran -3-carbaldehyde. Particularly preferred ketones are, for example, diisopropyl ketone, 3-methyl-2-pentanone, 2-methylcyclohexanone or β-ionones. The ingredients used in the activators in the form of a metal salt, which also includes metal complexes and metal oxides, are preferably one or more metal salts or in particular one or more salts of organic and / or inorganic acids with metals, e.g. selected from copper and iron , Vanadium, manganese, cerium, cobalt, zirconium, or bismuth, or mixtures of two or more thereof. In particular, the metal salts are selected from the group consisting of vanadium, iron, manganese and copper, in particular in the form of salts or complexes with inorganic acid residues, such as sulfate and / or carbonate residues and / or organic acid residues, for example carboxylate residues - The organic acids are preferably saturated - such as carboxylates with CH ₃ , C2-C2o-alkyl, a C6-C24-aryl radical or CyCso-aralkyl radical, for example octoate, for example 2-ethylhexanoate (isooctanoate), neodecanoate, or acetylacetonate. Manganese carboxylates such as Mn acetate or Mn octoate, copper carbonates such as copper octoate or copper naphthenate, copper quinolates, iron carboxylates such as iron octoate and / or vanadium carboxylates and / or the group of metal salts with inorganic acids, which for example iron chloride, iron sulfate, are particularly preferred , Copper sulfate and copper chloride includes.

Such activators are known or can be prepared by processes known per se and are preferably present in a proportion of 0.01 to 20, for example 0.1 to 5% by weight.

Based on the hardener component, the proportion of imine in a possible preferred embodiment of the invention in the case of radical polymerization is 0.5 to 90% by weight, in particular 0.9 to 30% by weight, in the case of polymerization by polyaddition at 5 to 95% by weight, preferably at 10 to 80% by weight.

The total proportion of the hardener in a coating or adhesive system according to the invention is preferably in a range from 1 to 60% by weight, e.g. 2 to 50% by weight.

Anchoring elements, when used without a drill hole or gap (which also includes a “recess”), are elements to be fastened over a large area, such as adapters etc. (such as columns) are those made of metal, such as undercut anchors, threaded rods, screws, drill anchors, bolts or the like, and it can also be nails or other pin-shaped connecting elements. Parameters, insofar as they are mentioned in the context of the present application, are determined by methods known to the person skilled in the art, in particular as described in the examples.

Experimental part

The following examples illustrate the invention without restricting its scope; however, they themselves represent advantageous embodiments of the invention.

In the following examples, the respective unmarked components of the model formulations are mixed beforehand. Polymerization is triggered by adding and mixing in the ^{component marked with an “x”.}

The determination methods for the determination of parameters are also valid for the general part of the description:

Determination of the gel time

The gel time is determined manually with a commercially available stopwatch and a commercially available thermometer at room temperature (approx. 23 ° C). For this purpose, all components are mixed and the temperature of the sample is measured immediately after mixing. The sample itself is in a plastic beaker. The evaluation is based on DIN 16945 (1989-03). The gel time is the time it takes for the temperature to rise above 35 ° C. This corresponds to a temperature increase of approx. 10 K.

Pull-out tests from concrete

For pull-out tests with threaded rods M12, according to ETAG 001 PART 5 (publisher DIBT, Berlin 2008), proceed as follows:

First, drill holes (diameter 14 mm; depth 84 mm) are made in a horizontal concrete test body (concrete type C20 / 25) with a hammer drill. The drill holes are cleaned with a hand blower and a hand brush. The boreholes are then filled to two thirds with the respective hardenable compound to be tested for fastening purposes. A threaded rod is pressed in by hand for each borehole. The excess mortar is removed with a spatula. After 1 hour at room temperature, the threaded rod is pulled until failure while measuring the failure load.

Determination of the tensile shear strength The final strength after 24 hours is determined using the tensile shear strength according to DIN EN ISO 4587 (2003-03). For this purpose, beech wood test pieces (100 x 25 x 5 mm) are glued (adhesive surface 13 x 25 mm) and after a curing time of 24 h at a temperature of 23 ° C with a universal testing machine Z010 from Zwick GmbH & Co. KG (BT1-FR010TH.A50 ) tested.

During use or the method, the surfaces to be bonded can be exposed to the mixture from the adhesive system over the entire common area or only in certain areas.

The following constituents and abbreviations are used to produce the example formulations below.

Table 1: Components and abbreviations used

Example 1: General Working Instructions I: Synthesis of Aldimines The respective amine is placed in a round bottom flask. The aldehyde is slowly added from a dropping funnel with vigorous stirring, the mixture heating up. For the use of the aldimine according to the invention as an initiator, the volatile constituents do not have to be removed. The resulting water of reaction separates from the aldimine depending on the amine used (“hydrophobic” amines). The residual water remaining in the aldimine does not interfere with the use as an initiator. When using “hydrophilic” amines, there is no phase separation. For use as a hardener for polyaddition-curable reactive resins, the volatile constituents are removed by distillation under reduced pressure. Following the distillation, the aldimine is also dried over a molecular sieve. Optionally, the aldehyde can also be initially charged and the amine added dropwise. The conversion (freedom from carbonyl or imine groups detectable by IR spectroscopy is checked by means of FT-IR.

Example 2: Simplified resin formulation

The following raw materials are mixed for the simplified resin recipes:

Table 2: Simplified resin formulation I (HRI) technical product - slightly varying degrees of ethoxylation possible (but always the same in the examples listed)

Example 3: Determination of the gel times of the aldimine according to the invention in comparison to VPLS2142 with radical starter b2)

In order to demonstrate the advantages of the aldimine according to the invention as a hardener system imine-metal salt for cold-curing vinyl ester resins compared to commercially available aldimines and ketimines, example formulations with the above-described resin formulation I and various metal salts are created. The aldimine according to the invention made from isobutyraldehyde in a mixture with Jeffamine ED600 is used as a free-radical initiator. The commercially available aldimine (CSTICO®phen VP LS 2142) consists of isobutyraldehyde and Isophoronediamine and the sample ketimine (Desmophen VPLS2965A) consist of methyl isobutyl ketone and isophoronediamine. The following table 3 lists the gel times and the maximum temperatures reached during the polymerizations:

Table 3: Gel times determined with radical initiators b2) and varying metal salts x added as a hardening trigger

It can be seen from Table 3 that when using equimolar amounts of imine with the aldimine according to the invention, significantly more exothermic and faster polymerizations of vinyl ester resins at room temperature are achieved. Without wishing to be bound by this theory, it is assumed that this is due to the chemical structure of the aldimine or amine used according to the invention, which is a copolymer of oxyethylene and oxypropylene units (aminooxypropylene-capped poly (oxyethylene). The ketimine of isophoronediamine and methyl isobutyl ketone did not polymerize within 12 hours.

Example 4: Gel times of the amine according to the invention with radical initiators b1) and varying metal salts In order to further demonstrate the advantages of the aldimine or amine according to the invention shown in Example 3, gel times are determined using radical starters b1) in combination with varying metal salts. A pure polyoxypropylenediamine (D230) is used as a comparison amine in order to reinforce the above-mentioned theory. Example formulations are produced with resin formulation I and various metal salts. Table 4 below shows the gel times and the maximum temperatures reached during the curing reactions.

Table 4: Determined gel times with free radical starter components (mixture of amine and isob)

(with in-situ synthesis of the imines) and varying metal salts x added as a hardening trigger

Table 4 shows that the aldimine or amine according to the invention, which is a copolymer of oxyethylene and oxypropylene units, triggers significantly more exothermic and faster polymerizations. Here, too, equimolar amounts of imine are used. In addition, Table 4 shows that radical initiators b1) in combination with metal salts also trigger polymerizations of unsaturated reactive resins at room temperature.

Example 5: Pull-out tests from concrete with radical starters b2)

Settlement tests are carried out according to the above parameters for “pull-out tests from concrete”.

Table 5: Formulations in% by weight for carrying out setting tests and determined bond stresses with radical starters b2) ^x added as a hardening trigger

The starting materials of the aldimines can be assigned accordingly on the basis of the abbreviations used in the designations and the abovementioned Table 1 for abbreviations. Table 5 shows that the copolymer structure of the aldimine or amine according to the invention from oxyethylene and oxypropylene units leads to higher bond stresses in direct comparison with pure oxypropylene (D230) and oxyethylene (EDR148) aldimines or amines.

Example 6: Tensile shear strengths of the aldimine according to the invention (b2) with polyaddition-curable reactive resins (Ba2)

In order to demonstrate the applicability of the aldimine according to the invention as an adhesive system, beech test specimens are glued to one another and the tensile shear strength is determined after 24 hours. Table 6 below shows the compositions and the tensile shear strengths determined.

Table 6: Determined tensile shear strengths of the aldimine according to the invention (b2)

¹ isocyanate prepolymer: TDI-based, NCO content: 11.1%, viscosity at 23 ° C, spindle 7, 10 rpm based on DIN EN ISO 2555: 94,400 mPa-s, residual monomer content <0.1%.

Claims

Expectations:

1. Imine, obtainable by reacting (i) an amino-functionalized polyoxyalkylene whose polyoxyalkylene chains are a copolymer of oxyethylene and oxypropylene units, these polyoxyalkylene chains carrying alkoxy groups containing primary amino groups, and (ii) a ketone and / or aldehyde with a hydrogen atom on the carbon atom in alpha position to the carbonyl group.

2. Imine according to claim 1, which can be obtained by reacting the amino-functionalized polyoxyalkylene (i), each bonded to the terminal oxyalkylene group with a primary amino group, with an alkanaldehyde (ii) having a hydrogen atom on the carbon atom in the alpha position to the carbonyl group .

3. Imine according to claim 1, obtainable by reacting the amino-functionalized polyoxyalkylene (i) with isobutyraldehyde (ii).

4. Imine according to one of claims 1 to 3, characterized in that the amino-functionalized polyoxyalkylene (i) carries two terminal 2-aminopropyloxy groups.

5. Imine according to one of the preceding claims, characterized in that the amino-functionalized polyoxyalkylene (i) has the following formula:

NH2-CH (CH3) -CH2- [0-CH2-CH (CH3) -] i (0-CH2-CH2) m [0-CH2-CH _(CH3) -] n NH 2 where I and n each independently on average for 1 to 10, preferably 3 to 4, in particular about 3.6; and m is 1 to 50, preferably 8 to 10, in particular about 9, stand _.

6. Imine according to claim 5, characterized in that in the formula I and n stand for approximately 3.6 on average and m stands for approximately 9 on average.

7. Imine according to one of claims 1 to 6, characterized in that it has an average molecular weight of 2000 g / mol or lower.

8. Imine according to one of claims 1 to 7 in a (in particular equilibrium) mixture with its starting materials (i) amino-functional polyoxyalkylene and (ii) ketone and / or preferably aldehyde.

9. Mixture of (i) an amino-functional polyoxyalkylene as defined in one of claims 1, 4, 5 or 6 and (ii) an aldehyde (preferred) and / or ketone as defined in each of claims 1 to 3.

10. Mixture according to claim 9 as part of a coating system or adhesive system or adhesive.

11. Hardener as an initiator for a free-radically curing system and / or for compounds curable by polyaddition, in particular an epoxy or an isocyanate with two or more epoxy or isocyanate groups each, which in the case of the free-radically curable compounds (case A) includes the initiator system below :

(A) at least one activator in the form of a metal salt and, as free radical initiator (b1), an amino-functional polyoxyalkylene (i) as defined in one of the preceding embodiments in a mixture with an aldehyde (preferred) and / or ketone (ii) as in one of the preceding embodiments Are defined; or (b2) an imine as defined in any one of claims 1 to 8, or a mixture of components (b1) and (b2); or in the case of compounds curable by polyaddition (case B) represents the following constituent:

(b2) an imine as defined in any one of claims 1 to 8.

12. Coating or in particular adhesive system, containing a hardener according to claim 11, and as reactive resin either (Aa) a radically polymerizable reactive resin (case A) or a reactive resin containing epoxy groups (Ba1) or in particular isocyanate groups (Ba2) (case B), or a mixture of (Aa) and (Ba).

13. Coating or in particular adhesive system according to claim 12, wherein the reactive resin is a radically curable according to (Aa), in particular one of the formula where a and b each independently represent a number greater than or equal to 0 with the proviso that preferably at least one of the values is greater than 0, preferably both are 1 or greater.

14. Coating or in particular adhesive system according to claim 12, case B, wherein the reactive resin is a reactive resin containing isocyanate groups according to (Ba2), in particular a prepolymer containing at least two isocyanate groups.

15. Coating or in particular adhesive system according to claim 12 or 13 in the form of a multi-component, in particular two-component system, which contains a reactive resin according to (Aa) or (Ba) in one component and the hardener according to claim 12 in another component.

16. Coating or in particular adhesive system according to claim 14 in the form of a one-component system, preferably a polyaddition-curing lacquer or a polyaddition-curing adhesive.

17. Use of an adhesive system according to one of claims 12 to 16

(a) for gluing objects together or

(b) for adhering an object to a stationary substrate.

18. Use according to claim 17, case (b), wherein the object is a swimming pool, room, bathroom or kitchen accessory or an adapter element for receiving such an accessory; a plate or block, preferably made of metal, glass, plastic, concrete or stone; Fibers, especially high-modulus fibers, preferably carbon fibers, in particular for Reinforcement of structures, for example walls, pillars or ceilings or floors; a component such as a plate, a disk or a block, for example made of stone, glass or plastic; or - each designed as a flat mat and as a free material or as a composite material or material - a fleece, a woven fabric, a knitted fabric, a flat material obtained by knitting, a material obtained by tufting, preferably each with high-modulus fibers, for example made of glass fiber, Carbon fiber and / or plastic fiber, in the case of a composite material with a plastic matrix, is to be understood; and a substrate is to be understood as a building substrate, in particular a wall, a wall, a ceiling or a floor in the building sector, preferably made of masonry, concrete, free or glazed ceramic, or also made of glass, wood, metal or plastic.

19. Use according to claim 18 of an adhesive system according to one of claims 12 to 16 for gluing an anchoring element in a hole or a depression in the substrate, in particular in a borehole.

20. Use according to claim 18 of a coating system according to any one of claims 12 to 16 for coating a substrate, the substrate preferably being a building substrate, in particular masonry or concrete.

21. A method for coating a substrate with a coating system according to any one of claims 12 to 16, wherein the coating system, if necessary with or after mixing of components thereof which do not harden alone, is applied and hardened with polymerization.

22. Procedure

(a) for gluing objects together or

(b) for gluing an object to a stationary substrate, wherein an adhesive system according to one of claims 12 to 16, if necessary with or after the mixing of otherwise non-reactive components thereof, on one or more areas to be glued of one or more of the areas to be glued Objects are applied and areas to be bonded are brought into contact with one another and the adhesive system is cured with polymerization, the method in particular including the use according to one of claims 17 to 19.